text:
The BJOC
Bi- and trinuclear copper(I) complexes of 1,2,3-triazole-tethered NHC ligands: synthesis, structure, and catalytic properties
Shaojin Gu1,
Jiehao Du1,
Jingjing Huang1,
Huan Xia1,2,
Ling Yang1,
Weilin Xu1 and
Chunxin Lu2
Shaojin Gu
School of Materials Science and Engineering, Wuhan Textile University, Wuhan 430200, People's Republic of China
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Jiehao Du
Jingjing Huang
Huan Xia
College of Biological, Chemical Sciences and Engineering, Jiaxing University, Jiaxing 314001, People's Republic of China
Ling Yang
Chunxin Lu
1School of Materials Science and Engineering, Wuhan Textile University, Wuhan 430200, People's Republic of China
2College of Biological, Chemical Sciences and Engineering, Jiaxing University, Jiaxing 314001, People's Republic of China
Corresponding author email
Associate Editor: I. Marek
Beilstein J. Org. Chem. 2016, 12, 863–873. doi:10.3762/bjoc.12.85
Received 12 Jan 2016, Accepted 10 Apr 2016, Published 03 May 2016
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A series of copper complexes (3–6) stabilized by 1,2,3-triazole-tethered N-heterocyclic carbene ligands have been prepared via simple reaction of imidazolium salts with copper powder in good yields. The structures of bi- and trinuclear copper complexes were fully characterized by NMR, elemental analysis (EA), and X-ray crystallography. In particular, [Cu2(L2)2](PF6)2 (3) and [Cu2(L3)2](PF6)2 (4) were dinuclear copper complexes. Complexes [Cu3(L4)2](PF6)3 (5) and [Cu3(L5)2](PF6)3 (6) consist of a triangular Cu3 core. These structures vary depending on the imidazolium backbone and N substituents. The copper–NHC complexes tested are highly active for the Cu-catalyzed azide–alkyne cycloaddition (CuAAC) reaction in an air atmosphere at room temperature in a CH3CN solution. Complex 4 is the most efficient catalyst among these polynuclear complexes in an air atmosphere at room temperature.
Keywords: copper; CuAAC reaction; : N-heterocylic carbene; 1,2,3-triazole
Graphical Abstract
N-Heterocyclic carbene (NHC) have interesting electronic and structural properties. This resulted in their use as versatile ligands in organometallic chemistry and homogeneous catalysis [1-12]. A number of transition metal complexes of NHCs containing pyridine [13], pyrimidine [14], pyrazole [15,16], naphthyridine [17], pyridazine [18], and phenanthroline [19,20] donating groups have been studied in metal-catalyzed organic transformations. Recently, the easy synthesis and versatile coordination ability of 1,2,3-triazoles have led to an explosion of interest in coordination chemistry [21] and homogeneous catalysis [22-26]. Although a number of metal complexes containing 1,4-disubstituted-1,2,3-triazole ligands were well studied, reports concerning their preparation and use of 1,4-disubstituted-1,2,3-triazoles bearing NHC ligands are rare [22,23]. Elsevier et al. [23] reported several of palladium(II) complexes containing a heterobidentate N-heterocyclic carbene-triazolyl ligand. These palladium(II) complexes are active precatalysts in the transfer semihydrogenation of alkynes to Z-alkenes. Messerle et al. [26] synthesized a series of new cationic Rh(I), Rh(III) and Ir(III) complexes containing hybrid bidentate N-heterocyclic carbene-1,2,3-triazolyl donors. We [27] have synthesized a series of nonsymmetrical pincer palladium and platinum complexes containing 1,2,3-triazole-tethered NHC ligands. The obtained palladium complexes displayed high activity in aqueous Suzuki–Miyaura cross-coupling reactions.
We are interested in the synthesis and use of functionalized NHC ligands [20,28-31]. Herein, the synthesis, structural characterization, and catalytic properties of a few copper-1,2,3-triazole-tethered NHC complexes is reported.
Synthesis and spectroscopic characterization
The imidazolium salts (1a–e) were prepared according to the reported procedure in 61–90% yields [27]. These imidazolium salts have been characterized by NMR spectroscopy. The 1H NMR spectra of these imidazolium salts show singlet peaks between 10.04 and 10.89 ppm in DMSO-d6. As seen in Scheme 1, copper–NHC complexes 3–6 can be obtained in 52–90% yields via directly reacting the corresponding imidazolium salts with an excess of copper powder in CH3CN at 50 °C for 5 h.
As shown in Scheme 1, reactions of the pyrimidine imidazolium salt 1a with copper powder in acetonitrile afforded a light yellow Cu(II) complex. In complex 2, the carbenic carbon atom was oxidized into carbonyl, which is similar with the reported pyrimidyl-imidazole complex [32]. However, a red binuclear Cu(I) complex 3 was obtained in 57% yield when we reacted pyrimidyl benzimidazolium salt 1b with copper powder. Furtherly, we got a yellow Cu(I)–NHC complex 4 in about 70% yield from pyridine imidazolium salt 1c and copper powder (Scheme 1). In addition, a triangular Cu(I) complex 6 can be obtained when a flexible ligand was used. Complex 6 consists of a triangular Cu3 core bridged by three NHCs, which is similar with the published Cu3 complexes containing flexible ligands [33]. Interestingly, we can also obtain a similar triangular Cu3 complex 5 rather than a binuclear copper complex using a rigid pyridine benzimidazolium salt 1d. These results demonstrated that the structures vary depending on the N substituents and on the imidazolium backbone. Fine adjustment of the structure of the ligand can lead to different structures.
Scheme 1: Synthesis of copper complexes 2–6.
Jump to Scheme 1
All of the prepared copper–NHC complexes are stable in air. They were fully characterized by NMR, elemental analysis (EA), and X-ray crystallography. The generation of these copper–NHC complexes were confirmed by the absence of the 1H NMR resonance signal of the acidic imidazolium protons between 10.04 and 10.89 ppm. The 1H NMR spectra of all the complexes display only one set of resonance signals assignable to the corresponding ligands, indicating two or three magnetically equivalent ligands. 13C NMR spectra of the copper(I) complexes showed their carbenic carbon resonances at 177.6–191.2 ppm, which are in the normal range of 157.6–216 ppm [34,35].
Single crystal X-ray diffraction studies
To obtain additional insight into the coordination and supramolecular properties, suitable single crystals of all the copper complexes were obtained for single-crystal X-ray diffraction analysis. Crystals were grown by slow diffusion of diethyl ether into an acetonitrile solution of the copper complex at room temperature.
Green-yellow single crystals of complex 2 suitable for an X-ray diffraction study were grown from acetonitrile solution and diethyl ether. The molecular structure of complex 2 in the solid state is depicted in Figure 1 along with the principal bond lengths and angles. Complex 2 crystallizes in the orthorhombic space group Pnna. The remaining atoms of the cation are related by a crystallographic 2-fold symmetry. In complex 2, the copper ion is four-coordinate in a distorted square planar ligand environment of two nitrogen atoms and two oxyen atoms. The Cu–O bonds are in trans configuration and Cu–O distances are shorter than Cu–N distances. The two ligands are arranged in head-to-tail manner. And the Ntriazole did not participate in the corrdination.
Figure 1: X-ray diffraction structure of copper(II) complex 2 with thermal ellipsoids drawn at 30% probability. The anion and hydrogen atoms are omitted for clarity. Selected bond distances (Å) and angles (°): Cu1-O1 1.931(4), Cu1-N6 2.042(5); O1-Cu1-O1A 180.0(3), O1-Cu1-N6A 90.5(2), O1-Cu1-N6 89.5(2), N6-Cu1-N6A 180.00(8). Symmetry transformations used to generate equivalent atoms: −X, Y, 0.5−Z.
Figure 1: X-ray diffraction structure of copper(II) complex 2 with thermal ellipsoids drawn at 30% probabilit...
Single crystals of complex 3 suitable for an X-ray diffraction study were grown from acetonitrile solution and diethyl ether. The molecular structure of complex 3 is depicted in Figure 2. Complex 3 crystallizes in the monoclinic space group C2/c. The Cu(I) complex contains two crystallographically equivalent Cu centers, which are doubly bridged by two L2 ligands. The two ligands are arranged in head-to-tail manner. The copper ions are each tri-coordinated by one carbene carbon atom, one nitrogen from pyrimidine, and one nitrogen atom of the triazole rings from two different L2 ligands. The Cu–carbene bond distances are 1.896(6) and 1.899(5) Å, which are comparable to the known Cu(I)–NHC complexes [36-39]. The Cu1–Cu2 separation is 2.7867(7) Å, showing a weak metal−metal interaction.
Figure 2: ORTEP the cationic section of [Cu2(L2)2](PF6)2 (3). Thermal ellipsoids are drawn at the 30% probability level. Hydrogen atoms and anions have been removed for clarity. Selected bond distances (Å) and angles (°): Cu2-C5 1.896(3), Cu2-N14 1.911(3), Cu2-N1 2.362(3), Cu2-Cu1 2.7867(7), Cu1-C26 1.898(3), Cu1-N7 1.915(3), Cu1-N8 2.340(3); C5-Cu2-N14 173.37(13), C5-Cu2-N1 77.64(13), N14-Cu2-N1 108.15(12), C5-Cu2-Cu1 69.80(9), N14-Cu2-Cu1 111.70(8), N1-Cu2-Cu1 98.90(7), C26-Cu1-N7 167.08(15), C26-Cu1-N8 78.22(13), N7-Cu1-N8 111.77(13), C26-Cu1-Cu2 73.57(9).
Figure 2: ORTEP the cationic section of [Cu2(L2)2](PF6)2 (3). Thermal ellipsoids are drawn at the 30% probabi...
The molecular structure of complex 4 is depicted in Figure 3. Complex 4 consists of the cation unit [Cu2(L3)2]2+ and two hexafluorophosphate anions. Complex 4 crystallizes in the triclinic space group P-1. The two ligands are also arranged in head-to-tail manner. Each copper ion is three-coordinate in a trigonal planar ligand environment of two nitrogen atoms and one NHC carbon center. The Cu–carbene bond distances are 1.888(6) and 1.899(5) Å which are similar with reported copper-carbene complexes (1.85–2.18 Å) [40]. The Cu1–Cu2 separation is 2.6413(12) Å is shorter than in complex 3, and slightly higher than reported Cu–Cu separations (2.4907 to 2.5150 Å) of the triangular Cu(I)–NHC clusters [33], showing a weak metal–metal interaction.
Figure 3: ORTEP drawing of [Cu2(L3)2](PF6)2 (4). Thermal ellipsoids are drawn at the 30% probability level. Hydrogen atoms and anions have been removed for clarity. Selected bond distances (Å) and angles (°): Cu1-C26 1.888(6), Cu1-N5 1.912(5), Cu1-N7 2.289(5), Cu1-Cu2 2.6413(12), Cu2-C8 1.899(5), Cu2-N11 1.922(4), Cu2-N1 2.311(5); C26-Cu1-N5 159.2(2), C26-Cu1-N7 79.0(2), N5-Cu1-N7 116.65(19), C26-Cu1-Cu2 72.49(17), N5-Cu1-Cu2 113.20(15), N7-Cu1-Cu2 105.13(12), C8-Cu2-N11 166.1(2), C8-Cu2-N1 78.6(2), N11-Cu2-N1 110.5(2), C8-Cu2-Cu1 70.45(16), N11-Cu2-Cu1-116.14(15), N1- Cu2-Cu1 102.03(13).
Figure 3: ORTEP drawing of [Cu2(L3)2](PF6)2 (4). Thermal ellipsoids are drawn at the 30% probability level. H...
Complex 5 was also characterized via X-ray diffraction. It's structure is shown in Figure 4. Complex 5 consists of two independent molecules in the unit cell. Here, only one molecule was given in Figure 4. The molecule structure consists of a triangular Cu3 core bridged by three NHCs ligands. Each NHC forms the 3c-2e bond with two Cu(I) ions with almost equal bond distances (average 2.085 Å), longer than normal Cu–NHC bonds and reported triangular Cu3 complexes [33,41]. The Cu3 cores of complex 5 possess nearly equilateral angles close to 60°, whereas in complex 6, the core is crystallographically restrained to an equilateral triangle. The Cu–Cu distances are around 2.4887 Å and are shorten than that of complexe 6, which may be attributed to more rigid ligand.
Figure 4: ORTEP drawing of [Cu3(L4)3](PF6)3 (5). Thermal ellipsoids are drawn at the 30% probability level. Hydrogen atoms and anions have been removed for clarity. Selected bond distances (Å) and angles (°): Cu2-N17 2.015(5), Cu2-C50 2.074(6), Cu2-N19 2.107(6), Cu2-C72 2.142(6), Cu2-Cu4 2.4899(11), Cu2-Cu3 2.4928(11), Cu3-N11 2.038(5), Cu3-C27 2.069(6), Cu3-C50 2.113(6), Cu3-N13 2.133(5), Cu3-Cu4 2.4833(10), Cu4-N22 2.043(5), Cu4-C72 2.044(7), Cu4-C27 2.071(6), Cu4-N7 2.086(6); N17-Cu2-C50 94.8(2), N17-Cu2-N19 112.1(2), C50-Cu2-N19 106.8(2), N17-Cu2-C72 93.5(2), C50- Cu2-C72 165.4(2), N19-Cu2-C72 81.0(2), N17-Cu2-Cu4 125.46(18), C50-Cu2-Cu4 113.86(16), N19-Cu2-Cu4 102.90(19), C72-Cu2-Cu4 51.72(17), N17-Cu2-Cu3 129.13(16), C50-Cu2-Cu3 54.18(16), N19-Cu2-Cu3 115.04(17), C72-Cu2-Cu3 111.50(17), Cu4-Cu2-Cu3 59.79(3), N11-Cu3-C27 94.1(2), N11-Cu3-C50 90.9(2), C27-Cu3-C50 163.7(2), N11-Cu3-N13 112.2(2), C27-Cu3-N13 112.1(2), C50-Cu3-N13 80.1(2), N11-Cu3-Cu4 131.09(16), C27-Cu3-Cu4 53.18(17), C50-Cu3-Cu4 112.70(16), N13-Cu3-Cu4 113.70(15), N11-Cu3-Cu2 128.00(15), C27-Cu3-Cu2 112.99(17), C50-Cu3-Cu2 52.76(16), N13-Cu3-Cu2 97.90(16), Cu4-Cu3-Cu2 60.05(3), N22-Cu4-C72 94.4(2), N22-Cu4-C27 92.5(2), C72-Cu4-C27 167.8(2), N22 -Cu4-N7 99.9(2), C72-Cu4-N7 107.5(2), C27-Cu4-N7 81.1(2), N22-Cu4-Cu3 134.20(17), C72-Cu4-Cu3 115.49(17), C27-Cu4-Cu3 53.10(17), N7-Cu4-Cu3 102.67(18), N22-Cu4-Cu2 134.48(17), C72-Cu4-Cu2 55.33(17), C27-Cu4-Cu2 113.02(17), N7-Cu4 -Cu2 120.11(16), Cu3- Cu4- Cu2 60.16(3).
Complex 6 has also been characterized by single crystal X-ray diffraction (Figure 5). Complex 6 crystallizes in the hexagonal space group R3c, which is different to the reported trinuclear copper(I) complex containing the symmetric 1,3-bis(2-pyridinylmethyl)benzimidazolylidene ligand (monoclinic, P21/c) [33] and to the trinuclear copper(I) complex containing a symmetric 1,3-bis(triazole)benzimidazolylidene ligand (monoclinic, C2/c) [38]. Three copper atoms are bridged by three NpyridineCNtriazole NHC ligands forming a Cu3 ring with three Cu–Cu–Cu angles of 60.0. The geometry of the copper center can be described as distorted trigonal planar. Each copper ion is coordinated by one pyridine, one triazole, and two benzimidazolylidene ligands displaying a distorted tetrahedral geometry. The Cu–Cu distance is around 2.5145(12) Å showing a weak metal–metal interaction, which is similar with the reported triangle Cu(I) complexes and is shorter than in complexes 3 and 4. The Cu–N and Cu–C bond distances fall in the range of 2.092(5)–2.152(5) Å and 2.024(6)–2.092(6) Å, respectively, which are slightly longer than in dinuclear complexes 3 and 4. Benzimidazolylidene acts as a bridging ligand in a u2 mode and bonded equally to two Cu(I) ions, which is only observed in a few silver(I) and copper(I) complexes.
Figure 5: ORTEP drawing of [Cu3(L5)3](PF6)3 (6). Thermal ellipsoids are drawn at the 30% probability level. Hydrogen atoms and anions have been removed for clarity. Selected bond distances (Å) and angles (°): Cu1-C26 2.092(6), Cu1-N5 2.092(5) , Cu1-C26A 2.024(6), Cu1- N9A 2. 152(5), Cu1-Cu1A 2.5141(11), Cu1-Cu1B 2.5141(11); C26-Cu1-N5 101.8(2), C26-Cu1-C26A 163.7(2), N5-Cu1-C26 92.5(2), C26A-Cu1-N9 92.0(2), Cu1-Cu1A-Cu1B 60.0. Symmetry transformations used to generate equivalent atoms: 1−x, 1−y, −z.
Catalytic application in CuAAC reactions
Inspired by the catalytic activity of Cu(I) species supported by NHC ligand in Cu-catalyzed azide–alkyne cycloaddition (CuAAC) reaction under mild conditions, copper complexes 2–6 were investigated in the CuAAC reaction of azide and phenylacetylene. Firstly, we compared the catalytic activity of different complexes with a complex loading of 0.5 mol %. The reactions were monitored by 1H NMR analysis at different time points within 4 h (Figure 6). As seen in Figure 6, the yield increased with the extension of reaction time. The results showed that complex 4 displays the best activities for the CuAAC reaction of benzyl azide and phenylacetylene giving a conversion of 95%. To further examine the catalytic efficiency of complex 4, a variation of the catalyst loading from 0.1 to 0.25 to 0.5 mol % within 5 h was performed to give the expected product in yields of 17%, 48%, and 100%. As expected, the coupling reaction with low catalyst loading results in incomplete conversion.
Figure 6: Yield vs reaction time of different copper complex. The reaction was carried out in acetonitrile-d3 at 25 °C using 0.5 mol % copper complex, yields were determined by 1H NMR spectra, hexamethylbenzene was used as internal standard.
Figure 6: Yield vs reaction time of different copper complex. The reaction was carried out in acetonitrile-d3...
Subsequently the catalytic activity of different solvents was tested at a Cu loading of 0.5 mol % (Table 1). Moderate catalytic activities were obtained for DMSO or without solvent. When CH3CN was used, the reaction gave an excellent yield (Table 1, entry 4). However, only a moderate yield was obtained when a CH3CN/H2O solvent mixture was used (Table 1, entry 6). Thus, CH3CN was selected as the optimal solvent.
Table 1: CuAAC reaction with different solventsa.
yield %b
1 neat 4 50
2 H2O 4 22
3 DMSO 4 53
4 CH3CN 4 95
5 t-BuOH/H2O (1:1) 4 trace
6 CH3CN/H2O (1:1) 4 59
aReaction carried out using 0.5 mol % of complex 4 with different solvents. bYields were determined by 1H NMR spectra and are reported after 4 h, hexamethylbenzene was used as internal standard.
Having optimized the reaction conditions, we extended the CuAAC reaction to other azides and alkynes at room temperature in CH3CN. As shown in Table 2 (entries 1–5), (azidomethyl)benzene, azidobenzene, (2-azidoethyl)benzene, and 2-(azidomethyl)pyridine could react with phenylacetylene in more than 83% yield (Table 2, entries 1–4). What is more, methyl 1-benzyl-1H-1,2,3-triazole-4-carboxylate could be afforded in 85% yield via reacting methyl propiolate with (azidomethyl)benzene. This promising catalytic behavior of complex 4 prompted us to extend our studies toward a one-pot synthesis of 1,2,3-triazoles from alkyl halides, sodium azide, and alkynes. The three-component version has already been successfully performed and described in previous work [20]. As displayed in Table 2, the reactions proceeded smoothly to completion, and the products were isolated in good to excellent yields (83–95%).
Table 2: CuAAC Reaction using complex 4 as catalyst.
isolated yield %
1a 94 [42]
6b 90 [42]
aReaction conditions: azide 0.5 mmol, ethynylbenzene 0.6 mmol, catalyst 0.5 mol %, CH3CN 3 mL, rt, 6 h. bReaction conditions: alkyl halide 0.5 mmol, NaN3 0.6 mmol, ethynylbenzene 0.6 mmol, catalyst 0.5 mol %, CH3CN/H2O 1:1 (3 mL), rt, 16 h.
In summary, a series of di-, and trinuclear copper(I) complexes (3–6) stablized by 1,2,3-triazole-tethered N-heterocyclic carbene ligands have been prepared via simple reactions of imidazolium salts with copper powder in good yields. These complexes have been fully characterized by NMR, elemental analysis (EA) and X-ray crystallography. Fine adjustment of the structure of the ligand can lead to different structures. All the Cu–NHC complexes showed high catalyst activity in CuAAC reactions at room temperature. Among these complexes, complex 4 is the most efficient catalyst in an air atmosphere at room temperature.
All the chemicals were obtained from commercial suppliers and were used without further purification. Elemental analyses were performed on a Flash EA1112 instrument. 1H and 13C NMR spectra were recorded on a Bruker Avance-400 (400 MHz) spectrometer or a Varian 600 MHz NMR spectrometer. Chemical shifts (δ) are expressed in ppm downfield to TMS at δ = 0 ppm and coupling constants (J) are expressed in Hz.
Synthesis of 3-((1-benzyl-1H-1,2,3-triazol-4-yl)methyl)-1-(pyrimidin-2-yl)-1H-benzo[d]imidazol-3-ium hexafluorophosphate [(HL2)PF6] (1b): Analogously as described in a published work [27], (azidomethyl)benzene (160 mg, 1.2 mmol), copper sulfate pentahydrate (12.5 mg, 0.05 mmol), sodium ascorbate (20 mg, 0.1 mmol), and 3-(prop-2-yn-1-yl)-1-(pyrimidin-2-yl)-1H-benzo[d]imidazol-3-ium bromide (314 mg, 1 mmol) were added to a Schlenk tube containing 2 mL of water and tert-butyl alcohol (1:1). After the heterogeneous mixture was stirred vigorously for 24 h at 50 °C, the reaction mixture was diluted with water (20 mL). The obtained yellow solution was dropwise added to the aqueous solution of NH4PF6. A white precipitate was collected by filtration and dried. Yield: 315 mg, 61%. 1H NMR (400 MHz, DMSO-d6) δ 10.89 (s, 1H), 9.14 (d, J = 4.9 Hz, 2H), 8.83 (d, J = 8.1 Hz, 1H), 8.39 (s, 1H), 8.17 (d, J = 8.0 Hz, 1H), 7.79 (br, 3H), 7.34–7.30 (m, 5H), 6.06 (s, 2H), 5.63 (s, 2H); 13C NMR (101 MHz, DMSO-d6) δ 160.34, 159.78, 143.41, 140.45, 136.12, 132.14, 129.62, 129.26, 128.69, 128.49, 127.79, 125.52, 53.47, 42.95.
Synthesis of 3-((1-benzyl-1H-1,2,3-triazol-4-yl)methyl)-1-(pyridin-2-yl)-1H-imidazol-3-ium hexafluorophosphate [(HL3)PF6] (1c): Similarly as described in a previous procedure [27], a mixture of (azidomethyl)benzene (160 mg, 1.2 mmol), copper sulfate pentahydrate (12.5 mg, 0.05 mmol) and sodium ascorbate (20 mg, 0.1 mmol), 3-(prop-2-ynyl)-1-(pyridin-2-yl)-1H-imidazol-3-ium bromide (265 mg, 1 mmol) was added to 2 mL of water and tert-butyl alcohol (1:1). The heterogeneous mixture was stirred vigorously for 24 h at 50 °C. The reaction mixture was diluted with water (20 mL), and the yellow solution was dropwise added to the aqueous solution of NH4PF6. A white precipitate was collected by filtration and dried. Yield: 415 mg, 90%. 1H NMR (400 MHz, DMSO-d6) δ 10.19 (s, 1H), 8.69–8.63 (m, 1H), 8.54 (t, J = 1.9 Hz, 1H), 8.35 (d, J = 2.4 Hz, 1H), 8.31–8.17 (m, 1H), 8.03 (q, J = 4.3, 3.5 Hz, 2H), 7.70–7.61 (m, 1H), 7.36 (qd, J = 7.0, 6.5, 2.5 Hz, 5H), 5.65 (dd, J = 5.1, 2.4 Hz, 4H), 3.39 (s, 1H); 13C NMR (101 MHz, DMSO-d6) δ 149.69, 146.78, 141.06, 141.02, 135.68, 129.29, 128.76, 128.55, 125.77, 125.23, 124.14, 120.07, 114.75, 53.49, 44.85.
Synthesis of 3-((1-benzyl-1H-1,2,3-triazol-4-yl)methyl)-1-(pyridin-2-yl)-1H-benzo[d]imidazol-3-ium hexafluorophosphate [(HL4)PF6] (1d): Similarly as described in a previous procedure [27], the imidazolium salt was prepared similarly as for [(HL3)PF6] from (azidomethyl)benzene (160 mg, 1.2 mmol), copper sulfate pentahydrate (12.5 mg, 0.05 mmol), sodium ascorbate (20 mg, 0.1 mmol), and 3-(prop-2-yn-1-yl)-1-(pyridin-2-yl)-1H-benzo[d]imidazol-3-ium bromide (314 mg, 1 mmol). Yield: 317 mg, 62%. 1H NMR (400 MHz, DMSO-d6) δ 10.60 (s, 1H), 8.75 (d, J = 4.7 Hz, 1H), 8.46–8.31 (m, 2H), 8.25 (t, J = 8.0 Hz, 1H), 8.19–8.10 (m, 1H), 8.02 (d, J = 8.2 Hz, 1H), 7.79–7.65 (m, 3H), 7.31 (dt, J = 21.5, 7.4 Hz, 7H), 5.95 (s, 2H), 5.59 (d, J = 5.1 Hz, 2H); 13C NMR (101 MHz, DMSO-d6) δ 149.97, 147.61, 143.07, 141.07, 140.46, 136.13, 131.72, 130.09, 129.27, 128.74, 128.50, 128.30, 127.73, 125.73, 125.50, 117.68, 116.38, 114.80, 53.42, 42.83.
Synthesis of 3-((1-benzyl-1H-1,2,3-triazol-4-yl)methyl)-1-(pyridin-2-ylmethyl)-1H-benzo[d]imidazol-3-ium hexafluorophosphate [(HL5)PF6] (1e): Similarly as described in previous procedure [27], the imidazolium salt was prepared similarly as for [(HL3)PF6] from (azidomethyl)benzene (160 mg, 1.2 mmol), and 3-(prop-2-yn-1-yl)-1-(pyridin-2-ylmethyl)-1H-benzo[d]imidazol-3-ium bromide (328 g, 1 mmol). Yield: 390 mg, 74%.1H NMR (400 MHz, DMSO-d6) δ 10.04 (s, 1H, NCHN), 8.46 (d, J = 4.8 Hz, 1H, 2-Py), 8.39 (s, 1H, triazole), 8.10 (d, J = 8.0 Hz, 1H, 4-Py), 7.94–7.90 (m, 3H), 7.73–7.59 (m, 3H), 7.46–7.27 (m, 6H, phenyl+benzene), 5.95 (s, 4H, CH2), 5.63 (s, 2H, CH2);13C NMR (101 MHz, DMSO-d6) δ 153.34, 150.04, 143.67, 140.07, 138.02, 136.14, 131.80, 131.29, 129.27, 128.74, 128.48, 127.33, 127.16, 125.33, 124.19, 123.20, 114.48, 114.41, 53.5, 51.4, 42.3.
General procedure for the preparation of Cu(I)–NHC complexes and Cu(II) complex: Analogously as described in [39], all the copper complexes were prepared by the following route: imidazolium salt (0.2 mmol) and an excess of copper powder (64 mg, 1.0 mmol) were placed in 3 mL of MeCN to form a heterogeneous mixture solution. After the mixture was stirred at 50 °C for 10 h under air, the solution was filtered through Celite. Single crystals suitable for X-ray diffraction analysis were grown from acetonitrile solution and diethyl ether.
Synthesis of [Cu-((1-benzyl-1H-1,2,3-triazol-4-yl)methyl)-3-(pyrimidin-2-yl)-1,3-dihydro-2H-imidazol-2-one)2](PF6)2 (2): This complex was synthesized by the reaction of [H(L1)](PF6) (1a; 93 mg, 0.2 mmol) with copper powder (64 mg, 1.0 mmol) at 50 °C for 10 h. Yield: 79 mg (75%), light green crystals. Anal. calcd for C34H30CuF12N14O2P2. 0.5 CH3CN: C, 40.39; H, 3.05; N, 19.52; found: C, 40.73; H, 2.95; N, 19.15.
Synthesis of [Cu2(L2)2](PF6)2 (3): This complex was synthesized by the reaction of [HL2](PF6) (1b; 102 mg, 0.2 mmol) with copper powder (64 mg, 1.0 mmol) at 50 oC for 10 h. Yield: 66 mg (57%), red crystals. 1H NMR (600 MHz, acetonitrile-d3) δ 8.75 (d, J = 8.1 Hz, 2H, benzimidazole), 8.70 (d, J = 4.9 Hz, 4H, pyrimidine), 7.88 (s, 2H, triazole), 7.79 (d, J = 7.8 Hz, 2H, benzimidazole), 7.59–7.54 (m, 2H, benzimidazole), 7.52 (t, J = 7.2 Hz, 2H, benzimidazole), 7.36 (t, J = 4.9 Hz, 2H, pyrimidine), 7.31–7.29 (m, 6H, phenyl), 7.19–7.18 (m, 4H, phenyl), 5.61 (s, 4H, -CH2-), 5.38 (s, 4H, -CH2-); 13C NMR (151 MHz, acetonitrile-d3) δ 191.23 (Cu-C), 158.73, 157.33 142.39, 136.17 135.75, 132.61, 129.94, 129.67, 129.17, 126.34, 126.19, 125.58, 120.66, 116.95, 112.75, 54.12, 43.41; Anal. calcd for C42H34Cu2F12N14P2: C, 43.80; H, 2.98; N, 17.02; found: C, 43.51; H, 2.85; N, 16.95.
Synthesis of [Cu2(L3)2](PF6)2 (4): The compound was prepared similarly as for complex 3 from [HL3](PF6) (90 mg, 0.20 mmol) with copper powder (64 mg, 1.0 mmol) at 50 °C for 10 h, orange yellow solid. Yield: 71 mg, 68%. 1H NMR (600 MHz, acetonitrile-d3) δ 7.96 (s, 1H, triazole), 7.90 (br, 1H, 2-py), 7.83 (br, 1H, imidazole), 7.76 (s, 1H, 4-py), 7.57 (br, 1H, imidazole), 7.41 (s, 1H, 5-py), 7.37 (d, J = 7.8 Hz, 3H, phenyl), 7.30–7.22 (m, 3H, phenyl + 3-py), 5.47 (s, 2H), 5.38 (s, 2H); 13C NMR (151 MHz, acetonitrile-d3) δ 181.20 (Cu-C), 149.68, 147.26, 140.72, 138.41, 134.71, 129.02, 128.89, 128.80, 128.28, 128.04, 123.96, 123.48, 112.13, 54.36, 45.69; Anal. calcd for C36H32Cu2F12N12P2: C, 41.19; H, 3.07; N, 16.01; found: C, 41.25; H, 3.31; N, 15.46.
Synthesis of [Cu3(L4)3](PF6)3 (5): The compound was prepared similarly as for complex 3 from [HL4](PF6) (106 mg, 0.20 mmol) with copper powder (64 mg, 1.0 mmol) at 50 °C for 10 h, light yellow solid. Yield: 93 mg, 52%. 1H NMR (600 MHz, acetone-d6) δ 8.77 (d, J = 8.1 Hz, 1H, 2-py), 8.46 (td, J = 8.0, 1.8 Hz, 1H, 4-py), 8.33 (s, 1H, triazole), 8.23–8.20 (m, 1H), 7.90 (dd, J = 5.1, 1.5 Hz, 1H, benzimidazole), 7.84–7.81 (m, 1H, benzimidazole), 7.68–7.60 (m, 2H, benzimidazole), 7.44 (dd, J = 7.6, 5.0 Hz, 1H, 5-py), 7.33–7.31 (m, 3H, phenyl), 6.94–6.92 (m, 2H, phenyl), 5.84 (d, J = 15.8 Hz, 1H), 5.37 (d, J = 15.8 Hz, 1H), 5.18 (s, 2H); 13C NMR (151 MHz, DMSO-d6) δ 178.99 (Cu-C), 149.61, 148.44, 142.25, 140.55, 136.19, 134.91, 133.34, 129.31, 128.93, 128.09, 126.05, 125.82, 124.48, 124.27, 119.09, 118.51 (CH3CN), 112.74, 111.59, 54.13, 41.17, 1.56(CH3CN); Anal. calcd for C132H108Cu6F36N36P6. 3CH3CN: C, 46.39; H, 3.30; N, 15.29; found: C, 45.87; H, 3.40; N, 15.30.
Synthesis of [Cu3(L5)3](PF6)3 (6): The compound was prepared similarly as for complex 3 from [HL5](PF6) (106 mg, 0.20 mmol) with copper powder (64 mg, 1.0 mmol) at 50 °C for 10 h, light yellow solid. Yield: 106 mg, 90%. 1H NMR (600 MHz, nitromethane-d3) δ 8.13 (s, 1H, triazole), 7.92 (td, J = 7.8, 1.8 Hz, 1H, pyridine), 7.77 (d, J = 7.8 Hz, 1H, pyridine), 7.59 (d, J = 7.8, 1H, pyridine), 7.61–7.36 (m, 6H, phenyl + benzimidazole), 7.14–7.08 (m, 2H, benzimidazole), 6.95 (ddd, J = 7.5, 5.2, 1.1 Hz, 1H, pyridine), 6.49–6.45 (d, J = 4.8 Hz,1H, benzimidazole), 5.40 (d, J = 15.0 Hz, 1H, -CH2-), 5.30 (d, J = 15.0 Hz, 1H, -CH2-), 5.27 (d, J = 15.0 Hz, 1H, -CH2-), 5.26 (d, J = 15.6 Hz, 1H, -CH2-), 5.21 (d, J = 15.0 Hz, 1H, -CH2-), 4.98 (d, J = 15.6 Hz, 1H, -CH2-); 13C NMR (150 MHz, nitromethane-d3) 177.57 (Cu-C), 151.99, 148.85, 141.78, 139.93, 135.15, 134.68, 133.85, 129.16, 128.98, 128.81, 128.12, 125.04, 124.62, 124.35, 123.79, 110.58, 110.26, 54.49, 51.29, 40.72; Anal. calcd for C69H60Cu3F18N18P3: C, 46.90; H, 3.42; Cu, 10.79; N, 14.27; found: C, 46.35; H, 3.31; N, 13.95.
General procedure for the copper-catalyzed CuAAC reaction: Analogously as described in [31], in a 10 mL Schlenk tube, azide (0.5 mmol), alkyne (0.6 mmol), and 0.5 mol % copper complex were dissolved in 3.0 mL of CH3CN. After the mixture was stirred at rt under air for a desired time, the reaction was stopped by the addition of H2O (2 mL) to the resultant mixture. Then the mixture was extracted with CH2Cl2. The organic layer was separated from the aqueous phase. After the organic phase was dried over MgSO4, the solution was filtered and concentrated under vacuum. The residue was purified by flash chromatography (silica gel, petroleum ether/ethyl acetate, 3:1) to give the desired product
X-ray diffraction analysis
Analogously as described in [27], single-crystal X-ray diffraction data were collected at 298(2) K on a Siemens Smart/CCD area-detector or Oxford Diffraction Gemini A Ultra diffractometer with a Mo Kα radiation (λ = 0.71073 Å) by using an ω-2θ scan mode. Unit-cell dimensions were obtained with least-squares refinement. Data collection and reduction were performed using the SMART and SAINT software [46]. The structures were solved by direct methods, and the non-hydrogen atoms were subjected to anisotropic refinement by full-matrix least squares on F2 using the SHELXTXL package [47]. Hydrogen atom positions for all of the structures were calculated and allowed to ride on their respective C atoms with the C–H distances of 0.93–0.97 Å and Uiso(H) = 1.2 − 1.5Ueq(C). Disordered solvent molecules that could not be modeled successfully were removed with SQUEEZE [48]. Further details of the structural analysis are summarized in Table 3.
Table 3: Crystallographic data for complexes 2–6.
CCDC number 1424013 1424014 1424015 1424016 1424017
formula C70H63Cu2F24N29O4P4 C42H34Cu2F12N14P2 C36H32Cu2F12N12P2 C278H237Cu12F72N79P12 C69H60Cu3F18N18P3
Fw. 2081.47 1161.93 1049.76 7186.59 1766.88
crystal system orthorhombic monoclinic triclinic hexagonal hexagonal
space group Pnna C2/c P-1 R3c R3c
a/Å 14.0847(15) 34.298(3) 12.9626(10) 28.178(3) 21.4692(13)
b/Å 14.5426(16) 13.2602(12) 13.0382(9) 28.178(3) 21.4692(13)
c/Å 22.599(2) 26.605(4) 13.1663(10) 16.3997(19) 71.858(9)
β/deg 90.00 129.8310(10) 80.661(6) 90.00 90.00
V/Å3 4629.0(9) 9291.9(19) 2111.7(3) 45655(10) 28684(4)
Z 2 8 2 6 12
D/g cm−3 1.493 1.661 1.651 1.568 1.228
Reflns collected 18121 10632 7571 21009 5624
ind reflns, Rint 12510, 0.0545 7828, 0.0250 4679, 0.0467 15722, 0.0869 3716, 0.0650
goodness-of-fit on F2 1.063 1.018 1.023 1.031 1.157
R1, wR2 [I > 2σ(I)] 0.0869, 0.2496 0.0562, 0.1652 0.0696, 0.1774 0.0622, 0.1353 0.0688, 0.2044
R1, wR2 (all data) 0.1338, 0.3001 0.0779, 0.1858 0.1122, 0.2172 0.0917, 0.1543 0.1200, 0.2623
Supporting Information File 1: X-ray crystallographic data in cif format CCDC 1424013–1424017.
Format: CIF Size: 146.7 KB Download
The authors thank the National Natural Science Foundation of China (21202127), and the Educational Commission of the Hubei Province (Q20151606) for financial support. Shaojin Gu gratefully acknowledges financial support from the China Scholarship Council (201308420278).
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41. Catalano, V. J.; Munro, L. B.; Strasser, C. E.; Samin, A. F. Inorg. Chem. 2011, 50, 8465–8476. doi:10.1021/ic201053t
40. Pouy, M. J.; Delp, S. A.; Uddin, J.; Ramdeen, V. M.; Cochrane, N. A.; Fortman, G. C.; Gunnoe, T. B.; Cundari, T. R.; Sabat, M.; Myers, W. H. ACS Catal. 2012, 2, 2182–2193. doi:10.1021/cs300544w
47. SHELXS-97 and SHELXL-97, Program for X-ray Crystal Structure Refinement; G. M. Sheldrick: University of Göttingen, Germany, 1997.
48. Spek, A. L. PLATON, A Multipurpose Crystallographic Tool; University of Utrecht: Netherlands, 1998.
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Advancements in the mechanistic understanding of the copper-catalyzed azide–alkyne cycloaddition
Regina Berg and Bernd F. Straub
Synthesis and structures of ruthenium–NHC complexes and their catalysis in hydrogen transfer reaction
Chao Chen, Chunxin Lu, Qing Zheng, Shengliang Ni, Min Zhang and Wanzhi Chen
Liquid-assisted grinding and ion pairing regulates percentage conversion and diastereoselectivity of the Wittig reaction under mechanochemical conditions
Kendra Leahy Denlinger, Lianna Ortiz-Trankina, Preston Carr, Kingsley Benson, Daniel C. Waddell and James Mack
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text:
The Garg Synthesis of (-)-N-Methylwelwitindolinone C
Of the several welwitindolinones, (-)-N-Methylwelwitindolinone C (3) uniquely reverses P-glycoprotein mediated multiple drug resistance. The preparation of 3 reported (J. Am. Chem. Soc. 2011, 133, 15797. ) by Neil K. Garg of UCLA illustrates the power in complex target-directed synthesis of late stage C-H functionalization.
The starting material 7 for this enantiospecific synthesis was prepared following the Natsume strategy (Chem. Pharm. Bull. 1994, 42, 1393. ) in the enantiomeric series. Commercial carvone 4 was reduced and protected, then oxidized and equilibrated to the dienone 6. The pivalate efficiently directed the Cu-catalyzed conjugate addition of vinyl magnesium bromide, delivering 7.
Hydrolysis of 7 gave 8, to which the bromoindole 9 was added in a conjugate sense to give the adduct as a mixture of diastereomers, of which 1 was the more stable. Exposure of 1 to NaNH2 in tBuOH presumably generated the benzyne [indolyne] 10, which cyclized to the ketone 2.
The silyl ether 2 was deprotected and the alcohol was oxidized to give the diketone, which was selectively carried on to the enol triflate and thus to the stannane 11. The alkenyl chloride of the natural product was installed by the oxidation of 11 with CuCl2. Further oxidation with N-bromosuccinimide then delivered the oxindole 12.
In the last stage of the synthesis, it was necessary to selectively aminate one of the bridgehead C-H's of 12. To this end, the ketone was reduced and carried on to the carbamate 13. Attempts to oxidatively cyclize 13 with Rh catalysts failed, but Ag was successful, delivering 14. The final conversion of 15 to (-)-N-Methylwelwitindolinone C (3) was achieved by exposure to the Kim reagent (16).
D. F. Taber, Org. Chem. Highlights 2012, June 4.
URL: https://www.organic-chemistry.org/Highlights/2012/04June.shtm

redpajama_set_name: RedPajamaCommonCrawl


text:
Q: Slice Qstring from right hand side I have a qstring of directory structure and need to take the second last element after "/" into a new qstring
"C:/Users/emb/Documents/AutoConnectTest/02/Job_0"

How to save 02 into a new QString

A: You can use QString split function.
Splits the string into substrings wherever sep occurs, and returns the list of those strings.
this code split all section by "/" and merge two second from last.
QString string = "C:/Users/emb/Documents/AutoConnectTest/02/Job_0";
QStringList lst = string.split('/');
qDebug() << lst[lst.count()-2] + "/" + lst[lst.count()-1];

Output:
"02/Job_0"

redpajama_set_name: RedPajamaStackExchange


A exotic global party is healing and beautiful bringing the world of fruit and herbs together in your cup.
Tea Docent says "An exotic, global blend of medicinal hibiscus from Jamaica, healing lemongrass from Southeast Asi and purifying Australian eucalyptus. American blackberry and apples, vision-enhancing carrots and citamin-rich oranges join in to bring one healthy, beautiful and delicious world together in your cup!"
"This herbal tisane is naturally flavored in Germany and contains no caffeine"
This special blend contains the highest quality raw materials from around the world tested, controlled and blended in Germany. Compliance with EU standards means every tea is certified to HACCP(Hazard Analysis and Critical Control Points), ensuring a high level of food safety.


"Product images provided by shop owners are not enough for me when I consider making an online purchase!". Explore this extension to give your customers a chance to experience what actual products look like and decide to place an order without hesitance.
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In order to decide which images are suitable to display, admin can approve/ disapprove/ delete one by one or multiple customer image requests.
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This is the must-have extension for fashion stores. It is an effective way to get feedback from customers and prove the product quality.


rules at the bottom of this post for convenience.
Mainly, if a player uses two chips of different sizes to call a raise, he might be forced to make a minimum re raise when his intent was only to call.
Yet another player using two chips of identical size, thinking he was raising, might be relegated to just call.
less than a call. His intent was to raise but he failed to say raise so his action is just a call.
Player C, seeing the action before him, puts in 2 chips, one is $1000T and one is $500T and says nothing.
more of the raise so he must now add $300 to his bet to complete the full raise.
experienced, savy tournament player and I'm thinking a solution can be found to prevent these type situations.
Or am I missing something altogether?
no-limit and pot limit, an all-in wager of less than a full raise does not reopen the betting to a player who has already acted.
chips without declaring raise. Placing chips of mixed denominations in the pot is governed by the 50% standard in Rule 31.
I don't believe there is a 'conflict' between the rules but there is quite a bit of agreement among us that a language change to rule 31 for that bit to say MORE THAN 50%. That way you eliminate one of the problems and I think the multiple denom chip thing is easy to understand and a player will learn to throw in a third small chip in the future, or declare his action.
You would do well to check out this thread: http://www.pokertda.com/forum/index.php?topic=265.0. It discusses the relationship of rules #30, #31, and #33 and some of the changes that will likely be discussed at this years TDA Rules Summit.
Unless a raise has been declared, placing multiple chips in the pot that add to less than double the bet one is facing will be deemed a call if removal of any one chip leaves less than the bet the player could have called.
Under that July 2009 version of the rule, the "conflict" mentioned by higavin would not exist. In both cases -- playing two T1000 chips or playing one T1000 and one T500 -- the action would be ruled a call because "removal of any one chip" would leave less than T1100, which is the bet the player could have called.
The current Rule 33 as quoted above is from the TDA Rules Version 2009.2.0 (released Sept. 15, 2009). I wonder if the drafters/editors of the rule considered situations such as this when writing the rule.
Personally, I prefer the original version of Rule 33 that applied to all multiple chip plays and not only those of "same-denomination" chips.
I have always assumed that the example you give of the multiple different denomination chips would still be a call. However....after looking at rule #33 I can clearly see how this created confusion. Oddvark, I will have to agree with you on this one, the old rule may have been better. If I were dealing I would have given the player 400 change from his 1000 and 500. Yet the way the rule is written, I would have been wrong.
Jasper, take a closer look at the original question and I'm sure you will see that, the 1000 and the 500 chip would qualify as over 50% and dictate that the player complete the raise to 1800. Add #33 to this years list. The perfect example given by higavin made the difference for me.
Your right Nick, I didn't study the example well enough I guess. It is a perfect example of two different situations from which one could perceive a conflict between the rules.
I think Oddvark's example of what may have been an earlier version of the rule would make it so that multiple chips could be governed by a sort of modified "single chip rule" and make those situations all CALLS. That way the player would have to take more time to declare a raise and less time worrying about goofing up on just making a call.
Though, I am with higavin in that it's not that difficult for a player to make his intentions known.
I do think those two rules are easy enough to administrate though and players generally are careful to declare a 'call' when they know they are putting in chips valued at more than bet size.
That's very true. Too bad we couldn't make it mandatory that whenever any player puts multiple chips into the pot he must announce his intentions. Thinking out loud....I know that will never happen.


text:
Q: Rinex Header GPS Position Coordinate System I am extracting data from rinex observation files and would like to convert the approximate position to latitude and longitude using Proj.4. The rinex standard states that these coordinates are WGS84, which I assume refers to the ellipsoid. What are the Proj4 parameters I need to do the conversion? If this is not possible is there another route I can take? Specifically I'm using the pyproj Python library. The correct coordinates should be close to (45.4343,-123.5516).
I am using RTKLib to process the observations, but want to automate downloading the base station/CORS files.
I did just find this code that performs the conversion. I've ported it to Python and it works well for my needs. Still if there is a way to get Proj4 to do this that would be ideal as I use that library for other projects.
Here is the Python I've tested:
In [29]: prj = pyproj.Proj(proj='geocent',ellps='WGS84',datum='WGS84')

In [30]: prj(-2478053.2006,-3736604.9657)
Out[30]: (1e+30, 1e+30)

In [31]: prj(-2478053.2006,-3736604.9657,inverse=True)
Out[31]: (-22.260730649602785, -33.5664935140521)

Here is an example header.
     2.00           OBSERVATION DATA    M (MIXED)           RINEX VERSION / TYPE
                                        20180413 230424 UTC PGM / RUN BY / DATE
28jxmqr6                                                    MARKER NAME
                                                            MARKER NUMBER
                    off                                     OBSERVER / AGENCY
100037              BE-GPS-3300         2.1.47              REC # / TYPE / VERS
                                                            ANT # / TYPE
 -2478053.2006 -3736604.9657  4521684.4805                  APPROX POSITION XYZ
        0.0000        0.0000        0.0000                  ANTENNA: DELTA H/E/N
     1     1                                                WAVELENGTH FACT L1/2
     4    C1    L1    C2    L2                              # / TYPES OF OBSERV
  2018     4    13    19     8   50.5000000     GPS         TIME OF FIRST OBS
  2018     4    13    19    23   28.0000000     GPS         TIME OF LAST OBS
                                                            END OF HEADER

A: The geocentric coordinates can be converted to latitude, longitude, and altitude by using the pyproj.transform function. The Proj.__call__ method does not accept Z values, which are required for the transformation.
In [6]: p1 = pyproj.Proj(proj='geocent',ellps='WGS84',datum='WGS84',units='m',no_defs=True)

In [7]: p2 = pyproj.Proj(init='epsg:4326')

In [8]: pyproj.transform(p1,p2,-2478053.2006,-3736604.9657,4521684.4805)
Out[8]: (-123.55166435788638, 45.43449642806122, 450.48841851670295)

The output is equivalent to the following cs2cs input:
cs2cs +proj=geocent +ellps=WGS84 +datum=WGS84 +no_defs +units=m +to +init=epsg:4326 -f "%.8f"
-2478053.2006 -3736604.9657  4521684.4805
-123.55166436   45.43449643 450.48841852

A: I don't think a normal projection library is going to do the conversion for you.
While these coordinates are WGS84, they are cartesian (XYZ) coordinates, and not geodetic (Lat/Lon).
This forum post says that you can use the program GeoConv to do the conversion.
Maybe you should have a look at the RTKLib and see if it can proces the file for you?


text:
NSA employee spied on nine women without detection, internal file shows
Twelve cases of unauthorised surveillance documented in letter from NSA's inspector general to senator Chuck Grassley
Paul Lewis in Washington
@PaulLewis
Fri 27 Sep 2013 17.08 EDT First published on Fri 27 Sep 2013 17.08 EDT
General Keith Alexander said abuse of the NSA's powerful monitoring tools were 'with very rare exception' unintentional mistakes. Photo: Alex Wong/Getty Images
A National Security Agency employee was able to secretly intercept the phone calls of nine foreign women for six years without ever being detected by his managers, the agency's internal watchdog has revealed.
The unauthorised abuse of the NSA's surveillance tools only came to light after one of the women, who happened to be a US government employee, told a colleague that she suspected the man – with whom she was having a sexual relationship – was listening to her calls.
The case is among 12 documented in a letter from the NSA's inspector general to a leading member of Congress, who asked for a breakdown of cases in which the agency's powerful surveillance apparatus was deliberately abused by staff. One relates to a member of the US military who, on the first day he gained access to the surveillance system, used it to spy on six email addresses belonging to former girlfriends.
The letter, from Dr George Ellard, only lists cases that were investigated and later "substantiated" by his office. But it raises the possibility that there are many more cases that go undetected. In a quarter of the cases, the NSA only found out about the misconduct after the employee confessed.
It also reveals limited disciplinary action taken against NSA staff found to have abused the system. In seven cases, individuals guilty of abusing their powers resigned or retired before disciplinary action could be taken. Two civilian employees kept their jobs – and, it appears, their security clearance – and escaped with only a written warning after they were found to have conducted unauthorised interceptions.
The abuses – technically breaches of the law – did not result in a single prosecution, even though more than half of the cases were referred to the Department of Justice. The DoJ did not respond to a request for information about why no charges were brought.
The NSA's director, Gen Keith Alexander, referred to the 12 cases in testimony to a congressional hearing on Thursday. He told senators on the intelligence committee that abuse of the NSA's powerful monitoring tools were "with very rare exception" unintentional mistakes.
"The press claimed evidence of thousands of privacy violations. This is false and misleading," he said.
"According to NSA's independent inspector general, there have been only 12 substantiated case of willful violation over 10 years. Essentially, one per year."
He added: "Today, NSA has a privacy compliance program any leader of a large, complex organization would be proud of."
However, the small number cases depicted in the inspector general's letter, which was published by Republican senator Chuck Grassley, could betray a far larger number that NSA managers never uncovered.
One of the cases emerged in 2011 ,when an NSA employee based abroad admitted during a lie-detector case that he had obtained details about his girlfriend's telephone calls "out of curiosity". He retired last year.
In a similar case, from 2005, an NSA employee admitted to obtaining his partner's phone data to determine whether she was "involved" with any foreign government officials. In a third, a female NSA employee said she listened to calls on an unknown foreign telephone number she discovered stored on his cell phone, suspecting he "had been unfaithful".
In another case, from two years ago, which was only discovered during an investigation another matter, a woman employee of the agency confessed that she had obtained information about the phone of "her foreign-national boyfriend and other foreign nationals". She later told investigators she often used the NSA's surveillance tools to investigate the phone numbers of people she met socially, to ensure they were "not shady characters".
The case of the male NSA employee who spied on nine women occurred between 1998 and 2003. The letter states that the member of staff twice collected communications of an American, and "tasked nine telephone numbers of female foreign nationals, without a valid foreign intelligence purpose, and listened to collected phone conversations".


Domino's Pizza is one of the most popular pizza chain and is a delivery company for different varieties of pizza. In today's world, Domino's has been equivalent to quality, freshness and good service. This fast food company has continued to grow by leaps and bounds. The company's innovative ideas, the commitment to provide quality products and its dedication to the customer base have helped it to maintain its position at the top.
Tom Monaghan and his brother James launched Domino's in the year 1960. The next year Tom bought his brother's share with a trade of Volkswagen Beetle. The company was then renamed Domino's Pizza. Dominos opened its first outlet in India in the city of New Delhi. Later it opened other outlets in almost all the cities of India and at present, it has more than 500 outlets in India.
The chief competitors of this coolest dug-out are Pizza Hut, KFC, McDonald and Subways.
Domino's is widely known for its quality and fresh pizza. The boxes for the food products are specially designed to keep everything fresh and hot. The products offered are of both vegetarian and non-vegetarian variety. In order to seize the market Domino's has worked on a unique concept of localizing the flavors.
Domino's pizza comes in three different sizes – small, medium and large. In the varieties, Country Special Pizza, Mexican Green Wave Pizza, Zesty Chicken pizza, Seventh Heaven Pizza, Chicken and Prawn Pizza, Grand Supreme Pizza, Chicken and Camembert Pizza are some of the popular pizzas.
Besides pizzas, Domino's also deals in some other food items. Calzone pockets, Garlic Bread Sticks, Stuffed Garlic Bread Sticks, Taco Indiana, Pasta Italiano (white sauce), Chicken Wings, Choco Lava Cake, Spicy Baked Chicken and Butterscotch Mousse Cake are also available here. Beverages like Thumps-up, Fanta and Coke have been introduced in the menu.
Dominos also gives a choice in the matter of crust like theFresh Pan Pizza and Cheese burst pizza. It has also started offering options including whole-wheat crust and any other company has yet not utilized this option. The buyer also has a choice on the toppings. Extra cheese on a pizza and Dips like Roasted Pepper Dip and Cheesy Jalapeno Dip are available on demand.
Domino's main target is the lower middle class and middle class income group. Best of quality with reasonable pricing is its motto. Dominos has come up with a uniform and consistent pricing policy. This keeps the base price in check and helps the company to attract customers. If you look at the competition, then Domino's has been evenly prized with Pizza hut. But the prices are high as compared to KFC and McDonalds and hence the price conscious customers will prefer the indirect competitor – McDonalds and KFC above Domino's.
Affordability is the key to the tremendous success of this reputed company. To maintain the price level many new and innovative schemes are launched on regular basis. It always gives its customers value for one's money. Special discounts are offered at regular intervals. For Wednesdays, a special scheme was launched where one free pizza was offered with one buy. Many free food items on purchase of selected and exclusive products are some of the methods to lower the prices and attract the customers. Pizzas are available in three sizes large, medium and regular so that one can buy whichever is affordable to them.
Domino's pizza has always maintained a direct channel with its customer base. The customers either call or send a message by telephone for the pizza delivery. Consumers can also place their order online through the official website of Dominos. In both the cases, the packaged food product is delivered and subsequently received by the buyer at the mentioned address. If the order does not reach the buyer in allotted thirty minutes, then the buyer does not have to pay for it. The order is delivered free of charge. The delivery boys are the real heroes of this organization. The detail of every route is decided beforehand and after an order is placed, this route is followed so that minimum time is taken.
One of the most common methods of eating a pizza is to dine-in the Dominos outlet. Dominos has many outlets in very good locations. Most of the shopping malls and main streets have a section for Domino's pizza. Domino's is currently located in 73 countries and has more than 10000 stores.
Domino's idea of maintaining direct contact with its consumer base is one of the leading factors that have taken the company to unachievable heights. Its policy of door-to-door deliveries is amazing. Nearly every individual knows that Domino's will deliver the pizza in thirty minutes flat. Domino's sales depend on telemarketing and the efficiency of their trained delivery boys.
Besides evaluating their own strength and weaknesses, Dominos has also been observant of their competitors. McDonalds KFC, Subway, Pizza Hut and Burger King are some of the important competitors of Domino's. The one field where the other companies have been simply unable to give competition is in delivering the pizzas on time.
To promote its food products, Dominos is always introducing new schemes and offers in order to maintain its grip on its customers. The home delivery is always free of charge. Sometimes the company offers a 50% discount on the second pizza. At other times, the company introduces schemes like one small pizza free on one large pizza. Sometimes lucky coupons are also awarded to loyal buyers. The most regular and common scheme is of giving a coke free on every purchase. Thus, the advertising team is actively involved in the marketing and promotional strategy to boost up the sales.
The visual media of television has been utilized to the maximum capacity. Many beautiful ads for domino's pizza with reputed actors have been aired and they all have been very popular with the masses. Most ads of Domino's are targeted to be product introduction or ads or the brand's reminder ads so that people look at the ad and order a Domino's Pizza. Domino's has surely changed the concept of eating amongst the Indian Household. Ads for Domino's pizza can also be seen in newspapers and magazines.
hello Hitesh, i want to open desi pizza stall ,do u plz tell me authorization detail for that .and what time does it take to approve from formalities .
Hi Ashutosh. I think initially Shop establishment is a must. I also think Service tax registration will be required. It will cost you around 25000. I dont think in services VAT registration is required. It is required only if you cross turnover of 4 lakhs. A CA will be able to help you better. He will also be able to help you with the IT returns later on so it is important that you save your expense bills etc. So best would be to immediately get in touch with a CA.


text:
Videogame News
Microsoft's Purchase of Activision Changing the Gaming Landscape
By Rosawrites
As a tech giant, Microsoft has long been a monopolist. For its games division headed by CEO of Microsoft Gaming, Philip Spencer, which has the Xbox console as the focal point, the monopolist continues to expand its reach and foundation in the gaming world. In a massive all-cash deal wherein each share costs $95.00 with a total value of $68.7 billion, Activision Blizzard will soon be in the hands of Microsoft. Microsoft's play in the gaming business would allow them ownership over games such as Call of Duty, World of Warcraft, Candy Crush, Diablo, and Overwatch from the studios of Activision, Blizzard, and King. Aside from the initially mentioned studios, Double Fine, Ninja Theory, and Obsidian Entertainment are studios previously added to the growing gaming business of Microsoft.
Microsoft's Stance on Activision Blizzard Deal
The company plans to include both new and old games from Activision Blizzard's array of games in its catalog into its cloud subscription service called Game Pass. The purchase aims for players to have a gaming experience with ease, according to the collective emphasis of Nadella, Microsoft CFO Amy Hood, Spencer, and Activision Blizzard CEO Bobby Kotick. The gaming industry is bound to change with this leap taken by the Microsoft Corporation. Moreover, another goal stated by Spencer is to reach an increased number of players. A new category of entertainment will soon be available for more players. Hence, the device-agnostic future Microsoft envisioned meets reality gradually as big-name titles become its possessions.
Crash Course on How Big Companies Work
There is no secret to how big and powerful companies attain immense success. It is, however, through adaptability. For instance, while other big companies are left in the dust and inevitably knocked out of business, others such as Microsoft remain competitive. Spotting technological trends and exploiting key software technologies became its advantageous abilities. The reasons emerged from new research by Harvard Business School professors Marco Iansiti and Alan MacCormack. Despite the hefty amount of money required to purchase the video-game publisher, this strategic deal will bring long-term gains to Microsoft.
What's In It for Microsoft?
Through this power move by the company, mobile gaming also becomes a target for expansion as metaverse platforms continue development. World-class content; and an inclusive, accessible, and safe gaming environment for players and creators summarize the investment goal of Microsoft. Additionally, in this deal, the independence of the gaming company does not become recipient to compromise. Microsoft still allows independence and creativity in developers to ensue. Also, along with the deal are 10000 employees of the gaming company.
Aside from this merger of Microsoft with Activision, Microsoft has had numerous successful game mergers that happened in the past. In 1996, the first game it acquired was Exos, a company for video game controllers. In the same year, it acquired Electric Gravity. In 1999, added to the list was FASA Interactive and Access software. Come to 2000, Bungie, Netgames, and Digital Anvil also merged. Ensemble Studios, Rare, Lionhead Studios, Massive Incorporated, Twisted Pixel Games, Press Play, and Mojang, to name a few, comprise the companies acquired by Microsoft. Over the span of three decades, the company had myriads of successful game mergers. In the past five years, more game companies added to the long list of mergers and acquisitions of Microsoft.
Victories of Microsoft and Activision
The Xbox celebrated its 20th-anniversary last year and today remains one of the largest companies standing in the console business. and it became a contributor to the growth and change in console gaming over the years. To add, the release of Forza Horizon 5 of Microsoft in 2021 became the Xbox Game Studios strongest launch as it garnered 4.5 million players in a week.
For Activision, it developed the famed games that many players enjoy. It bears the top spot in being a worldwide developer, publisher, and distributor of interactive entertainment. The target of interactive entertainment produced by Activision is gaming consoles, hand-held platforms, and PC. Call of Duty, Crash, and SpyroTM are among the popular franchises that raked in players and profit for Activision.
Microsoft-Activision Deal Effect on Sony and Nintendo
The acquisition of Activision by Microsoft poses a threat to the home of PlayStation - Sony. Sony took a critical blow after the deal became public with a 13% downwards swoop in the shares of the maker of the PlayStation, which was their worst stock price plunge since 2008. Gaming content is the cause for concern for Sony as Microsoft leveled up its gaming content. Also, with Microsoft's Game Pass cloud subscription service, a strong challenge persists for the PlayStation series of Sony.
In comparison to Nintendo, Sony suffers a heavier impact. Only minimal blow has reached Nintendo as it leans more toward concepts and content. The head-on clash is between Sony and Microsoft as they operate likely, while a small corporation such as Nintendo remains separate, strong, and unbothered.
Yay or Nay?
The deal will close in 2023, and only good claims about the entertainment and metaverse platform potential of the merger have been released by Microsoft. Furthermore, in the gaming industry, the future of Xbox will be secured once the deal is closed. Also, with the help of Microsoft in the form of resources, Activision Blizzard could approach game improvement and development notably. The merger sounds promising, but players will have to see if it pushes through approval. By then, gamers can yay or nay in finality as the current impression for the merger is guarded optimism.
ideogames
Steam Rides Out of Black Friday to 31 Million + Users
Evil West Catches the BULLET of some rough review scores and some BIG Performance issues
The Witcher 3: Wild Hunt Next Gen Update Announced for Dec 14th!


text:
legislative news » outlook »
In Memory of Susan Campbell Brownsberger
Posted byWill Brownsberger	 February 10, 2021 February 12, 2021 267 Comments on In Memory of Susan Campbell Brownsberger
When my mother received a definitive diagnosis of pancreatic cancer, she faced death with realism and equanimity. The final indignities tried her courage, but her grace sustained us as we grieved through her swift decline.
She was a beloved daughter, sister, wife, mother, grandmother, great grandmother, and friend to many. She was also a critically-acclaimed translator of Russian literature.
Her last major life project, which she completed only weeks before cancer began to tighten its final grip, was a family history. For years, she pored over genealogical records and available documents and produced a collection of narratives that deepened the family's sense of connection to American history and ideals.
She taught her children from an early age to take American history seriously. She brought us to the Lexington Green and the Old North Bridge where the "embattled farmers stood and fired the shot heard around the world." The revolution of common people against monarchs who styled themselves as divinely-appointed eventually spread from there across Europe.
She taught us early that Jefferson's declaration that "all men are created equal" was neither complete nor fully realized at the time of the revolution.
She took pride in the intellectual leadership of Massachusetts and taught us that leading abolitionists spoke out in Boston. The war to end slavery figured large in the songs she sang with us and the poetry she read to us.
She always choked up reading "Barbara Frietchie," identifying with the heroine of that poem, who snatches up a Union flag shot down by an advancing column of Confederate soldiers. "'Shoot if you must this old grey head, But spare your country's flag,' she said." In the poem, the heroine's moral force prevails and the Union flag waves over the long Confederate columns advancing through the town.
Mom's father's family was in Ohio before the Civil War. One branch ran a station on the underground railroad. They corresponded with John Brown while he was in prison before he was hanged for the raid on Harper's Ferry. Men from his family wore blue into battle in the Civil War. Her father's grandfather was shot in both thighs in the battle of Cloyd's Mountain, Virginia where he lay for three days before being picked up.
She also spoke with reverence of her father's younger brother Bob's bravery in WWII. After Japanese torpedoes set the carrier U.S.S. Wasp aflame in the Coral Sea, he was among the last men to leave the ship before it sank. She collected a volume of family letters which told more of that story.
She lived for a year in Tokyo with her newborn son while her husband served in Korea. She learned to speak some Japanese, formed friendships with her neighbors there, and grew to love Japanese culture.
During the Vietnam War, she and my father took us to the anti-war demonstrations on Boston Common.
As she taught us with gravity about American history, she also taught us by word and deed to respect every person as an individual. She took an interest in everyone's story, respected everyone's perspective and was never quick to judge.
She was devoted to family and to community and to service broadly. As a translator of Russian literature, she opened new vistas for English-speaking readers. She worked hard to fully appreciate the words of her authors and translated them with empathy for the human struggles behind the words.
She imparted to her children a reverence for the founding ideals of the American republic, a recognition of our failure to live up to those ideals, a commitment to service, and most importantly, respect and empathy for every individual. She died as she lived – with grace and courage.
I'm so grateful to all who have taken the time to share thoughts or send condolences. Each comment means a lot to me and to my family.
Posted byWill Brownsberger February 10, 2021 February 12, 2021 Posted inOutlook
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She sounds like a remarkable women. I lost my Mom last month as well… It is hard when your anchor is gone…
Marie Winfield says:
What a wonderful remembrance! I celebrate her rich and wonderful life with you, Senator Brownsberger.
Liz King says:
So sorry about your loss. She sounds like a wonderful woman. You and the rest of the family will cherish the family history for a long time, I'm sure.
Sylvia E Green says:
Your Mother was a remarkable woman. Your career and tribute
demonstrates her phenominal success in raising a son that you
are. You certainly have my sympathy at this time.
Will, I am so sorry for your loss – she sounds like a remarkable human being. My thoughts are with you and yours.
Richard J Carlson says:
Will – sorry for your loss. It sounds like you had a great relationship with your mother, something to always cherish. Sympathies to you and your family.
-rich
Jerome Spencer says:
Mr.Browns burger as angry as i always seem i'm so very sorry to hear about your lost you have my deepest condolence and from what i read your mom taught a very good lesson to be learned
Maggie Huff-Rousselle says:
This is a beautiful tribute to your mother and perhaps help me understand why you are such an excellent example as an elected official and the role people like you can play when and if they choose to.
Michael Simons says:
Dear Will –
My deepest condolences. Your mom is amazing and although I am sad for your loss – I can see her shining influence in you and much more.
sherrie lookner says:
Sorry for your loss. She sounds like an amazing character whose legacy will live on.
Nina Grimaldi says:
You are your mother's son and I am grateful for that! As a Russian language and lit student, I also have great admiration for your mother's academic achievements! So sorry for your loss.
Fran Yuan says:
I'm so sorry to hear of your loss, Will. What a life to look back on, though. She clearly gave you a lot of her own values, knowledge and sensibilities. It sounds like she was a remarkable person. Our deepest condolences.
Jennifer Christian says:
Very sorry for your loss, Will. What a remarkable person and wonderful role model she was. And you listened and learned!
ELOISE MCGAW says:
What a wonderful tribute Will. I can see how her spirit will live on in you and your children. I am so sorry for this loss, as we all know how hard it is to lose our parent. Much love to you.
Betty Lim King says:
Your mother was a remarkable human being and an inspirational American. Her values and ideals live in you and are reflected in your own exemplary life and courageous political path.
Very touching an brave of Will to write
Lesley Christos says:
My condolences to the Brownsberger family, Will thank you for sharing a piece of your mother's legacy.
Fred Bouchard says:
Like mother, like son.
Frank Hartmann says:
Yes, Fred said it right
Marie F says:
Will, thank you for sharing. I am deeply sorry for your loss, and in reading this, see how the example of your mother's life, her beliefs, and work is reflected in you and the work you do. Sending thoughts for you and your family in this difficult time.
Kathleen young says:
Dear Will
Thank you for sharing these reflections .What a beautiful testimony to your mom's wonderful spirit. She must have been so proud and happy that you so effectively live out the values she imparted. We send our sympathy to you and your family . Kathy
Gretchen Dunoyer says:
I'm so very sorry for your loss. A mother of such grace, wisdom, intelligence and stature is a true gift, not only to her immediate family and children, but to the world. Thank you for sharing this, and sending much love from Jean and Gretchen Dunoyer.
Meryl Ray says:
Dear Will and Brownsberger Family,
I remember meeting your mom and dad at the Winnbrook School many years ago when you were running for Selectman, I believe, Will? Your parents were just lovely..your mom a poised and beautiful woman. Such a loss. We will remember you and your family prayerfully. Merry and Terry
My sincere condolences on the loss of your remarkable mother. She must have been proud to see you serve Massachusetts so well.
Sorry for your loss and what she went through. What a wonderful person she nurtured and raised. A good life and loving family. Many happy memories. May she Rest In Peace.
Stephen Sala says:
A very nice memory and tribute …
Stephen Sala
What a beautiful tribute you've shared. We're all beneficiaries of her intelligence, compassion, and many contributions. May her memory be a blessing to you and your family.
Sorry for your loss Will. It sounds like you inherited much from your mother, and that you were fortunate to have her be such a wonderful and long lived part of your life.
Michael Wark says:
My deepest condoloences to your family and friends. This was so well-written and more importantly moving and imparted a glimpse into how wonderful your mother was to those who didn't know her.
Lison Baselis-Bitoun says:
Your Mom was a courageous woman who taught you well. My deepest sympathies. May you keep always important memories of her. She deserves to be remembered.
Pat and Ken Davis says:
We are so sorry for your loss. Your mother was an outstanding women, as the tribute clearly states. How wonderful that you have all those amazing memories and a documented family history .Her legacy lives on.
Pat and Ken Davis
Jessie Bennett says:
I am so sorry for your loss, Will, especially during this time when the comfort of our loved ones' presence is more difficult to come by. This is a beautiful tribute to her and her values, which clearly live on in her son.
Sally Eyring says:
I'm so sorry for your loss. She sounds amazing, and we are all richer for having had her in our community.
David Patterson says:
TenBroeck and I send you our sympathy and want you to know how a son's writing about his mother deeply affected both of us. Thank you.
Ken Stalberg says:
Thank you, Will. Your mother represents everything I love about this country. With the impeachment trial happening now, the contrast between her courage and values and the craven cowardice in the Senate could not be more clear. It's easy to see where your strength and compassion come from. We are thinking of you.
Paula Rosenstock says:
Dearest Senator Brownsberger, What a beautiful and touching tribute to your beloved mother. It is clear she was an extraordinary person. As is Jewish tradition during these times, I will say may your mother's memory be a blessing. Wishing you strength and healing to you and your family.
Paula Rosenstock
State Representative Jay Livingstone says:
I'm so sorry for your loss. Thank you for your eloquent post regarding your impressive mother.
Madeleine C says:
Thank you for sharing your mother's story. What an inspiration, and what a beautiful life. So sorry for your loss.
CATHERINE DALEY says:
Beautiful tribute
JudyF says:
wow your mom sounds like an incredibly thoughtful and loving human being. So sorry for your loss.
Sorry for your loss, Senator. My heartfelt condolences to you and your family.
Arthur Robillard says:
She sounds like a deep, empathetic and authentically good person. How much better life would be if there were more like her. I will pray for her.
John Merrifield says:
Dear Will, I have known Sue for sixty years. Much of the history in your memorial was unknown to me. But the elements I did recognize were precisely true, for which both Carole and I are thankful.
Will, my condolences. While I didn't know your family history (which is quite remarkable) or your mother's work, it always was a pleasure seeing her. Your mother always seemed like such an upbeat, positive force. Along with many others I will miss her.
Che says:
Heartfelt condolences, sir; and in humble respect and gratitude for your words full of love for your mom. Che
Thomas M Jones says:
Sending my deepest condolences. Your tribute is so beautifully and lovingly written.
My sympathy to you and your family.
Caroline Reeves says:
You honor your mother with this beautiful memorial. And when it's hard, remember, she will always be with you, that is the magic of mothers. My deepest sympathies to your whole family–sounds like a life well lived and loved, with lessons for us all.
Sibylle says:
Will, I am so sorry you lost your mother! She sounds like an amazing woman. Your words help to explain a bit why you are in public office.
How wonderful that she researched your history & left you with such personal & historical family stories. Sending you & your family my sympathy-
Susan B. Jones says:
Will, I am so sorry to learn this news. Over the years, I have enjoyed running into Susan as I went about my life. I would always stop to chat with her whether at march or a meeting or in the street or on the T. Another hole left unfillable. My condolences to all of you.
Rachel Heller says:
I am so sorry for your loss. Losing your mother is so incredibly painful. It is clear that her spirit will live within you, your work, and your studies of history. She sounds remarkable. I hope memories of her bring comfort. I am thinking of you and your family.
Nathaniel Harrison says:
Senator Brownsberger,
This is a compelling tribute and her life and legacy an inspiration. You have my deepest sympathy.
Rich Hickey says:
Will, so sorry for your loss. I remember your beautiful mom way back when I did work on her Russell Ave home. Like my mom she was a gigantic influence on your life. May she rest in pease. Rich Hickey
Kathy Markham says:
Will, I am so sorry for your loss. No matter how old we are when a parent passes, the loss is deep. Your tribute to her is beautiful and you have good memories of your Mother and a family history to hang onto.
Charles and Eleni Sacre says:
My wife Eleni and I present our most sincere condolences to you and to all your family.
A remarkable lady, a role model to all mothers and human beings, May her soul rest in the peace of the Lord.
Anne Benaquist says:
I'm so sorry to hear of your mother's death. Your essay has added many new admirers (like me) to the family and friends who mourn her passing. What a great woman. Thanks for sharing.
Linda Montagna says:
Thank you for sharing this beautiful tribute of your Mom. I imagine you both having had wonderful conversations. She has certainly left a beautiful legacy and I'm sad for your loss.
Louise Civetti says:
What an incredible woman. This beautifully written tribute reflects her influence on you. Her legacy will live on. My sincere condolences on the loss of your mom. It is never easy to lose a parent.
Will, I am really sorry for your loss. I saw your mother last year and indeed – she was a really gracious and warm person. My deepest sympathy for you and your family.
Anu Narayanan says:
Senator – Really sorry for your loss. Thank you for taking the time to write/share this beautiful tribute to your mother. Sounds like she was a wonderful human being; empathetic, patriotic and a remarkable person. Sending you and your family prayers.
Judith Feinleib says:
I met your mother when you were first elected to the Senate. In addition to all you have said, she was an elegant lady. May your grief be short and your memories be sweet.


text:
Progressive Unilateral Encephalopathy of Childhood (Rasmussen's Syndrome): A Reappraisal
Eileen P.G. Vining, John M. Freeman, Jason Brandt, Benjamin S. Carson, Sumio Uematsu
Summary: Twelve children with Rasmussen's encephalitis underwent hemispherectomy and have been followed for an average of 9.15 years. Our decision‐making process leads to early, rather than late operation. Because hemiplegia is inevitable with or without operation, earlier operation may allow such children to resume a more normal life. We postulate that earlier operation may prevent some of the intellectual decline that accompanies the continued seizures and their treatment. In view of the variable pathologic findings and lack of evidence of a viral etiology, we suggest either use of the term "progressive unilateral encephalopathy of childhood" or "Rasmussen's syndrome" in recognition of its heritage.
Hemispherectomy
Neurologic examination
Rasmussen's encephalitis
Dive into the research topics of 'Progressive Unilateral Encephalopathy of Childhood (Rasmussen's Syndrome): A Reappraisal'. Together they form a unique fingerprint.
Encephalitis Medicine & Life Sciences 100%
Brain Diseases Medicine & Life Sciences 89%
Hemispherectomy Medicine & Life Sciences 72%
Hemiplegia Medicine & Life Sciences 57%
Seizures Medicine & Life Sciences 36%
Vining, E. P. G., Freeman, J. M., Brandt, J., Carson, B. S., & Uematsu, S. (1993). Progressive Unilateral Encephalopathy of Childhood (Rasmussen's Syndrome): A Reappraisal. Epilepsia, 34(4), 639-650. https://doi.org/10.1111/j.1528-1157.1993.tb00441.x
Progressive Unilateral Encephalopathy of Childhood (Rasmussen's Syndrome) : A Reappraisal. / Vining, Eileen P.G.; Freeman, John M.; Brandt, Jason et al.
In: Epilepsia, Vol. 34, No. 4, 07.1993, p. 639-650.
Vining, EPG, Freeman, JM, Brandt, J, Carson, BS & Uematsu, S 1993, 'Progressive Unilateral Encephalopathy of Childhood (Rasmussen's Syndrome): A Reappraisal', Epilepsia, vol. 34, no. 4, pp. 639-650. https://doi.org/10.1111/j.1528-1157.1993.tb00441.x
Vining EPG, Freeman JM, Brandt J, Carson BS, Uematsu S. Progressive Unilateral Encephalopathy of Childhood (Rasmussen's Syndrome): A Reappraisal. Epilepsia. 1993 Jul;34(4):639-650. doi: 10.1111/j.1528-1157.1993.tb00441.x
Vining, Eileen P.G. ; Freeman, John M. ; Brandt, Jason et al. / Progressive Unilateral Encephalopathy of Childhood (Rasmussen's Syndrome) : A Reappraisal. In: Epilepsia. 1993 ; Vol. 34, No. 4. pp. 639-650.
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title = "Progressive Unilateral Encephalopathy of Childhood (Rasmussen's Syndrome): A Reappraisal",
abstract = "Summary: Twelve children with Rasmussen's encephalitis underwent hemispherectomy and have been followed for an average of 9.15 years. Our decision‐making process leads to early, rather than late operation. Because hemiplegia is inevitable with or without operation, earlier operation may allow such children to resume a more normal life. We postulate that earlier operation may prevent some of the intellectual decline that accompanies the continued seizures and their treatment. In view of the variable pathologic findings and lack of evidence of a viral etiology, we suggest either use of the term "progressive unilateral encephalopathy of childhood" or "Rasmussen's syndrome" in recognition of its heritage.",
keywords = "Electroencephalography, Epilepsy surgery, Hemispherectomy, Intelligence, Neurologic examination, Neurosurgery, Rasmussen's encephalitis",
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T2 - A Reappraisal
AU - Vining, Eileen P.G.
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AU - Uematsu, Sumio
N2 - Summary: Twelve children with Rasmussen's encephalitis underwent hemispherectomy and have been followed for an average of 9.15 years. Our decision‐making process leads to early, rather than late operation. Because hemiplegia is inevitable with or without operation, earlier operation may allow such children to resume a more normal life. We postulate that earlier operation may prevent some of the intellectual decline that accompanies the continued seizures and their treatment. In view of the variable pathologic findings and lack of evidence of a viral etiology, we suggest either use of the term "progressive unilateral encephalopathy of childhood" or "Rasmussen's syndrome" in recognition of its heritage.
AB - Summary: Twelve children with Rasmussen's encephalitis underwent hemispherectomy and have been followed for an average of 9.15 years. Our decision‐making process leads to early, rather than late operation. Because hemiplegia is inevitable with or without operation, earlier operation may allow such children to resume a more normal life. We postulate that earlier operation may prevent some of the intellectual decline that accompanies the continued seizures and their treatment. In view of the variable pathologic findings and lack of evidence of a viral etiology, we suggest either use of the term "progressive unilateral encephalopathy of childhood" or "Rasmussen's syndrome" in recognition of its heritage.
KW - Electroencephalography
KW - Epilepsy surgery
KW - Hemispherectomy
KW - Intelligence
KW - Neurologic examination
KW - Neurosurgery
KW - Rasmussen's encephalitis
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JF - Epilepsia