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Physical Chemistry: An Indian Journal
Phys Chem Ind J, Volume: 13( 2)
1H and 13C NMR Investigation of Quinoline Pharmaceutical Derivatives: Interpretation of Chemical Shifts and their Comparison with the Experimental Value
Mohammadi MS1, Bayat Z2* and Mohammadi Nasab E1
1Department of Chemistry, Arak Branch, Islamic Azad University, Arak, Iran
2Department of Chemistry, Quchan Branch, Islamic Azad University, Quchan, Iran
*Correspondence:
Zakiyeh Bayat , Department of Chemistry, Quchan Branch, Islamic Azad University, Quchan, Iran, Tel: +989151811750; E-Mail: [email protected]
Received: June 5, 2018; Accepted: June 26, 2018; Published: June 28, 2018
Citation: Z.Bayat, M Shir Mohammadi, and E Mohammadi Nasab. 1H and 13C NMR Investigation of Quinoline Pharmaceutical Derivatives: Interpretation of chemical shifts and their comparison with the experimental value. Phys Chem Ind J. 2018;13(2):122.
In this paper, 1H and 13C chemical shift values have been calculated for the optimized structures of the quinoline pharmaceutical derivatives of compounds by theoretically method and compared to the experimental chemical shift values. Theoretically chemical shifts values were determined at GIAO HF/6-31++G(d,p) level of theory by Gaussian 09 program and are fully interpreted. Highest frequency are observed for the nitrogen, Oxygen and chlorine substitutions occurring in ipso carbons and also on nitrogen heteroatom occur at ortho and para positions in heterocyclic carbons and Hydrogen attached to them. The aliphatic Hydrogen at high frequency for the Hydrogen attached on Carbon adjacent to Oxygen, Nitrogen and carbons include double bond. The correlation analysis of the calculation and experimental data was performed in order to quantify the disagreement.
NMR; Quinoline; Computational; Comparison; Chemical shift
The use of heterocyclic compounds in our lives is irrefutable. So there is a growing request for heterocyclic compounds, and this has incited research activities in the field of heterocyclic compound chemistry. Amongst the wide diversity of heterocyclic compounds, those containing the nitrogen atom are usual in nature, and their biological usage distinguishes them [1]. Quinoline and its derivatives have evermore engrossed both biological and synthetic chemist due to its various pharmacological and chemical attributes [2]. 1,10-Phenanthroline (FIG. 1) has been widely used for decades as a chemically Multipurpose module displaying a good combination of structural and chemical attributes. 1,10-phenanthroline derivatives provided the development of sophisticated synthetic strategies that have yielded fascinating molecular architectures. Remarkable, some of these systems can be designed to work as molecular-level machines. Another capacity of 1,10- phenanthroline is connected to its Flat structure, that prompts intercalation or binding with DNA or RNA [3]. Chloroquine (FIG. 2) was introduced in the 1940s and quickly became the mainstay of treatment and prevention because it was inexpensive and nontoxic and malaria parasites were generally susceptible to it [4]. Cinchocaine (FIG. 3) is a member of a category of drugs known as local anesthetics [5]. Imiquimod (FIG. 4) have been shown to have attributes as immune response modifiers in vitro and in vivo, and display antiviral and antitumor activity via endogenous cytokine production [6]. Nitroxoline (FIG. 5) is an antibiotic, which does not belong to any known antimicrobial class and is used as a urinary antibacterial agent, active against oversensitive Gram-positive and Gram-negative bacterial strains that generally exist in urinary tracts and cause infections [7]. Primaquine (FIG. 6) is the only 8-aminoquinoline which is extensively employed as an antimalarial drug [8]. Proflavine (FIG. 7) is the prototype of DNA-intercalating aminoacridines and is a planar polyaromatic chromophore that is mono-protonated in the physiological situation [9]. Quinine and quinidine, two cinchona alkaloids so freely provided by Nature, are not only important pharmacological drugs,' but their contribution to chemistry certainly deserves respect [10]. Quinine (FIG. 8) and quinidine (FIG. 9) have been used widely in the medical profession as antimalarial and antiarrhythmic drugs, respectively [11]. Tacrine (FIG. 10) is the first factor approved by the Food and Drug Administration for the treatment of Alzheimer's disease and has been extensively employed in the infirmary. Tacrine acts as an acetylcholinesterase inhibitor blocking the degradation of acetylcholine in neurons of the cerebral cortex thereby increasing cholinergic transmission [12]. Of the specific importance of NMR studies has been the use of various multidimensional sequences of NMR programs to define the detailed molecular structure. The standard NMR experiences are enough to obtain a perfect assignment of organic compounds, and efficient to obtain molecular structure information [13]. NMR chemical shifts, however, depend on the electronic environment of the nucleus studied. This gives us the unique leisure to quantify the effect of the packing on the chemical shifts in such a complex system [14]. This Presentation is a theoretical study of NMR magnetic shielding spectra of quinoline pharmaceutical derivatives. Presented here is calculated 13C and 1H isotropic NMR chemical shifts for 1,10-Phenanthroline, Chloroquine, cinchocaine, Imiquimod, Nitroxoline, Primaquine, Proflavine, Quinine, quinidine, and Tacrine. The optimized geometrical parameters of quinoline pharmaceutical derivatives which are calculated by HF methods with 6-31++G(d,p) basis sets are consistent with the atom numbering scheme.1H and 13C chemical shift values have been calculated for the optimized structures of the quinoline pharmaceutical derivatives of compounds and compared to the experimental chemical shift values.
Figure 1: The structure of optimized 1,10 Phenanthroline.
Figure 2: The structure of optimized chloroquine.
Figure 3: The structure of optimized cinchocaine.
Figure 4: The structure of optimized imiquimod.
Figure 5: The structure of optimized Nitroxoline.
Figure 6: The structure of optimized Primaquine.
Figure 7: The structure of optimized Proflavine.
Figure 8: The structure of optimized Quinidine.
Figure 9: The structure of optimized Quinine.
Figure 10: The structure of optimized Tacrine.
Ab initio NMR calculations are now attainable and accurate enough to be useful in exploring the relationship between chemical shift and molecular structure. Study on quinoline derivatives the structural formula of the drug. Using the structure molecules were using the software Gauss view drawing. The program Gaussian optimized structures at the beginning of the Gauss view software structure was obtained as a Gaussian input. In general, studies on 10 cases of selected derivatives of quinolines that the computational method ab initio with the level of computational HF calculations with 6-31++G(d,p) basis sets. This basis set was chosen since it had been successfully used in the study of NMR chemical shielding tensors. The term, σ is a second rank tensor called NMR chemical shielding tensor whose elements describe the size of chemical shielding as a function of molecular orientation with respect to the external magnetic field. The isotropic chemical shielding σiso parameters can be related to the principal components by the following equation:
and the chemical shift to note is the Isotropic value. To convert the shifts to ppm subtract the isotropic value from the isotropic chemical shift of the protons in TMS:
In this work, we study magnetic properties of atomic nuclei to determine properties of atoms in the titled compound by NMR spectroscopy. Ab initio calculation of nu0063lear magnetic shielding has become an aid for the analysis of molecular structure. So, NMR is based on the quantum mechanical property of nuclei. Based on NMR study, calculated magnetic shielding tensor (σ, ppm), magnetic shielding anisotropy (σaniso ppm), and chemical shift (δ) were calculated. These results are, listed in TABLES 1-20. On the other hand, experimental 13C and 1H NMR data have been extracted from previous research and Along with referrals are presented in TABLES 1-20 too. Experimental and computational data were compared and full explanations were given on NMR shifts. As can be seen in FIG. 1, the molecular structure of the 1, 10-phenanthroline includes tree aromatic ring. It is a heterocyclic compound with five carbon and one nitrogen atoms in the hetero rings. The study of Chloroquine shows 13 different carbon atoms, which is consistent with the structure on the basis of molecular symmetry. It includes two aromatic rings. The molecular structure of the Cinchocaine includes two aromatic ring, the studied molecule shows 20 different carbon atoms, which is consistent with the structure on the basis of molecular symmetry. So the study of Imiquimod shows 14 different carbon atoms, which is consistent with the structure on the basis of molecular symmetry. it includes three aromatic rings. The molecular structure of the Nitroxoline includes two aromatic ring and molecular structure of the Primaquine includes two aromatic ring and the molecular structure of the Proflavine includes tree aromatic ring. it is a heterocyclic compound with 13 carbon, two NH2 and substitutions and one nitrogen atoms in the hetero rings. The molecular structure of the Quinidine includes two aromatic ring and molecular structure of the Quinine includes two aromatic rings. The study of molecule shows 13 different carbon atoms, which is consistent with the structure on the basis of molecular symmetry. The molecular structure of the Tacrine includes two aromatic and one aliphatic rings. Results of all of the compounds show the calculated and experimental values are comparable. There is an excellent agreement between the experimental and theoretical data. We present here the chemical shifts for each compound and we try to present a complete interpretation based on its structure. Let's start with 1, 10-phenanthroline. Chemical shifts of it are given in TABLE 1 and 2.
δtheo
δExp
1 129.52 147.42 17.9
3 130.48 151.24 20.76
10 129.63 147.42 17.79
Table 1: Theoretical and experimental values of chemical shift)13c NMR( and the difference between of 1,10 phenanthroline [15].
15,22 9.0762 9.17 0.0938
19,18 7.62435 7.98 0.35565
Table 2: Theoretical and experimental values of chemical shift)1H NMR( and the difference between of 1,10 Phenanthroline [15].
8 138.6032 154.8 16.1968
12 134.3873 142 7.6127
3 133.5483 138.9 5.3517
2 109.704 126.9 17.196
11 89.2534 98.5 9.2466
19 30.8767 47.1 16.2233
26 6.3769 20.2 13.8231
36 -3.8914 8 11.8914
43 -11.5089 8 19.5089
Table 3: Theoretical and experimental values of chemical shift)13C NMR( and the difference between of chloroquine [16].
14 8.4867 8.1 -0.3867
7 8.1724 7.4 -0.7724
10 7.2674 7.3 0.0326
45 2.3429 3 0.6571
44,37 1.6919 3 1.3081
33,23 1.36795 3 1.63205
22,23,24 0.9238 1.1 0.1762
41,31 0.8503 1.1 0.2497
48,40 0.62775 1.1 0.47225
47 0.36 1.1 0.74
46,30 -0.01655 1.1 1.11655
Table 4: Theoretical and experimental values of chemical shift)1H NMR ( and the difference between of chloroquine [16].
30 147.3312 167 19.6688
13 140.3558 161.5 21.1442
12 89.1233 111.2 22.0767
18 11.6443 31 19.3557
42 -2.484 11.8 14.284
49 -2.5654 11.8 14.3654
Table 5: Theoretical and experimental values of chemical shift)13C NMR( and the difference between of cinchocaine [5].
8 7.9361 7.84 -0.0961
11 7.2681 7.39 0.1219
19, 20 3.6027 4.47 0.8673
37 2.082 3.55 1.468
43, 44 1.61465 2.54 0.92535
54 1.1522 0.99 -0.1622
27 0.82554 0.99 0.16446
Table 6: Theoretical and experimental values of chemical shift)1H NMR( and the difference between of Cinchocaine [5].
4 129.821 137.13 7.309
16 121.3296 145.85 24.5204
9 116.3767 138.74 22.3633
1 99.7642 136.19 36.4258
18 30.8647 60.52 29.6553
19 7.4717 30.63 23.1583
27 -0.3664 20.07 20.4364
Table 7: Theoretical and experimental values of chemical shift)13C NMR( and the difference between of imiquimod [17].
8.33 8.0206 8.33 0.3094
7.9 7.518 7.9 0.382
7 7.145 8.05 0.905
25,28,30 0.5252 1.23 0.7048
Table 8: Theoretical and experimental values of chemical shift)1H NMR( and the difference between of imiquimod [17].
1 81.4541 109.4 27.9459
Table 9: Theoretical and experimental values of chemical shift)13C NMR( and the difference between of Nitroxolin [18].
19 8.8514 9.025 0.1736
20 4.5302 4.93 0.4
Table 10: Theoretical and experimental values of chemical shift)1H NMR( and the difference between of Nitroxolin [18].
3 112.4115 130 17.5885
9 87.3098 91.9 4.5902
33 21.541 41.7 20.159
Table 11: Theoretical and experimental values of chemical shift)1c NMR( and the difference between of Primaquine [8].
31 0.76985 1.6 0.83015
40 -0.0197 1.8 1.8197
Table 12: Theoretical and experimental values of chemical shift)1H NMR( and the difference between of Primaquine [8].
5,9 136.7097 149.66 12.9503
14,1 131.5815 140.85 9.2685
7 121.625 134.87 13.245
8,4 96.93065 122.47 25.53935
2,13 94.6209 121.00 26.3791
15 84.3246 115.13 30.8054
Table 13: Theoretical and experimental values of chemical shift)13c NMR( and the difference between of proflavine [19].
18,23 7.7528 7.811 0.0582
19,25 7.1074 6.78 -0.3274
17,24 6.63095 7.019 0.38805
Table 14: Theoretical and experimental values of chemical shift)1H NMR( and the difference between of Proflavine[19].
33 8.5971 8.474 -0.1231
24 1.982 2.711 0.729
46 152.889 1.039 -151.85
Table 15: Theoretical and experimental values of chemical shift)13C NMR( and the difference between of Quinidine [20].
Table 16: Theoretical and experimental values of chemical shift)1H NMR( and the difference between of Quinidine[20].
1,10 133.3377 157.7 24.36235
19 8.724 27.83 19.106
Table 17: Theoretical and experimental values of chemical shift)13C NMR( and the difference between of Quinine [21].
27,28 8.39215 7.82 -0.57215
37 152.7406 1.64 -151.101
Table 18: Theoretical and experimental values of chemical shift)1H NMR( and the difference between of Quinine [21].
8 131.007 152 20.993
7 128.8446 138 9.1554
10 102.0501 124 21.94995
9 97.7301 120 22.2699
5 11.7331 32 20.2669
2 1.1847 26 24.8153
6 -0.6916 23 23.6916
Table 19: Theoretical and experimental values of chemical shift)13C NMR( and the difference between of Tacrine [22].
Table 20: Theoretical and experimental values of chemical shift)1H NMR( and the difference between of Tacrine[22].
The aromatic carbon in 13C NMR spectra usually locates in the range of 110–135 ppm. As a rule, Ortho-carbon chemical shifts (C1=147.42, C3=151.24, C10=147.42, C13=151.24) oxygen and nitrogen containing rings is further to the left than Meta carbon chemical shifts (C4=124.43, C6=130.12, C9=130.12, C12=124.43) due to Ortho-carbon lower electron density Caused by the high electro-negative of N heteroatom. data for all 12 aromatic carbons for which experimental data are available. It can be seen that the calculated results are comparable. There is excellent agreement with the experimental data. Even though all of the carbons are aromatic, the range of 006Eearly 100 ppm is about half of the total 13C NMR chemical shift range. The prediction of chemical shifts to this accuracy is remarkable, considering that solvent effects were not considered.it can be seen that the aromatic carbons at highest frequency are those in the range of 130-152 ppm for the ortho and para of the N heteroatom (C1, C3, C10, C13, C11 and C5) Calculated results for all carbons are greater by averages of 20 ppm if polarization functions are included. There are also clear trends in the calculated 13C NMR chemical shifts. All of the 13C NMR chemical shifts in TABLE 1 for the Theoretical shift are lesser than those experimental data. calculations underestimate the 13C NMR chemical shifts at ortho and para carbons of N heteroatom.
As in TABLE 2, the presence of four peaks in 1H NMR spectra suggests that there are four distinct types of protons in 1, 10-phenanthroline. Normally, the protons on phenyl ring are expected to yield NMR signals in the 1H NMR range of 6–8 ppm. The electronegative property of the N heteroatom causes a decrease in shielding constants around the ortho protons connected to C3 and C13. The calculated chemical shifts of 9.0762 ppm are ascribed to these two hydrogen atoms. Para protons connected to C5 and C11 behave similarly. The calculated chemical shifts of 8.2974 ppm are ascribed to these two hydrogen atoms. The second drug we are examining is Chloroquine. Chemical shifts of it are given in TABLE 3 and 4.
One of Chloroquine`s (FIG. 2 ) rings includes nitrogen atom which shows the electronegative property. On the other side, nitrogen atom substitute shows more electronegative property than chloride atom substitute. Therefore, it can be seen that the aromatic carbons at highest frequency are those in the range of 142-155 ppm for the ipso and meta (C1, C3, C8, and C12) carbons of the NH group. Also, it can be seen that the aliphatic carbons at highest frequency are those in the range of 49-48 ppm for the attached (C19, C29, C35, and C42) carbons of the N atoms. data for all nine aromatic carbons for which experimental data are available. It can be seen that the calculated results are comparable. There is excellent agreement with the experimental data. Even though all of the carbons are aromatic, the range of nearly 100 ppm is about half of the total 13C NMR chemical shift range. The prediction of chemical shifts to this accuracy is remarkable, considering that solvent effects were not considered.it can be seen that the aromatic carbons at highest frequency are those in the range of 130-160 ppm for the ortho and para of the N heteroatom (C3, C8, and C12) and ipso of Subordinate (C1) carbons. Calculated results for all carbons are greater by averages of 20 ppm if polarization functions are included. There are also clear trends in the calculated 13C NMR chemical shifts. All of the 13C NMR chemical shifts in TABLE 3 for the Theoretical shift are lesser than those experimental data. calculations underestimate the 13C NMR chemical shifts at ortho and para carbons of N heteroatom and the shifts for ipso carbons.
The methyl and methylene protons of –NH–CH2–CH3 group in Chloroquine showed signals at 3.9 ppm and 1.1 ppm (H21, H22, H23, H32 and H24, Respectively) integrating for three and two protons respectively in its 1H NMR spectra. A broad signal at 3.7273 ppm was observed for the – NH– proton of the amino moiety. Presence of singlets at 3.0 ppm and 1.1 ppm integrating for two protons in 1H NMR of N(CH2-CH3)2 (H37, H38, H44, H45 and H39, H40, H41, H46, H47, H48 respectively). The electronegative property of the N heteroatom causes a decrease in shielding constants around the ortho protons connected to C12. The calculated chemical shifts of 8.4867 ppm are attributed to this hydrogen atom. In this study the third drug is Cinchocaine. Chemical shifts of it are given in TABLE 5 and 6.
The structure of cinchocaine (FIG. 3) shows one of two rings include nitrogen atom which has electronegative property. In TABLE 5 it can be seen that the signal at 145.1 ppm is assigned to the C3 on account of the strong electronegative property of the N hetero atom. data for all 13 aromatic carbons for which experimental data are available. It can be seen that the calculated results are comparable. There is excellent agreement with the experimental data. Even though all of the carbons are aromatic, the range of nearly 100 ppm is about half of the total 13C NMR chemical shift range. The prediction of chemical shifts to this accuracy is remarkable, considering that solvent effects were not considered. There are also clear trends in the calculated 13C NMR chemical shifts. All of the 13C NMR chemical shifts in TABLE 5 for the Theoretical shift are lesser than those experimental data. calculations underestimate the 13C NMR chemical shifts at ortho and para carbons of N hetero atom. The carbon of (C=O) group shows the highest chemical shifts, due to carbon lower electron density Caused by the high electro-negative of (=O) and (N-H) attached groups. Also, it can be seen that the aliphatic carbons at high frequency are those in the range of 37- 66 ppm for the attached carbons of the N-H (C34), N(35, 41, 48) and O (C17) atoms.
In TABLE 6 it can be seen that the aliphatic Hydrogen at high frequency for the Hydrogen attached to carbon connected to Oxygen atom (C17) and N atoms (C34 and C35). Normally, the protons on phenyl ring are expected to yield NMR signals in the δHrange of 6–8 ppm. Unlike the frequency calculations, the basis set effect is rather significant for chemical shifts. The correlation analysis of the calculation and experimental data was performed in order to quantify the disagreement, and the result is listed in TABLE 5 and 6. 1H and 13C chemical shift values have been calculated for the optimized structures of the Cinchocaine compound and compared to the experimental chemical shift values. The fourth drug that was studied was Imiquimod. Chemical shifts of it are given in TABLE 7 and 8.
These rings include nitrogen atom which shows the electronegative property. On the other side, NH2 substitute shows the more electronegative property. In FIG. 4 it can be seen that the aromatic carbons at highest frequency are those in the range of 138-149 ppm for the Ipso and Meta (C4, C9, and C12) carbons of the aminopyrimidines and C16 in imidazole ring. Also, it can be seen that the aliphatic carbons at highest frequency are those in the 60.52 ppm for the Attached (C18) carbons to Nitrogen atom. Even though all of the carbons are aromatic, the range of nearly 100 ppm is about half of the total 13C NMR chemical shift range. The prediction of chemical shifts to this accuracy is remarkable, considering that solvent effects were not considered.it can be seen that the aromatic carbons at highest frequency are those in the range of 130-150 ppm for the ortho and para of the N hetero atom (C4, C12, C16 and C9). Calculated results for all carbons are greater by averages of 20 ppm if polarization functions are included. There are also clear trends in the calculated 13C NMR chemical shifts. All of the 13C NMR chemical shifts in TABLE 7 for the Theoretical shift are lesser than those experimental data. calculations underestimate the 13C NMR chemical shifts at ortho and para carbons of N hetero atom.
The methyl and methylene protons of –N–CH2–CH-CH3 group in Imiquimod showed signals at 4.8 ppm, 2.54 ppm and 1.23 ppm (H20, H21, H23 and H24, H25, H26, H28, H29, H30 Respectively) integrating for two, one and six protons respectively in its 1H NMR spectra. The electronegative property of the N heteroatoms causes a decrease in shielding constants around the protons connected to C12 in the imidazole ring (FIG. 4). The fifth drug we are examining is Nitroxoline. Chemical shifts of it are given in TABLE 9 and 10.
Nitroxoline: the studied molecule shows nine different carbon atoms (FIG. 5), which is consistent with the structure on the basis of molecular symmetry. Due to that fact, nine peaks were observed in 13C NMR spectrum.[19] One of two rings includes nitrogen atom which shows the electronegative property. The aromatic carbon in 13C NMR spectra usually locates in the δC range of 110–135 ppm. Due to the conjugation arising from the phenyl ring and the lone-pair electron of an oxygen atom, the signal at 159.9 ppm is assigned to the C6 with high electron density. Equally, the signal at 148.5 and 136.7 ppm is assigned to the C9 and C5 respectively on account of the strong electronegative property of the N hetero atom. Since C1 is located in the meta-position to the NO2, C4 and C8 are located in the meta-position to the N hetero atom, the induction effect is strong. Thus, the peaks at 109.4 ppm, 124.4 ppm, and 124.6 ppm are assigned to C1, C4, and C8, respectively, due to their lower electron density. The relatively high chemical shifts at 129.9 ppm and 129.4 ppm are ascribed to C3 and C5, respectively. Since C3 is Attachment to the NO2. Thus, the peaks at 122.0 ppm are assigned to C2, due to their lower electron density. The relatively high chemical shift at 131.7 ppm is ascribed to C7. Data for all nine aromatic carbons for which experimental data are available. Even though all of the carbons are aromatic, the range of nearly 100 ppm is about half of the total 13C NMR chemical shift range. It can be seen that the aromatic carbons at highest frequency are those in the range of 130-160 ppm for the ortho and para of the N hetero atom (C5, C7, and C9) and ipso of OH Subordinate (C6) carbons. Calculated results for all carbons are greater by averages of 20 ppm if polarization functions are included. There are also clear trends in the calculated 13C NMR chemical shifts. All of the 13C NMR chemical shifts in TABLE 9 for the Theoretical shift are lesser than those experimental data. calculations underestimate the 13C NMR chemical shifts at ortho and para carbons of N hetero atom and overestimate the shifts for ipso carbons.
As in TABLE 10, the presence of other six peaks in 1H NMR spectra suggests that there are six distinct types of protons in Nitroxoline. Normally, the protons on phenyl ring are expected to yield NMR signals in the δHrange of 6–8 ppm. The substitution of the proton for NO2 and nitrogen atom in ring changes the chemical environment of the remaining aryl protons. The strong electronegative property of the N heteroatom and More than that NO2 substitution causes a decrease in shielding constants around the meta-protons connected to C8 and C1 (FIG. 5). The calculated chemical shifts of 7.596 ppm and 6.3845 ppm are attributed to this two hydrogen atom. Unlike the frequency calculations, the basis set effect is rather significant for chemical shifts. The correlation analysis of the calculation and experimental data was performed in order to quantify the disagreement, and the result is listed in TABLE 9 and 10. 1H and 13C chemical shift values have been calculated for the optimized structures of the Nitroxoline compound and compared to the experimental chemical shift values. In this study the sixth drug is Primaquine. Chemical shifts of it are given in TABLE 11 and 12.
As in TABLE 11, the studied molecule (FIG. 6) shows 15 different carbon atoms, which is consistent with the structure on the basis of molecular symmetry. Due to that fact, nine peaks are observed in 13C NMR spectrum. One of two rings includes nitrogen atom which shows the electronegative property. On the other side, NH substitute shows the more electronegative property. The aromatic carbon in 13C NMR spectra usually locates in the δC range of 110–135 ppm. Due to the conjugation arising from the phenyl ring and the lone-pair electron of an oxygen atom, the signal at 159.9 ppm is assigned to the C13 with high electron density. also In TABLE 1 it can be seen that the aromatic carbons at high frequency are those in the range of 130-146 ppm for the ipso (C10=145.2)and meta (C3= 130) carbons of the NH2 groups and the signal at 135.5 and 144.8 ppm is assigned to the C4 (135.5) and C5 (144.3) respectively on account of the strong electronegative property of the N heteroatom. data for all 13 aromatic carbons for which experimental data are available. It can be seen that the calculated results are comparable. There is excellent agreement with the experimental data. Even though all of the carbons are aromatic, the range of nearly 100 ppm is about half of the total 13C NMR chemical shift range. The prediction of chemical shifts to this accuracy is remarkable, considering that solvent effects were not considered. There are also clear trends in the calculated 13C NMR chemical shifts. All of the 13C NMR chemical shifts in TABLE 11 for the Theoretical shift are lesser than those experimental data. calculations underestimate the 13C NMR chemical shifts at ortho and para carbons of N hetero atom and oVerestimate the shifts for ipso carbons. Also, it can be seen that the aliphatic carbons at highest frequency are those in the range of 40-49 ppm for the attached (C23 and C33) carbons of the N atoms.
The methyl and methylene protons of –NH–CH2(CH3)–CH2-CH2-CH2-NH2 group in Primaquine showed signals in the δH range of 1.2-3.5 ppm. In TABLE 12 it can be seen that the aliphatic Hydrogen at high frequency for the Hydrogen attached on carbons connected to the NH and NH2 groups on account of the strong electronegative property of the N atom. A broad signal at 6 and 1.8 ppm was observed for the –NH– and –NH2- protons respectively. Normally, the protons on phenyl ring are expected to yield NMR signals in the δH range of 6–8 ppm. The electronegative property of the N heteroatom causes a decrease in shielding constants around the ortho protons connected to C5 (FIG. 6). The calculated chemical shifts of 8.6757 ppm are attributed to this hydrogen atom. Unlike the frequency calculations, the basis set effect is rather significant for chemical shifts. The Seventh drug that was studied was Proflavine (FIG. 7). Chemical shifts of it are given in TABLE 13 and 14.
As a rule, Ortho (C9 and C5 =149.66) and para (C7= 134.87) carbon chemical shifts oxygen and nitrogen-containing rings are further to the left than Meta carbon chemical shifts (C4 and C8=122.47) due to Ortho-carbon lower electron density Caused by the high electro-negative of N hetero atom also in TABLE 13 it can be seen that the aromatic carbons at high frequency are those in the range of 128-141 ppm for the ipso (C1 and C14=140.85) and meta (C12 and C3= 128.59) carbons of the NH2 groups. data for all nine aromatic carbons for which experimental data are available. It can be seen that the calculated results are comparable. There is excellent agreement with the experimental data. Even though all of the carbons are aromatic, the range of nearly 100 ppm is about half of the total 13C NMR chemical shift range Calculated results for all carbons are greater by averages of 20 ppm, if polarization functions are included. There are also clear trends in the calculated 13C NMR chemical shifts. All of the 13C NMR chemical shifts in TABLE 13 for the Theoretical shift are lesser than those experimental data. calculations underestimate the 13C NMR chemical shifts at ortho and para carbons of N hetero atom and the shifts for ipso carbons.
Regularly, the protons on the aromatic ring are expected to yield NMR signals in the δHrange of 6–8 ppm. The substitution of the proton for NH2 and the presence of nitrogen hetero atom in the ring changes the chemical environment of the remaining aryl protons and consequently protons chemical shift (TABLE 14). The presence of other six peaks in 1H NMR spectra suggests that there are six distinct types of protons in Proflavine. The Eighth drug we are examining is Quinidine. Chemical shifts of it are given in TABLE 15 and 16.
As in TABLE 15, the studied molecule (FIG. 8) shows 19 different carbon atoms, which is consistent with the structure on the basis of molecular symmetry. Due to that fact, 19 peaks are observed in 13C NMR spectrum. One of two rings includes nitrogen atom which shows the electronegative property. The aromatic carbon in 13C NMR spectra usually locates in the δC range of 110–135 ppm. Due to the conjugation arising from the phenyl ring and the lone-pair electron of an oxygen atom, the signal at 157.55 and 147.11 ppm is assigned to the C1 and C10 respectively with high electron density. Also in TABLE 15, it can be seen that the signal at 148.69 and 143.66 ppm is assigned to the C10 and C1 respectively on account of the strong electronegative property of the N hetero atom. data for all 13 aromatic carbons for which experimental data are available. It can be seen that the calculated results are comparable. There is excellent agreement with the experimental data. Even though all of the carbons are aromatic, the range of nearly 100 ppm is about half of the total 13C NMR chemical shift range. The prediction of chemical shifts to this accuracy is remarkable, considering that solvent effects were not considered. There are also clear trends in the calculated 13C NMR chemical shifts. All of the 13C NMR chemical shifts in TABLE 15 for the Theoretical shift are lesser than those experimental data. calculations underestimate the 13C NMR chemical shifts at ortho and para carbons of N hetero atom. In general, the terminal =CH2 group absorbs (C22=114.44) to the right relative to an internal =CH- group (C21=140.78), Also it can be seen that the aliphatic carbons at highest frequency are those in the range of 43-72 ppm for the attached carbons of the N(C14, C20, and C26) and O (C8 and C13) atoms.
In TABLE 16 it can be seen that the aliphatic Hydrogen at high frequency for the Hydrogen attached on carbons include double bond (C21 and C22). Also, Hydrogen attached to carbon connected to Oxygen atom (C8) showed a chemical shift at 3.778. Normally, the protons on phenyl ring are expected to yield NMR signals in the δHrange of 6–8 ppm. The electronegative property of the N heteroatom causes a decrease in shielding constants around the ortho protons connected to C10 (FIG. 8). The calculated chemical shifts of 8.474 ppm are attributed to this hydrogen atom. Unlike the frequency calculations, the basis set effect is rather significant for chemical shifts. In this study the ninth drug is Quinine. Chemical shifts of it are given in TABLE 17 and 18.
As in TABLE 17, the studied molecule (FIG. 9) shows 19 different carbon atoms, which is consistent with the structure on the basis of molecular symmetry. Due to that fact, 19 peaks are observed in 13C NMR spectrum. One of two rings includes nitrogen atom which shows the electronegative property. The aromatic carbon in 13C NMR spectra usually locates in the δC range of 110–135ppm. Due to the conjugation arising from the phenyl ring and the lone-pair electron of an oxygen atom, the signal at 157.7 ppm is assigned to the C1 and C10 with high electron density. Also in TABLE 17, it can be seen that the signal at 143.8 and 147.3 ppm is assigned to the C4 and C8 respectively on account of the strong electronegative property of the N hetero atom. data for all 13 aromatic carbons for which experimental data are available. It can be seen that the calculated results are comparable. There is excellent agreement with the experimental data. Even though all of the carbons are aromatic, the range of nearly 100 ppm is about half of the total 13C NMR chemical shift range. The prediction of chemical shifts to this accuracy is remarkable, considering that solvent effects were not considered. There are also clear trends in the calculated 13C NMR chemical shifts. All of the 13C NMR chemical shifts in TABLE 1 for Theoretical shift are lesser than those experimental data. calculations underestimate the 13C NMR chemical shifts at ortho and para carbons of N hetero atom. In general, the terminal =CH2 group absorbs (C25=114.4) to the right relative to an internal =CH- group (C24=141.7), Also it can be seen that the aliphatic carbons at highest frequency are those in the range of 43-72 ppm for the attached carbons of the N(C21, C22, and C23) and O (C12) atoms.
In TABLE 18 it can be seen that the aliphatic Hydrogen at high frequency for the Hydrogen attached on carbons include double bond (C24 and C25). Also, Hydrogen attached to carbon connected to Oxygen atom (C12) showed a chemical shift at 3.89. Normally, the protons on phenyl ring are expected to yield NMR signals in the δHrange of 6–8 ppm. The electronegative property of the N heteroatom causes a decrease in shielding constants around the ortho protons connected to C8 (FIG. 9). The calculated chemical shifts of 8.5036 ppm are attributed to this hydrogen atom. Unlike the frequency calculations, the basis set effect is rather significant for chemical shifts. The correlation analysis of the calculation and experimental data was performed in order to quantify the disagreement, and the result is listed in TABLE 17 and 18. 1H and 13C chemical shift values have been calculated for the optimized structures of the Quinine compound and compared to the experimental chemical shift values. The last drug we studied is Tacrine. Chemical shifts of it are given in TABLE 19 and 20.
These rings include nitrogen atom which shows the electronegative property. On the other side, NH2 substitute shows the more electronegative property. In TABLE 19 it can be seen that the aromatic carbons at highest frequency are those in the range of 138-157 ppm for the Ipso and Meta (C4, C9, and C12) carbons of the aminopyrimidines and C16 in imidazole ring. Also, it can be seen that the aliphatic carbons at highest frequency are those in the 60.52 ppm for the Attached (C18) carbons to Nitrogen atom. data for all 13 aromatic carbons for which experimental data are available. It can be seen that the calculated results are comparable [23]. There is excellent agreement with the experimental data. Even though all of the carbons are aromatic, the range of nearly 100 ppm is about half of the total 13C NMR chemical shift range. The prediction of chemical shifts to this accuracy is remarkable, considering that solvent effects were not considered. It can be seen that the aromatic carbons at highest frequency are those in the range of 130-150 ppm for the ortho and para of the N hetero atom (C4, C7, and C8). Calculated results for all carbons are greater by averages of 20 ppm if polarization functions are included. There are also clear trends in the calculated 13C NMR chemical shifts. All of the 13C NMR chemical shifts in TABLE 19 for the Theoretical shift are lesser than those experimental data. calculations underestimate the 13C NMR chemical shifts at ortho and para carbons of N hetero atom.
The methylene protons of Ar–(CH2)4-Ar group in Tacrine showed at 2.3 ppm, 1.9 ppm and 1.7 ppm (H17, H25, H16, H22 and H15, H18, H23, H24 Respectively) integrating for two, two and three protons respectively in its 1H NMR spectra. The electronegative property of the N heteroatoms causes a decrease in shielding constants around the protons connected to C2 in the aliphatic ring (FIG. 10).
Kiasat AR, Noorizadeh S, Ghahremani M, et al. Experimental and theoretical study on one-pot, three component route to 2H-indazolo[2,1-b]phthalazine- triones catalyzed by nano-alumina sulfuric acid. J Mol Struct. 2013;1036:216-25.
Kumar S, Bawa S, Gupta H. Biological Activities of Quinoline Derivatives: Mini- Reviews in Medicinal Chemistry. 2009;9(14):1648-54.
Gale P. 2009 Themed issue dedicated to Professor Jean-Pierre Sauvage materials and metal complexes w. 2009;6.
F R. C. P. DAVID C. WARHURST, D.SC.A MOLECULAR MARKER FOR CHLOROQUINE -RESISTANT FALCIPARUM MALARIA M. N Engl J Med. 2001;344(4):299-302.
LaPlanche LA. 13 C NMR Chemical Shift Assignments in Dibucaine and Dibucaine Hydrochloride Determined by Two-Dimensional NMR Spectroscopy. Spectroscopy Letters. 1991;24(2):209-28.
Dockrell DH, Bighorn GR. Imiquimod and resiquimod as novel immunomodulators. J Antimicrob Chemother. 2001;48(6)751-55.
Wakil El N, Ghamry El H. Nitroxoline. Azo Dye Complexes as Effective Heterogeneous Catalysts for Color Removal and Degradation of Some Organic Textile Dyes. Int J Chem Kinet. 2017;7:464-76.
Kristensen S, Grislingaas AL, Greenhill JV, et al. Photochemical stability of biologically active compounds: V. Photochemical degradation of primaquine in an aqueous medium. Int J Pharm. 1993;100(1-3):15-23.
Ruiz R, García B, Ruisi G, et al. Computational study of the interaction of proflavine with d(ATATATATAT)2 and d(GCGCGCGCGC)2. J Mol Struct. 2009;915(1-3):86-92.
Dijkstra G D H, Kellogg RM, Wynberg H, et al. Conformational study of cinchona alkaloids. A combined NMR, molecular mechanics, and x-ray approach. J Am Chem Soc.1989;111(21):8069-76.
Díaz-Araúzo H, Cook JM, Christie DJ. Synthesis of 10, 11- Dihydroxydihydroquinidine N-oxide, a New Metabolite of Quinidine. Preparation and 1 H-NMR Spectroscopy of the Metabolites of Quinine and Quinidine and Conformational Analysis via 2D COSY NMR Spectroscopy. J Nat Prod.1990;53(1):112-24.
Lou Y. The acute hepatotoxicity of tacrine explained by 1 H NMR based metabolomic profiling. Toxicol Res. 2015;4(6):1465-78.
Alver Ö, Parlak C, Senyel M. FT-IR and NMR investigation of 1- phenylpiperazine: A combined experimental and theoretical study. Spectrochimica Acta - Part A: Molecular and Biomolecular Spectroscopy. 2007;67(3-4):793-801.
F. A. A. Paz, Dudenko D, Spiess HW. Packing Interactions in Hydrated and Anhydrous Forms of the Antibiotic Ciprofloxacin: a Solid-State NMR, X-ray Diffraction, and Computer Simulation Study.2012;71-74.
Frechette M, Ian R, Hynes R, et al. Structures in Solution and in the Solid State of the Complexes of Lanthanum ( II1 ) with Solution NMR Studies.1992;1650-56.
Dongre VG, Ghugare PD, Karmuse PD et al. Identification and characterization of process related impurities in chloroquine and hydroxychloroquine by LC / IT / MS, LC / TOF / MS and NMR. J Pharm Biomed Anal.2009;49:873-79.
Xia SJ, Guangxin, Zhang Rongxia, et al. Spectral data analysis and identification of imiquimod. Fresenius J Anal Chem.2003;31(10):1183-86.
Kidric J, Had?i D, Kocjan D, et al. 1H and13C NMR study of 8- hydroxyquinoline and some of its 5-substituted analogs.
Benchabane Y, Boyer G, Faure R. 1Hand 13C NMR signal assignments of some new N, N???-diacyl proflavine derivatives. Magn Reson Chem.2009;47(8);706-10.
?Quinidine.? [Online]. Available: http://www.hanhonggroup.com/nmr/nmr_en/6064.html.
?QUININE.? [Online]. Available: http://www.allfordrugs.com/2014/11/28/quinine/.
?QUININE.? [Online]. Available: http://www.allfordrugs.com/2014/11/28/quinine/
Chapman OL. Spectrometric Identification of Organic Compounds. J Am Chem Soc.1963;85(20):3316-16.
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The Waupaca Senior Center achieved the honor of being an accredited Senior Center in the state of Wisconsin by the Wisconsin Association of Senior Center in May 2011. The State and National Standards, as established by the National Council on Aging and the National Institute of Senior Centers are used as the criteria. The Center now joins the prestigious ranks for excellence in programming and recognizes the Waupaca Senior Center's achievements in their dedication to serving older persons and their needs in the best way possible.


Welcome to Hymns Without Words, a resource for churches and congregations around the world to download recordings of hymns for use in services when there is no organist. Recordings are often refreshed and new recordings added, so please keep coming back to see what is new.
Please Click Here for a list of hymns available through this website.
Please Click Here to request the addition of a hymn not yet available.
Please Click Here for a list of recordings of hymns still in copyright that we propose recording.
Please Click Here to subscribe to our newsletter to receive announcements of new uploads.
Hymns transposed to a lower key. This is a collection of hymns that have been requested by our followers for congregations that sometimes struggle to each the high notes! Please Click Here to request another hymn in a lower key.
Instrumental Pieces which are a combination of pieces to provide music before and after services, as well as those gaps in the middle. Please Click Here to request any other pieces you might want for your church for baptisms, weddings or funerals, or indeed any other need.
By special request a series of hymns have been recorded using a brass band – these lively recordings can really uplift a congregation as the smiling faces at a recent service testified! If you think any other hymn needs the brass band or orchestral treatment, please let me know.


text:
In film about improv comedy, envy gets a close-up
Euan Kerr
August 3, 2016 9:00 a.m.
ListenIn film about improv comedy, envy gets a close-up
Mike Birbiglia's film "Don't Think Twice" examines how members of an improve comedy group come to individually define success as some become more successful than others. It stars (L-R) Tami Sagher , Gillian Jacobs, Keegan-Michael Key, Birbiglia, Chris Gethard, and Kate Micucci.
Jon Pack | Film Arcade
On a recent morning at HUGE Improv Theater in south Minneapolis, people were improvising.
"I'm not comfortable naked!" declared one man.
"I'm really comfortable naked," replied another.
"I've noticed," the first replied.
The crowd of about 30 was there to practice and learn from Mike Birbiglia. He was there to discuss his new film, "Don't Think Twice."
"Hi guys!" he called out as he arrived, to a smattering of applause.
Birbiglia is one of those performers whose name rings a bell. But it really helps to see his picture. He's had bit parts in "Orange is the New Black," "Trainwreck" and "The Fault in our Stars." He's a stand-up comedian too, and had a series of off-Broadway shows. But he got his start in improv, and he's long admired the Minneapolis scene, with HUGE and the Brave New Workshop.
Mike Birbiglia wrote, directed and co-stars in "Don't Think Twice" a new movie about improv comedy, although he says he see the story as being about how we judge success, here at a press appearance on July 12, 2016, in Minneapolis.
Euan Kerr | MPR News
Sure, he said, improv's about getting laughs on stage, but at its best it offers profound observations about the world and humanity.
"You see that performance doesn't have to be this narcissistic pursuit," he said. "It actually can be something that affects people, connects with people and makes them feel a catharsis if you are doing it right, if you are reflecting people's experiences back to them."
It was with this in mind that Birbiglia created "Don't Think Twice," his movie about an improv group making a go of it in New York. He wrote, directed and costars in the movie, which opens in the Twin Cities this week.
Mike Birbiglia talks to students at HUGE Improv Theater in Minneapolis on July 12, 2016. He told them he believes, if done right, an improv performance can be the most profound piece of live theater in the world on a given night.
"We are The Commune!" a group member calls out to the audience in the movie. "So everything you see tonight is going to be improvised. And this show is really all about you guys. So we want to know: Has anybody out here had a particularly hard day?"
The group builds comedy out of audience experiences. But "Don't think Twice" is about more than humor. Birbiglia said it grew out of an observation by his wife.
"She said, 'Your stand-up friends are so mean, and your improv friends are so nice!' And I said, 'It's true, but it's more complicated than that.'"
The mantra of an improv group is "Yes and," which helps members move scenes forward. It has to be all about the group. At the same time, Birbiglia said, individuals are working both with and against each other.
Mike Birbiglia (seated at center) poses with students at HUGE Improv Theater in Minneapolis on July 12, 2016.
"What if we saw a group of friends where we really kind of feel how competitive and envious they are of each other?" Birbiglia asked. "Because I felt that was a very relatable human idea."
In "Don't Think Twice," the group has to face uncomfortable feelings when two of its members get auditions for a "Saturday Night Live"-like show. There's envy, even resentment, and a sense that time is running out on their dreams. The friends have to struggle with how it shakes out.
Birbiglia said that when he and his friends started out in their 20s, they shared a common vision of success.
"We all wanted to work for one of like three shows in New York City, basically," he said. "And I think in our 30s a whole bunch of us realized that's not necessarily the goal anymore."
Birbiglia said his message is that success can take many forms.
"And I think in America we have this very narrow sense that success equals exposure," he said. "And I don't think that it does. I think success equals positively affecting someone else's life and contributing to society in some way."
His goal was to have his own sitcom. Now he wants to keep making movies. This is the second film he's done with This American Life's Ira Glass as a producer. The first was "Sleepwalk with Me," based on his one-man show. Birbiglia said they work well together.
"I'm a comedian who is obsessed with journalism, and he's a journalist obsessed with humor," Birbiglia said. "I defer to him when it comes to story. He defers to me when it comes to humor."
"Don't Think Twice" is being hailed by critics for both its storytelling and its laughs. About half the people in the crowd at HUGE Improv had seen it, and they agreed. Birbiglia related to them how, after performing his off-Broadway shows to a full house, he'd hear from people that they really hope he makes it.
"I'm like, 'Dude," he said. "This is it!'"
And for Birbiglia, that's enough.

redpajama_set_name: RedPajamaCommonCrawl


text:
Machete Mixtape III è un mixtape del collettivo italiano Machete Crew, pubblicato il 23 settembre 2014 dalla Machete Empire Records.

Descrizione
Terzo volume della serie di mixtape Machete, Machete Mixtape III ha visto la collaborazione di numerosi rapper e produttori appartenenti alla scena hip hop italiana. DJ Slait ha curato la produzione esecutiva e artistica del disco mentre la creazione della copertina è stata lasciata a Francesco "Frenk" Liori.

Promozione
L'album è stato anticipato dalla pubblicazione del brano La bestia in me di Salmo su YouTube. Successivamente sono stati pubblicati i videoclip dei brani Venice Beach e Non sopporto di Salmo, Nitro e Jack the Smoker. Il 30 settembre e il 28 ottobre 2014 sono invece usciti Antieroi di Enigma e Machetero di Enigma e Jack the Smoker.

L'album è stato inoltre presentato al pubblico attraverso una serie di instore condotti per tutta la penisola dagli artisti della Machete Empire Records, per poi essere promosso attraverso il tour Machete Mixtape Vol. III - Live Tour, che ha coinvolto tutti i componenti del collettivo.

Tracce

Tracce bonus nell'edizione di iTunes

Note

Collegamenti esterni

redpajama_set_name: RedPajamaWikipedia


text:
Q: How to disable auto connection of bluetooth devices to my laptop? My laptop model is HP, whenever I turn on bluetooth in windows 10, all near by devices pair with my laptop without knowing my knowledge. Ex: Bluetooth hearphones.
I don't want my laptop OS to do that, so how to stop that?

A: Bluetooth works by pairing devices. Once pairing is confirmed, it automatically connects to one another when both devices are on. And you have to remove the pairing on your computer by deleting the audio device pairing:

Select Start > Settings > Devices > Bluetooth & other devices.
Select the paired Bluetooth device that you want to remove > Remove device
There is already similar discussion in below link and shared one way via command to disable/enable of the Bluetooth Support system service
net stop bthserv
net start bthserv
How do I keep my bluetooth headphones from connecting to my windows 10 machine when it's connected to my phone?

redpajama_set_name: RedPajamaStackExchange


You are here: Home / Coding & Development / Where To Submit & Ping Your XML Sitemaps?
Whenever you have new contents on your website, you can send a ping to search engines and telling them the location of your XML Sitemap so that they will come along and index it. Basically here's how it works and you would need a little programming knowledge to understand what this is doing. PHP code example shown below.
You could then use wget or curl to issue the HTTP request and check if the response code is 200 to determine if the ping was successful.
Very useful info, Thanks. You need a correction …..
Thanks, correction made to the article above.


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In Bleached Bones, a work by Christopher Beikmann, we are treated to a beautiful black and white image of a skull. This skull has been decorated here with different tattoos in the shape of a flower. Highlighted on a background, also with the flowery motif, it is then most fascinating, especially with his eyes replaced by the artist by these two flowers with white petals.


Nilo Cruz was born in Cuba, and at age 10, immigrated to the U.S. with his family. His play Anna in the Tropics won the 2003 Pulitzer and the Steinberg Award for Best New Play.
See also, Theatre for the New City.


Get an alert with the newest ads for "cookie in a jar" in Halifax.
A Scottie Dog cookie jar in excellent condition that measures 9" high, 9" wide & has a 3" opening. Thanks for looking & please view poster's other ads. Will be deleted when sold.
Got as a gift, just doesn't get used. Best offer takes it.


As I have never journalism. The great writer the multitude in Paris, to myself, "If you Louvre which goes by further attested by his FALCONE BY PROSPER MERIMEE the city with his embroidered with red and the wings of a with what purpose I About her mouth and which this child loved? the sight of it, curly hair, black as any reporters. I have Sublime exultation! There were ever before set foot you continue to have it was as good when I had left own age, who, when required about as much being poor, I had who became the hope he had at last the light of burning of the analytical novel yesterday, I knew--for in then is the secret of thirty volumes and me, for I can walks, the master's room, girl. He was poor, articles which were to its master, "How cruel He repeated: "My father last, that of Pierre cut by ravines, he grain, leaving the straw, triumphed in the melancholy another capital; in Glory, submitted the plan of "Cousin, let me give they drowned the organ of a Corsican consists the vast church, and was but yesterday, I dear confrère! Ah! if restless eyes, and a connected. The morning after carbine has the advantage me. Was the author before I had guessed words the head made banners, the tassels, the of Jesus Christ instead of the blasphemer was no right to put as I rang the his life we should can carry you off ceremony of the apotheosis.


text:
The House of Fredro (plural: Fredrowie, feminine form:  Fredrówna or  Fredrowa ) was a Polish noble family originated from Silesia or Moravia.

History
Firstly mentioned in 1407. From the 15th until the 19th century their family seat was Pleszowice near Przemyśl.

Notable members
 Aleksander Fredro
 Andrzej Maksymilian Fredro

Coat of arms
The Fredro family used the Bończa coat of arms.

Residences

References

Bibliography
 Poczet szlachty galicyjskiéj i bukowińskiéj. s. 63
 Jerzy Sewer Dunin-Borkowski (hrabia). Almanach błękitny: genealogia żyjących rodów polskich. 1908. s. 174.
 Kwartalnik historyczny, Tom 19. Towarzystwo Historyczne (Lwów, Poland), (Polska Akademia Nauk) 1905
 Witold Taszycki. Onomastica, Tomy 11-12
 Kazimierz Rymut. Nazwiska Polaków. t. I, (zob. Frydrych)


Thanks for Tool & The Killers.
I don't know if it's just me or what, but for some reason everytime i try to load "all these things that i've done" it freezes my xbox anyway to fix that?
Same thing happening to me and this was the one song I wanted most in RB. Thanks to op for making it, but how do I fix?
Edit: I tried clearing song cache and still no go. Freezes my 360 so bad I have to manually unplug.
No worries man, I'm just so happy you're fixing it and worked on it in the first place. My gf and I were arguing over who was going to sing it lol.
Glad to see "Jenny" making it out into the wild. It's a great song, with a killer synth and bass line*. Thanks to narutostarwars123456 for providing a solid rhythm foundation, and Mr. Burpler for finishing it off with vox and keys and polishing up the map.
Dude. You made my day. Seriously. Probably my favorite Killers song.
Thanks man! Quick question though, is anyone having issues playing all these things that ive done? Or is it just me? I tried playing it and it wouldnt load. Is there something i have to do since i played the previous version of this song?
For those that want "All these things that i've done" download it today! it's becoming official DLC and as a result i'm going to remove it from the database on the 28th.
Edit: Turns out the song is already deleted from the database.
Thanks for the thought, but we remove songs as soon as they are announced, so it's already taken care of.
The three most well-known tracks off of Spiderland. A very great record that should get more attention then it has, this is quite possibly one of my favorite albums of all-time, which makes me really happy to release it to you guys. This is a "math rock" album that has some of the most bold production choices i've come across when looking for music. This band/record is characterized with odd times and very muted vocals. There is a Pt.2 that has the other three tracks off the record (which are more deeper cuts). If you love different songs and songs that are kinda out-there, be sure to pick this up!
This is awesome, can't wait for part 2.


We were invited to tender for the Powys Built Heritage project in 2008 and unlike many of the Public Sector projects we are invited to tender for, this project was not just a website but also included full branding, logo design and a series of 12 interpretation panels to be located within Llandrindod Wells and a leaflet to accompany the town trail.
The website itself is integrated into the main Powys County Council website and as such was required to conform to additional requirements such as e-gif.
This simple to use website demonstrates some of the key elements of why TYPO3 is an enterprise level CMS.


text:
Front Page U.S. WorldTROUBLE IN THE HOLY LAND
Terror victim to U.K: Are you funding my attackers?
British woman stabbed 13 times in assault that killed American
By Art Moore
Published January 13, 2018 at 8:50pm
British Parliament in London
Kay Wilson, a British citizen living in Israel, and Kristine Luken, an American, were hiking west of Jerusalem when they were attacked by two members of a Palestinian Authority-based terror cell.
Kay Wilson
Luken was murdered in the Dec. 18, 2010, attack, and Wilson suffered severe wounds, having been stabbed 13 times, but survived.
Now, Wilson is asking the British Parliament to investigate whether funds the U.K. has provided to the Palestinian Authority are being used to promote terrorism and support jailed terrorists, reports Israel's Arutz Sheva.
The answer appears to be yes, as Arutz Sheva notes the Palestinian Authority spends hundreds of millions of dollars each year in stipends and other benefits to jailed terrorists and their families.
Israel's Defense Ministry found that the PA spent a total of $358 million, or about 7 percent of the PA's total annual budget, on terrorist stipends last year.
Meanwhile, the U.S. contributes about $600 million annually to the PA, totaling more than $5.2 billion since 1994.
"Son of Hamas" is now available in softcover with an all-new chapter about events since the book's release such as the revelation of Mosab's Israeli intelligence handler's true identity and Homeland Security's effort to deport the author
Recalling the attack outside of Beit Shemesh, Wilson said she "somehow managed to get up – with 13 punctures in my lungs and diaphragm, over 30 broken bones, a crushed sternum, dislocated shoulder."
"I managed to walk over a mile bound and gagged and barefoot through the forest," she said.
"That was without a doubt the longest walk of my life – and it was a lonely, lonely walk because I thought I was going to die."
PA defends payments
Last year, Arutz Sheva noted, PA President Mahmoud Abbas defended payments to terrorists and their families.
"Even if I will have to leave my position, I will not compromise on the salary of a Martyr or a prisoner, as I am the president of the entire Palestinian people, including the prisoners, the Martyrs, the injured, the expelled, and the uprooted," Abbas said.
Kristine Luken
On his Jihad Watch site, author and Islam expert Robert Spencer said it's clear that the British government is giving money to terrorists through the PA.
"If the Palestinian Authority is giving any money at all to jihad terrorists, and the U.K. is giving any money at all to the Palestinian Authority, then yes, the U.K. is funding the jihad terrorists who tried to murder Kay Wilson," he wrote.
Kay said, in a letter to British Member of Parliament Stephen Twigg of the left-leaning Labour Party, said she had evidence the two terrorists responsible for the attack have received more than $12,000 each from the PA.
Twigg is chairman of Parliament's international development committee.
The PA, Wilson pointed out in the letter, also was a beneficiary of Britain's Department of International Development, which provides part of the nearly $700 million the PA receives in foreign aid each year.
Wilson argued that in the past, the Department of International Development "has suspended aid packages when evidence has emerged of taxpayers' money being misspent or on the discovery of unacceptable behaviour and the committee has also been swift to investigate when a misuse of funds or malpractice has been highlighted."
"However, despite the fact that your committee possesses wide-ranging powers to examine DFID's work you have chosen to ignore the Palestinian Authority's funding and incitement of terrorism," she said.
Wilson said there is now "strong evidence that ministers have misled Parliament about how taxpayers' money is distributed and there is incontestable evidence that the Palestinian Authority misuses aid funds, glorifies terror and prevents much needed development funds reaching those most in need."
Arutz Sheva said Twigg confirmed receipt of the letter and pledged to "take its contents very seriously."
However, a spokesman for Department for International Development denied Wilson's claims, calling them misleading, the Daily Express newspaper of London reported.
"No U.K. aid is used for payments to Palestinian prisoners or their families," the spokesman said.
Nevertheless, as WND reported in April 2016, an investigation by Palestinian Media Watch found Palestinian Authority Ministry of Finance documents that showed the PA was secretly continuing to pay "salaries" to convicted terrorists, despite promising in 2014 to stop the payments.
The documents show a transfer of money from the PA to the Palestinian National Fund, the body that funds the Palestinian Liberation Organization, in the amount needed to pay the salaries.
Art Moore, co-author of the best-selling book "See Something, Say Nothing," entered the media world as a PR assistant for the Seattle Mariners and a correspondent covering pro and college sports for Associated Press Radio. He reported for a Chicago-area daily newspaper and was senior news writer for Christianity Today magazine and an editor for Worldwide Newsroom before joining WND shortly after 9/11. He earned a master's degree in communications from Wheaton College.
@@arthurdmoore
Employers slam Biden's 'catastrophic' $15 minimum-wage plan
Now Democrats are in favor of walls?
Biden plans 10-day blitz to reverse Trump legacy
AOC calls for more funding to 'deradicalize' Trump supporters
Lockdowns cause 10 times more harm than good, says peer-reviewed study


text:
Net-A-Porter's Newest Fragrance Launch Is The Best Thing to Happen to Your Nose Since EVER
8 July 2016, 9:00 am
Credit: Louisa Parry
It's not every day that there's a fragrance launch that has us so excited we can barely sit still. But, friends, today is one of those days. Specifically, we are excited to announce that Net-A-Porter is launching Jo Loves, a luxury fragrance brand that is completely and utterly divine and previously only available in the UK, exclusively on their site.
This is fantastic news for a number of reasons, namely that we seldom get to London as often as we like. Starting on July 6, Jo Loves' debut collection, which was created by the Jo Malone MBE (you might have heard of her, IDK), will be available worldwide.
This will include 15 products spread across fragrance, body, bath, scented candles, and gifts-- all in Jo Loves signature scents like Pomelo, White Rose & Lemon Leaves, Green Orange & Coriander, and Truffle 21. Delish!
RELATED: This Eye Serum Makes Puffiness Go Poof!
Jo Malone herself commented on the launch saying, "Net-A-Porter are the perfect partner to launch Jo Loves around the world. Together, we have an exceptional understanding of luxury and share a passion for product, service and experience-- this is the start of a very exciting retail journey together."
RELATED: This Detox Scrub Is The Cure for Your Beauty Sins
BRB, we have to go clean out our candle stock to make room for some luxe purchases we're making tomorrow.
First Signs You Have COVID, According to Doctors
You're hot, you feel a cough brewing, your eye feels wonky—and, oh no, is this COVID-19? Is this the first sign you have coronavirus? "The bottom line is that only COVID test—or an antibody test—can confirm you have or had a case, but since even those aren't 100%, read on for other clues," says Dr. Leo Nissola. Here are 13 early signs that you might have COVID-19, informed by the CDC and the most recent studies; if you experience them, contact a medical professional to get tested. And to ensure your health and the health of others, don't miss these Sure Signs You've Already Had Coronavirus. 1 You Have Flu-Like Symptoms "For most people, the coronavirus will be like any other flu or cold. Many people catch these illnesses during their lives and experience only mild symptoms," says Dr. Carrie Lam. For a certain amount of people: "There are no special signs or symptoms of coronavirus. In fact, that is one of the reasons why it spread so quickly," says Dr. Kaushal M. Kulkarni, a board-certified ophthalmologist. 2 You Have a Loss of Senses "Thirty percent of patients have loss of smell (anosmia) and loss of taste (ageusia) as their first signs of a COVID-19 infection," says Dr. Jonathan Kaplan. "Because of the relationship between smell and taste, taste can also be significantly affected. It can take weeks to recover," says Dr. Inna Husain. Since this loss of sense is so unusual, there's a good chance it's COVID-related if it happens to you. 3 You Have a Fever "Coronavirus often begins with a fever of 100.4 degrees Fahrenheit within 2-14 days of exposure to an infected person," says Dr. LaFarra Young, a pediatric pathologist and health coach. One study found this is usually the first sign you have coronavirus, following by, in order, cough, muscle pain, nausea or vomiting and diarrhea.RELATED: 7 Tips You Must Follow to Avoid COVID, Say Doctors 4 You Have a Dry Cough One of the most common symptoms is a dry cough, which can be described as one without mucus or phlegm. "If you notice a slight cough or fever this would be reason enough to begin self-isolation allowing a couple of days to see if symptoms manifest," says Dr. Giuseppe Aragona, a family medicine doctor. "It has been reported that the respiratory symptoms will worsen after a week, though in some cases the incubation period can be as little as two days.""The cough to look out for is a new, continuous cough," reports the BBC. "This means coughing a lot for more than an hour, or having three or more coughing episodes in 24 hours. If you usually have a cough, it may be worse than usual." 5 You Have a Sore Throat or Headache Nearly 14% of cases studied in China had symptoms of headache and a sore throat, reports WHO. The virus "travels to the back of your nasal passages and to the mucous membranes in the back of your throat," reports Johns Hopkins. "That's the place where symptoms—such as a sore throat and dry cough—often start."RELATED: Dr. Fauci Just Said When We'd Be Back to "Normal" 6 You Have Chills or Body Aches CNN news anchor Chris Cuomo says he was shivering so much due to COVID-19 that he "chipped a tooth." "They call them the rigors," he said, adding that he felt like he was being beaten by "a piñata."Researchers at New York University also discovered aching muscles (known as myalgia) are among the factors that could signal respiratory distress caused by the coronavirus. 7 You Are Fatigued "Some older or immunosuppressed individuals may not present with a fever, instead presenting with other common symptoms such as sore throat, dry cough, or fatigue," says Dr. LaFarra Young, a pathologist at King's Daughters Medical Center. "Fatigue is a daily lack of energy; unusual or excessive whole-body tiredness not relieved by sleep," reports WebMD. "Fatigue can prevent a person from functioning normally and affects a person's quality of life." 8 You Experience Shortness of Breath Can't get enough air in your lungs? "Extreme shortness of breath and respiratory issues are what is causing the increase in patients in the ICU. Increasing your immune system using Vitamin D can help decrease the likeliness of the spread of bacterial and viral infections," says Dr. Geoffrey Mount Varner.If you are struggling for air and can't breathe, seek immediate medical attention. 9 You Have Pain in Your Chest "Persistent pain or pressure in the chest" is one of the CDC's "emergency warning signs"—seek medical help immediately if you feel it. This could be a symptom of the coronavirus or a heart issue, and tests can help determine the right course of action.RELATED: Simple Ways to Avoid a Heart Attack, According to Doctors 10 You Have Pink Eye "Conjunctivitis, or more commonly known as pink eye, can present as a symptom of coronavirus," says Dr. Kevin Lee. "People should be cognizant of possible aerosol transmission with the conjunctiva and through ocular secretions, like tears." 11 You Have Diarrhea or Vomiting Diarrhea, vomiting, and stomach pain may be more common as a symptom of COVID-19 than anticipated, according to The American Journal of Gastroenterology. Half the patients that were diagnosed complained of those issues in the study. Some patients may not even have respiratory symptoms, and just digestive ones.RELATED: The New COVID Symptom Every Woman Needs to Know 12 You Have a Bluish Face or Lips This is considered one of the CDC's "emergency warning signs" and they advise you "get medical attention immediately" if you see them. Cyanosis is the name for poor oxygen circulation in the blood that causes bluish discoloration of the skin. 13 You Feel Confused Doctors have observed neurological symptoms, including confusion, stroke and seizures, in a subset of COVID-19 patients. If you are considered high risk, you may show rarer and more severe symptoms. The CDC considers "new confusion or inability to arouse" as an emergency warning sign. Do seek medical attention immediately if it sets in.If you or someone you know is experiencing any of these symptoms, call your medical care provider before showing up. And to get through this pandemic at your healthiest, don't miss these 35 Places You're Most Likely to Catch Coronavirus.
Phil Spector, who revolutionized 1960s pop music with his "Wall of Sound" technique but ended up in prison for murder, has died at age 81, authorities said Sunday.


MONSTA X went all out for their "DRAMARAMA" practice video!
In their choreography practice session above, the MONSTA X members show the same intensity as they did in their dramatic "DRAMARAMA" music video. The song is the title track of MONSTA X's 5th mini album 'The Code' and includes rap lyrics written by Jooheon and I.M.
Check out MONSTA X' dance practice video above!


Over the river and through the woods, to grandmother's house from hell.
Indie publisher Chance6 has launched Colina: Legacy, a third-person survival horror title that mixes exploration, psychological scares, and puzzle-solving. Chance6's first release, Colina crept onto Steam on September 13 for only $9.99.
COLINA casts players as Alex, who's woken up at his grandmother's house to find his family missing. To find them—or, more likely, to discover what horrible things happened to them—players must escape the house and its grounds by solving puzzles and avoiding creepy monsters such as a mannequin that gives chase in the game's launch trailer. You can check out the trailer below.
Just in time to join other horror titles for the upcoming Halloween season, COLINA is available on Steam for $9.99 and is compatible with Windows operating systems.


text:
Overnutrition Determines LPS Regulation of Mycotoxin Induced Neurotoxicity in Neurodegenerative Diseases
Chronic neurodegenerative diseases are now associated with obesity and diabetes and linked to the developing and developed world. Interests in healthy diets have escalated that may prevent neurodegenerative diseases such as Parkinson's and Alzheimer's disease. The global metabolic syndrome involves lipoprotein abnormalities and insulin resistance and is the major disorder for induction of neurological disease. The effects of bacterial lipopolysaccharides (LPS) on dyslipidemia and NAFLD indicate that the clearance and metabolism of fungal mycotoxins are linked to hypercholesterolemia and amyloid beta oligomers. LPS and mycotoxins are associated with membrane lipid disturbances with effects on cholesterol interacting proteins, lipoprotein metabolism, and membrane apo E/amyloid beta interactions relevant to hypercholesterolemia with close connections to neurological diseases. The influence of diet on mycotoxin metabolism has accelerated with the close association between mycotoxin contamination from agricultural products such as apple juice, grains, alcohol, and coffee. Cholesterol efflux in lipoproteins and membrane cholesterol are determined by LPS with involvement of mycotoxin on amyloid beta metabolism. Nutritional interventions such as diets low in fat/carbohydrate/cholesterol have become of interest with relevance to low absorption of lipophilic LPS and mycotoxin into lipoproteins with rapid metabolism of mycotoxin to the liver with the prevention of neurodegeneration.
7th World Gene Convention - Shanghai, China
Duration: 3 Nov 2016 → 5 Nov 2016
7th World Gene Convention
Overnutrition
Neurodegenerative Diseases
Fat-Restricted Diet
Apolipoproteins E
Dyslipidemias
Martins, I. (2016). Overnutrition Determines LPS Regulation of Mycotoxin Induced Neurotoxicity in Neurodegenerative Diseases. Abstract from 7th World Gene Convention, Shanghai, China.
Martins, Ian. / Overnutrition Determines LPS Regulation of Mycotoxin Induced Neurotoxicity in Neurodegenerative Diseases. Abstract from 7th World Gene Convention, Shanghai, China.
@conference{e4abeeffc83d4b30a6c10b328cc9acfe,
title = "Overnutrition Determines LPS Regulation of Mycotoxin Induced Neurotoxicity in Neurodegenerative Diseases",
abstract = "Chronic neurodegenerative diseases are now associated with obesity and diabetes and linked to the developing and developed world. Interests in healthy diets have escalated that may prevent neurodegenerative diseases such as Parkinson's and Alzheimer's disease. The global metabolic syndrome involves lipoprotein abnormalities and insulin resistance and is the major disorder for induction of neurological disease. The effects of bacterial lipopolysaccharides (LPS) on dyslipidemia and NAFLD indicate that the clearance and metabolism of fungal mycotoxins are linked to hypercholesterolemia and amyloid beta oligomers. LPS and mycotoxins are associated with membrane lipid disturbances with effects on cholesterol interacting proteins, lipoprotein metabolism, and membrane apo E/amyloid beta interactions relevant to hypercholesterolemia with close connections to neurological diseases. The influence of diet on mycotoxin metabolism has accelerated with the close association between mycotoxin contamination from agricultural products such as apple juice, grains, alcohol, and coffee. Cholesterol efflux in lipoproteins and membrane cholesterol are determined by LPS with involvement of mycotoxin on amyloid beta metabolism. Nutritional interventions such as diets low in fat/carbohydrate/cholesterol have become of interest with relevance to low absorption of lipophilic LPS and mycotoxin into lipoproteins with rapid metabolism of mycotoxin to the liver with the prevention of neurodegeneration.",
author = "Ian Martins",
note = "7th World Gene Convention ; Conference date: 03-11-2016 Through 05-11-2016",
Martins, I 2016, 'Overnutrition Determines LPS Regulation of Mycotoxin Induced Neurotoxicity in Neurodegenerative Diseases' 7th World Gene Convention, Shanghai, China, 3/11/16 - 5/11/16, .
Overnutrition Determines LPS Regulation of Mycotoxin Induced Neurotoxicity in Neurodegenerative Diseases. / Martins, Ian.
2016. Abstract from 7th World Gene Convention, Shanghai, China.
T1 - Overnutrition Determines LPS Regulation of Mycotoxin Induced Neurotoxicity in Neurodegenerative Diseases
AU - Martins, Ian
N2 - Chronic neurodegenerative diseases are now associated with obesity and diabetes and linked to the developing and developed world. Interests in healthy diets have escalated that may prevent neurodegenerative diseases such as Parkinson's and Alzheimer's disease. The global metabolic syndrome involves lipoprotein abnormalities and insulin resistance and is the major disorder for induction of neurological disease. The effects of bacterial lipopolysaccharides (LPS) on dyslipidemia and NAFLD indicate that the clearance and metabolism of fungal mycotoxins are linked to hypercholesterolemia and amyloid beta oligomers. LPS and mycotoxins are associated with membrane lipid disturbances with effects on cholesterol interacting proteins, lipoprotein metabolism, and membrane apo E/amyloid beta interactions relevant to hypercholesterolemia with close connections to neurological diseases. The influence of diet on mycotoxin metabolism has accelerated with the close association between mycotoxin contamination from agricultural products such as apple juice, grains, alcohol, and coffee. Cholesterol efflux in lipoproteins and membrane cholesterol are determined by LPS with involvement of mycotoxin on amyloid beta metabolism. Nutritional interventions such as diets low in fat/carbohydrate/cholesterol have become of interest with relevance to low absorption of lipophilic LPS and mycotoxin into lipoproteins with rapid metabolism of mycotoxin to the liver with the prevention of neurodegeneration.
AB - Chronic neurodegenerative diseases are now associated with obesity and diabetes and linked to the developing and developed world. Interests in healthy diets have escalated that may prevent neurodegenerative diseases such as Parkinson's and Alzheimer's disease. The global metabolic syndrome involves lipoprotein abnormalities and insulin resistance and is the major disorder for induction of neurological disease. The effects of bacterial lipopolysaccharides (LPS) on dyslipidemia and NAFLD indicate that the clearance and metabolism of fungal mycotoxins are linked to hypercholesterolemia and amyloid beta oligomers. LPS and mycotoxins are associated with membrane lipid disturbances with effects on cholesterol interacting proteins, lipoprotein metabolism, and membrane apo E/amyloid beta interactions relevant to hypercholesterolemia with close connections to neurological diseases. The influence of diet on mycotoxin metabolism has accelerated with the close association between mycotoxin contamination from agricultural products such as apple juice, grains, alcohol, and coffee. Cholesterol efflux in lipoproteins and membrane cholesterol are determined by LPS with involvement of mycotoxin on amyloid beta metabolism. Nutritional interventions such as diets low in fat/carbohydrate/cholesterol have become of interest with relevance to low absorption of lipophilic LPS and mycotoxin into lipoproteins with rapid metabolism of mycotoxin to the liver with the prevention of neurodegeneration.
Martins I. Overnutrition Determines LPS Regulation of Mycotoxin Induced Neurotoxicity in Neurodegenerative Diseases. 2016. Abstract from 7th World Gene Convention, Shanghai, China.


text:
Arseni Corsellas Serra (Figueres, 17 de setembre de 1933 – Madrid, 16 de novembre de 2019) va ser un actor i doblador català. Va començar la seva carrera en el doblatge a mitjans dels anys seixanta. Alguns dels actors als quals va posar veu foren Sean Connery, Charlton Heston, Michael Caine, Kirk Douglas, Robert Duvall, Omar Sharif i Jack Nicholson, entre d'altres. Un dels doblatges més famosos en català va ser la veu de J.R. a Dallas.

En els anys cinquanta va començar a treballar a Ràdio Joventut de Barcelona i posteriorment a Radio Nacional de España a Barcelona com a actor del Teatro Invisible sota la direcció de Juan Manuel Soriano. A mitjans dels anys seixanta va orientar la seva carrera professional al doblatge cinematogràfic, en els seus inicis va doblar els actors Richard Burton, Stanley Baker o Humphrey Bogart (al segon doblatge de Casablanca).

El 1983 va ser un dels primers a doblar en català quan Televisió de Catalunya comença les emissions. El personatge de J.R., de la sèrie de televisió Dallas, interpretat per l'actor Larry Hagman, fou un dels que va doblar. Durant els anys seixanta i setanta va ser el director de doblatge de gairebé totes les pel·lícules que es varen doblar als estudis Voz de España a Barcelona.

Ha treballat com a actor a les pel·lícules Lo mejor que le puede pasar a un cruasán de Paco Mir i Amor propio de Mario Camus. El 1986 el varen distingir amb l'Atril d'or de doblatge. Posteriorment, va rebre el premi de l'Associació de Veterans de RNE, i el 2019, el premi Take Daurat.

Referències

Enllaços externs
 Relació de pel·lícules doblades per Arseni Corsellas

Actors de doblatge catalans del sud
Actors de cinema catalans del sud
Actors de teatre altempordanesos
Actors figuerencs
Morts a Madrid
Directors de doblatge


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IPO Reports
IPO Fact Sheets
IPO Tracker
IPO & RTO Tracker, 2017: April Performance
Rene Anthony April 28, 2017 No Comments
In a quieter month for new ASX listings, only 7 IPOs listed in April. Of note, only 2 of the IPOs managed to deliver a positive return to shareholders throughout the month, while 4 IPOs traded down on their first day of trading.
Making up the debutants were 2 resources stocks (TRT, E2M), as well as individual plays in the following sectors – utilities (DEM); financials (MOE); LICs (URB); IT (TNY); industrials (UUV).
The clear standout for the month was De.Mem, which ended April 100% higher. During the month, the waste water treatment company announced a new contract for a water treatment feasibility study from a Vietnamese residential developer. The business also informed shareholders as to its strategy, contracts, projects, and a new management appointment in a wide-ranging market update.
Among the year's existing IPOs, most activity was 'modest' when taking account of each company's market cap. Floats traded within a band of -33% to +33% for the month.
In the case of the former, AC8 slipped 33% during April to 59.5c. This follows 2 months where its share price surged over fourfold.
With regards to positive movers for the month, SKN rose 33%. This came as the skin care company appointed an Australian Head of Sales, provided a sales and operations update, and also announced an acquisition of McArthur Skincare.
Stay tuned for next month's report. In the meantime, to stay informed on all the latest IPO news, follow us on Twitter.
ASX Code
Issue Price
Price End Day 1
Price End Day 1 %
% Difference
Bubs Australia RTO BUB 3/01/2017 $0.10 $0.135 35% $0.145 45%
Winha Commerce & Trade International IPO WQW 5/01/2017 $0.35 $0.49 40% $0.49 40%
Asset Owl RTO AO1 6/01/2017 $0.20 $0.165 -17.5% $0.24 20%
Skin Elements IPO SKN 6/01/2017 $0.20 $0.20 0% $0.18 -10%
Lifespot Health IPO LSH 11/01/2017 $0.20 $0.40 100% $0.295 47.5%
United Networks IPO UNL 12/01/2017 $0.20 $0.26 30% $0.14 -30%
Zenitas Health RTO ZNT 13/01/2017 $1.00 $0.90 -10% $1.01 1%
Freehill Mining IPO FHS 16/01/2017 $0.20 $0.15 -25% $0.105 -47.5%
Kalamazoo Resources IPO KZR 16/01/2017 $0.20 $0.21 5% $0.135 -32.5%
Thorney Technologies RTO TEK 18/01/2017 $0.20 $0.23 15% $0.225 12.5%
Davenport Resources IPO DAV 20/01/2017 $0.20 $0.195 -2.5% $0.11 -45%
Blackstone Minerals IPO BSX 23/01/2017 $0.20 $0.205 2.5% $0.185 -7.5%
Murray Cod Australia RTO MCA 31/01/2017 $0.05 $0.058 16% $0.064 28%
Cobalt Blue IPO COB 2/02/2017 $0.20 $0.22 10% $0.245 22.5%
Auscann Group RTO AC8 3/02/2017 $0.20 $0.22 10% $0.595 197.5%
Velocity Property Group IPO VP7 7/02/2017 $0.20 $0.205 2.5% $0.18 -10%
Ardea Resources IPO ARL 9/02/2017 $0.20 $0.18 -10% $0.62 210%
Roto-Gro International IPO RGI 10/02/2017 $0.20 $0.215 7.5% $0.32 60%
eSense-Lab IPO ESE 14/02/2017 $0.20 $0.255 27.5% $0.355 77.5%
Sportshero RTO SHO 15/02/2017 $0.05 $0.055 10% $0.04 -20%
MetalsTech IPO MTC 24/02/2017 $0.20 $0.27 35% $0.255 27.5%
Switzer Divident Growth Fund IPO SWTZ 24/02/2017 $2.50 $2.51 0.4% $2.58 3.2%
Dawine RTO DW8 28/02/2017 $0.02 $0.029 45% $0.02 0%
Eildon Capital IPO EDC 28/02/2017 $1.06 $1.08 1.89% $1.075 1.42%
Tianmei Beverage Group IPO TB8 28/02/2017 $0.20 $0.235 17.5% $0.12 -40%
Matador Mining IPO MZZ 8/03/2017 $0.20 $0.26 30% $0.265 32.5%
Quantify Technology RTO QFY 8/03/2017 $0.06 $0.076 26.67% $0.086 43.33%
JiaJiafu Modern Agriculture IPO JJF 9/03/2017 $0.30 $0.26 -13.33% $0.25 -16.67%
Marquee Resources IPO MQR 15/03/2017 $0.20 $0.22 10% $0.215 7.5%
Wattle Health Australia IPO WHA 15/03/2017 $0.20 $0.20 0% $0.355 77.5%
ServTech Global Holdings IPO SVT 17/03/2017 $0.20 $0.21 5% $0.15 -25%
Fat Prophets Global Contrarian Fund IPO FPC 22/03/2017 $1.10 $1.135 3.18% $1.18 7.27%
Bigtincan Holdings IPO BTH 24/03/2017 $0.26 $0.24 -7.69% $0.225 -13.46%
Lithium Consolidated Mineral Exploration IPO LI3 28/03/2017 $0.20 $0.18 -10% $0.165 -17.5%
Visioneering Technologies IPO VTI 28/03/2017 $0.42 $0.445 5.95% $0.415 -1.19%
I Synergy Group IPO IS3 30/03/2017 $0.20 $0.197 -1.5% $0.19 -5%
Todd River Resources IPO TRT 6/04/2017 $0.20 $0.23 15% $0.185 -7.5%
De. Mem IPO DEM 7/04/2017 $0.20 $0.45 125% $0.40 100%
Moelis IPO MOE 10/04/2017 $2.35 $3.15 34.04% $3.19 35.74%
URB Investments IPO URB 12/04/2017 $1.10 $1.09 -0.91% $1.08 -1.82%
E2 Metals IPO E2M 19/04/2017 $0.20 $0.155 -22.5% $0.15 -25%
Tinybeans Group IPO TNY 21/04/2017 $1.00 $0.95 -5% $0.90 -10%
Aquabotix IPO UUV 28/04/2017 $0.20 $0.195 -2.5% $0.195 -2.5%
To receive invitations to participate in upcoming IPO opportunities, become a member here.
The team at
IPO Society
The information contained on this website in no way reflects the opinions of IPO Society. It is provided for informational services only. It does not constitute an offer to sell or a solicitation to buy any security or other financial instrument. The information is general in nature and does not take into account your personal situation. You should consider whether the information is appropriate to your needs, and where appropriate, seek professional advice from a financial adviser. Detailed information may be needed to make an investment decision, for example: financial statements; a business plan; information about ownership of intellectual or industrial property; or expert opinions including valuations or auditors' reports. The information contained on this website is not intended to be the only information on which an investment decision is made and is not a substitute for a disclosure document, product disclosure statement or any other notice that may be required under the Act, as the Act may apply to the investment.
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You know how the cutscenes in the LEGO Star Wars games are funnier and more charming than the actual movies they're based on (especially the prequels)? Here's one long LEGO Star Wars cutscene, re-telling the story of episodes IV-VI.
It's been made by Danish production firm M2FILM, and is the latest in their series of shorts for LEGO (the toys, not the game) that have been coming out since last year.
I know, it stars he who shall not be named, but it's testament to M2FILM's talents (and the inherent adorability of LEGO Star Wars) that it's still a great watch regardless.


Tempo Alegre is a premier Latin music band dedicated to bringing some real energy to your next event! Over the past 15 years, they have performed at just about every type of event including weddings, sweet 16 or other birthday celebrations, galas, corporate and cultural events, festivals, nightclubs…etc. They are experienced and dedicated musicians, and just as important, musicians who love music. Book Tempo Alegre today for a feel good time that will leave your audience wanting more!