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Home » SYNTHESIS AND SPECTROSCOPIC STUDIES OF COBALT (II) COMPLEXES WITH NITROGEN- OXYGEN AND NITROGEN SULPHUR DONOR LIGANDS
SYNTHESIS AND SPECTROSCOPIC STUDIES OF COBALT (II) COMPLEXES WITH NITROGEN- OXYGEN AND NITROGEN SULPHUR DONOR LIGANDS
Sulekh Chandra * 1, Smriti Raizada 2 and Sangeeta Sadwal 2
Department of Chemistry 1, Zakir Husain Delhi College, University of Delhi, Jawaharlal Nehru Marg, Delhi - 110002, New Delhi, India.
Department of Chemistry 2, M. M. H.College, Chaudhary Charan Singh University, Ghaziabad - 250001, Uttar Pradesh, India.
ABSTRACT: CoII complexes of ligands pyridine3carboxamide thiosemicarbazone (L1), pyridine 3 carboxamide semicarbazone (L2), pyridine2carboxamide thiosemicarbazone (L3) and pyridine 2 carboxamide semicarbazone (L4) have been synthesized. The ligands were characterized based on elemental analyses, IR, 1HNMR studies while the complexes were characterized by elemental analyses, molar conductance, magnetic moment, IR, electronic and EPR spectral studies. The complexes are not soluble in ordinary organic solvent but highly soluble in dimethylsulfoxide. The conductivity data show the nonelectrolytic nature of the complexes. Based on elemental analyses, molar conductance data and other spectral studies the complexes were found to have general composition [Co (L)2X2] (where L=L1, L2, L3 and L4, X = Cl–, ½SO42–,NO3-) and exhibit distorted octahedral geometries.
Pyridine carboxamide, Thiosemicarbazone, Semicarbazone, Schiff bases
INTRODUCTION: Nitrogen-containing metal chelates esp. schiff base ligands (-CH=N-) form important physiologically and pharmacologically compounds. Schiff bases are widely studied for their unparalleled recognition in biological systems 1 to comprehend the structures of biomolecules 2. Schiff bases can accommodate different metal centers esp. transition metals by different coordination modes allowing successful synthesis of homo and heterometallic complexes with wide-ranging stereochemistry 3.
Schiff bases derived from thiosemicarbazide, semicarbazide, and their metal complexes are of great significance for their pharmacological properties such as antimicrobial 4, antifungal 5, antitumor, antiviral 6, 7, anticancer 8-14.
It is documented that heterocyclic compounds play a significant role in many biological systems, especially N-donor ligand systems, being a component of several vitamins and drugs such as nicotinamide. Nicotinamide (pyridine -3- carboxamide) is known as a component of the vitamin B complex as well as a component of the coenzyme, nicotinamide adenine dinucleotide (NAD). Nicotinamide is a bioligand for human health which plays an important role in the metabolism of living cells, and some of its metal complexes are biologically active as antibacterial or insulin-mimetic agents.
Therefore, the structure of nicotinamide has been the subject of many studies. It is currently in the trial as a potential means of preventing the onset of Type I (insulin-dependent) diabetes mellitus in high-risk, first-degree relatives.
It has been classed as a food additive rather than a drug. Nicotinamide and picolinamide also serve as model compounds for the conformations of polypeptides and nucleic acids. The amide groups in picolinamide and nicotinamide can adopt a variety of tautomeric and rotameric structures in addition to forming interesting molecular associations via hydrogen bonding. Picolinamide (pyridine -2- carboxamide) introduces a novel twist in the carboxamide potential by its ability to form an intramolecular hydrogen bond between the amide and the pyridine ring.
The extensive research has been done in our lab 15 elucidating the coordination behavior of transition metal complexes (3d, 4d, 5d) with thiosemicarbazone which has been proved to be potent antitumor, antiviral, anticarcinogenic, antituberculosis 16, antioxidant, antibacterial activities, bactericidal and fungicidal agents 17, 18.
Recently thiosemicarbazone based ligands have been studied for their use as sensors 19. In this paper, we report the synthesis and spectral investigations of Co (II) complexes with semicarbazide and thiosemicarbazide based ligands: (L1), pyridine3carboxamide semicarbazone (L2), pyridine2carboxamide thiosemicarbazone (L3) and pyridine2carboxamide semicarbazone (L4) to study their structure-activity relation.
EXPERIMENTAL: All the chemicals used in the present work were of high purity, Anal. R grade, and procured from Sigma-Aldrich. Metal salts were purchased from E. Merck and used as received. The solvents used were either spectroscopic pure from SRL/BDH or purified by the recommended methods.
Synthesis of Ligands: Hot ethanolic solution (20 mL) of pyridine-3- carboxamide and pyridine-2 - carboxamide (0.91g, 0.01mol) was added to a hot ethanolic solution of thiosemicarbazide (1.22g, 0.01mol) in the presence of 0.5 mL acetic acid. The contents were refluxed at 70–80 ºC for about 8-10 hrs on a water bath with constant stirring. On cooling the contents L1 and L3 the yellow-colored compounds were separated. The completion of the reaction was confirmed by the TLC. The solvent was removed using a rotary evaporator, and light yellow colored solid was obtained. It was washed with cold ethanol and dried under vacuum over P4O10, yield 68%, melting point-198-200 ºC, soluble in water Fig. 1.
An aqueous solution (50 mL) of semicarbazide hydrochloride (5.55 g, 0.05 mol) added in an ethanolic solution (50 mL) of corresponding amide pyridine -3-carboxamide and pyridine-2- carboxamide (4.75 gm, 0.05 mol) in the presence of sodium acetate (4.1 g, 0.05 mol). The reaction mixture was stirred vigorously for an hour. The crystalline product L2, L4 which formed was collected by filtration in each case washed several times with hot water and dried in vacuum over P4O10 Fig. 1.
The characterization details are tabulated in Table1.
Preparation of Metal Complexes: Hot ethanolic solution of metal salts (1 mmol), cobalt chloride hexahydrate (0.237 g), or cobalt nitrate hexahydrate (0.291 g), was mixed with a hot ethanolic solution of the corresponding ligand (2 mmol) (L1, L2, L3, L4). The mixture was refluxed for 8-10 h at 70–80 ºC. On cooling the contents, the complex separated out in each case. It was filtered, washed with 50% ethanol, and dried under vacuum over P4O10. The characterization details are tabulated in Table 1.
Physical Measurements: The C, H, and N were analyzed on a Carlo-Erba 1106 elemental analyzer. Molar conductance was measured on an ELICO (CM82T) conductivity bridge. Magnetic susceptibilities were measured at room temperature on a Gouy balance using CuSO4⋅5H2O as calibrant IR spectra (KBr) were recorded on an FTIR spectrum BX-II spectrophotometer. The electronic spectra were recorded in DMSO on a Shimadzu UV mini-1240 spectrophotometer.The1H NMR spectrums were recorded on a Jeol FT-NMR Spectrometer using DMSO as a solvent. Thermogravimetry (TG) and Differential thermogravimetric analysis (DTA) for the metal complexes were carried out on a Perkin Elmer Diamond TG-DTA spectrometer for the determination of complex entrapped water.
RESULTS AND DISCUSSIONS:
Physical Properties: The analytical data of the ligands and its complexes with their physical properties are given in Table 1. All the complexes have shown good solubility in DMSO but they were found insoluble in ether, water, acetone, and benzene. The interaction of the ligand with metal salts in 1:1 molar ratio in EtOH yielded stable solid.
The elemental analysis and molar conductance of complexes in DMSO correspond to non-electrolyte nature with general composition. [Co (L)2 X2] (Where L= L1, L2, L3, L4; X=Cl-, NO3--, 1/2SO42-) .
TABLE 1: MOLAR CONDUCTANCE AND ELEMENTAL ANALYSIS DATA OF CO II COMPLEXES
Complexes Colour Molar conductance Yield
% Melting Point ºC Elemental analysis data found
(Calculated )
M C H N
Ligand (L1,L3)
C7H9N5S Pale yellow - 73 198 - 43.0
(42.95) 4.61
Ligand(L2,L4) C7H9N5O white - 64 190-194 - 46.91
(5.02) 39.11
[ Co(L1)2Cl2]
CoC14H18N10S2 Cl2 Pink 19
59 258 11.30
(11.32) 32.27
[ Co(L1)2SO4]
CoC14H18N10S3O4 Pink 20 63 235 10.76
(10.80) 30.6
(30.8) 3.31
[ Co(L1)2 (NO3 )2]
CoC14H18N12S2 O6 Reddish pink 19 68 234 10.24
CoC14H18N10O2 Cl2 Pink 20 65 220 12.06
CoC14H18N10 O6S Bluish pink 17 58 222 11.45
CoC14H18N12 O8 Reddish pink 15 57 246 10.84
CoC14H18N10S2 Cl2 Purple 15 60 255 11.30
[Co(L3)2SO4] CoC14H18N10S2 Cl2 Purple 21 62 274 10.76
[Co(L3)2(NO3)2] CoC14H18N10S2 Cl2 Reddish pink 21 59 251 10.24
[Co(L4)2Cl2] CoC14H18N10S2 Cl2 Red 19 58 253 12.06
[Co(L4)2SO4] CoC14H18N10S2 Cl2 Red 20 60 211 11.45
[Co(L4)2(NO3)2] CoC14H18N10S2 Cl2 Red 18 61 284 10.84
IR Spectra: IR spectra of the ligands show bands at ~3200-3300 and 3100-3400 cm−1 which may be assigned to [(NH2)] and [(NH)] groups, respectively. The bands due to [?(C=S)] appeared at~ 801 cm−1, [?(C=O)] at~1684 and the bands at ~1618 cm−1 may be assigned to symmetric or asymmetric [?(C=N)] group.
The assignments of the significant IR spectral bands of the metal complexes are shown in Table 2 which clearly show the shifting of the bands corresponding to ? (–C=N), (–C=S) and [?(C=O)] in ligands towards the lower side (around ca. 20–50 cm−1) on complexation. This suggests that the ligands act as bidentate chelating agent coordinating through the nitrogen of C=N group, sulfur of C=S group and oxygen of C=O.
TABLE 2: IMPORTANT IR BANDS AND ASSIGNMENT OF SEMICARBAZONE AND THIOSEMICARBAZONE BASED LIGANDS AND THEIR CO (II) COMPLEXES
Compound ν (C=N ) ν(C=O ) ν (NH ) ν (C-S ) ν (M-O/M-S )
(LI) 1618 - 3399 801
[ Co(L1)2Cl2] 1574 - 3269 764 430
[ Co(L1)2SO4] 1560 - 3292 756
[ Co(L1)2 (NO3 )2] 1580 - 3307 782 434
(L2) 1620 1684 3400 -
[ Co(L2)2Cl2] 1565 1678 3101 -
[ Co(L2)2SO4] 1549 1652 3102 -
[ Co(L2)2 (NO3 )2] 1591 1656 3258 -
(L3) 1628 - 3367 800
[ Co(L3)2Cl2] 1583 - 3275 780 _
[ Co(L3)2 (NO3 )2] 1565 - 3332 773 _
Electronic Spectra and Magnetic Moment: The magnetic moments of all the Co II complexes lies in the range 4.89-5.02 BM corresponding to three unpaired electrons. This indicates that the coordination takes place through the nitrogen atoms of the imine group, sulfur atom of >C=S, oxygen atom of >C=O group which corresponds to octahedral symmetry Table 3.
TABLE 3: MAGNETIC MOMENT AND ELECTRONIC SPECTRAL DATA OF COII COMPLEXES
Complexes μeff (BM) λ max(cm-1)
[ Co(L1)2Cl2] 4.95 8801, 18609, 22460
[ Co(L1)2 (NO3 )2] 4.89 8876, 19502, 23575
[ Co(L3)2 (NO3 )2] 5.00 8890, 18725, 2676
EPR Spectra: The X band EPR spectra of Co (II) complexes display the broad signal value of g in range g Π = 2.0001-2.0069, g┴ = 1.9763-2.0076 and g iso = 1.9895-2.0064 corresponding to the tetragonal symmetry around Co(II) atoms 20.
Thermal Analysis of Metal Complexes: Crystal water content in complex [Co (L1)2Cl2] (1) and its thermal stability was determined by the TGA and DTG techniques Fig. 2. The metal complex (1) show major weight loss above 133 ºC which shows that it is free of any entrapped water. The data obtained for other complexes was reprehensible. The complex (1) decomposes in two steps by oxidative degradations; in the final step (>690 ºC) results in the metallic oxide Co3O4 as stable residue. Data from the thermal analysis sustains the molecular formulas assigned for these complexes. It shows a total mass loss of 85.6% at 133-280 ºC, 50.9% at 280 ºC, 14.39% at 690 ºC.
FIG. 2: THERMO GRAVIMETRIC ANALYSIS (TGA) OF COBALT COMPLEX [Co (L1)2(Cl)2]
Suggested Structure of the Complexes: On the basis of the above spectral studies the following structure may be suggested for the complexes Fig. 3, 4.
CONCLUSION: The present work describes the facile synthesis of metal complexes with newly synthesized ligands. Spectral data confirms that the ligands are bidentate and metal complexes have distorted octahedral geometry which may be formulated as [Co (L)2X2] (where L = L1, L2, L3, L4; X=Cl-, NO3--,1/2SO42-). An interesting fact is that the ligand being water-soluble can be further studied for their applications as chelating agents, work for which is being carried out in our lab.
ACKNOWLEDGEMENT: The authors are thankful to the UGC New Delhi for financial assistance, IIT Mumbai, for recording EPR spectra and IIT Delhi, for recording NMR spectra.
CONFLICT OF INTEREST: Nil
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Chandra S, Raizada S and Sadwal S: Synthesis and spectroscopic studies of Cobalt (II) complexes with nitrogen- oxygen and nitrogen sulphur donor ligands. Int J Pharm Sci & Res 2014; 5(11): 4718-23. doi: 10.13040/IJPSR.0975-8232.5(11).4718-23.
Authors: S. Chandra *, S. Raizada and S. Sadwal
Authors Address: Department of Chemistry, Zakir Husain Delhi College, University of Delhi, Jawaharlal Nehru Marg, New Delhi, India.
Email: schandra_00@yahoo.com
Revised: 14 June 2014
DOI: 10.13040/IJPSR.0975-8232.5(11).4718-23

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What does Israel do with U.S Grants?
Thread: What does Israel do with U.S Grants?
Hello all, I am a new member, so please all welcome me to the real world of social disorder and chaos.
After reading some very interesting articles regarding the Jewish full control over U.S Media, Television channels, radio, and daily life, I came to the conclusion, how did these jews acquire such vast wealth, enough to buy major film companies, Tv shows, Radio channels, ETC which ranges in the way over the Billions of dollars? According to research, I came to the fact that The Jewish population of America in in the 2 percent range, but yet half of them are BILLIONAIRES and play in crucial roles and imprtant positions among Contemporary life in America? My best Preassumation would be that the 3+ Billions in grants and loans that the U.S are donating to the FilthyNation of Israel are being sent back to Jewish Intellectuals inside the U.S for the sole purpose of dominating America. I call all those who believe theat the Jews are nothing but worthy sub-humans, shall sread the message that Zionism is controlling life in America with the use of American money!!
[QUOTE=Virtus]Hello all, I am a new member, so please all welcome me to the real world of social disorder and chaos.
what makes you think that they're somehow getting grants to send to israel and back here to rule the world or whatever through the U.S.????
what are your sources??? and specifically what do you mean???
or are you just afraid that the jews are going to take over the world?


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Home » F1 blog » Is Max Verstappen better than Daniel Ricciardo?
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Is Max Verstappen better than Daniel Ricciardo?
by Motorsport.com
Max Verstappen VS Daniel Ricciardo
One of my friends asked me 'is Max Verstappen better than Daniel Ricciardo and who is better?' That was on the eve of Mexico Grand Prix. Of course, Verstappen is better, because he has everything that needs to become a world champion! But, Daniel Ricciardo is restrained and clever, told my friend. He deserves Formula 1 world champion's title. Completely different, almost opposite F1 drivers. Who's better? I decided to think about the qualities of true Formula 1 world champions.
Dare to risk.
Max Verstappen drives aggressive and it's no longer a secret. He is ready to take risks and almost never gives up his positions. Ricciardo has a little different style of driving. Daniel takes risks when it's necessary only.
I want to say that Verstappen operates at the limit of their capabilities and emotions in every race, and Daniel Ricciardo more restrained and thinking twice before doing, trying to not to show emotions.
Sometimes it reminds me, Nico Rosberg. However, the willingness to take a risk at any time distinguishes the champion.
Dare to be better, what's the matter who and what did say!
I think that's Verstappen's motto. Under his every successful lap with the best seconds, you can remember the same unsuccessful, and sometimes a failed lap. Despite the condemnation and reproaches, he continues to be better and learn by his mistakes.
Ricciardo hasn't such loudly moments, shows high-level driving, his mistakes don't allow to judge him as a Formula 1 driver. There is the only impulsiveness of characters.
Dare to go your own way. The greatest Formula 1 drivers choose their own ways. Yes, there were mistakes, there were fails. However, this is the reason to lead everyone to success. Senna, Schumacher, even Hamilton has his opinion, whatever it takes. That's what Ricciardo does: he leaves Red Bull F1 team since next year. In his own way, Max Verstappen has been choosing, when a disgruntled crowd whistles. They remain true to themselves, that's why they have more fans day by day.
Sometimes you think it's hard work or just luck? Why is one working and another lucky? However, success is always hard work with yourself, especially in such motorsport as Formula 1 racing.
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Granada from the 17th to 20th Century.
Following the conquest of Granada in 1492, the victorious Christians quickly established their presence, converting mosques into churches, building new churches, monasteries, convents and a large cathedral where the grand mosque had once stood. Much of what identified the city as Muslim still remained (the Alhambra, the Albaicín), but Christian architecture was evidence of a new direction in the destiny of the city.
The flurry of building in the 16th century slowed down in the 17th century as the city went into a long decline, as did much of the rest of Spain. There were sporadic attempts at industry in the 18th century, but as in the rest of Andalusia it failed to take root. Granada was no more than a provincial city with seemingly little ambition.
The situation did not improve in the 19th century. And but for a stroke of fortune Granada might easily have lost its most prized treasure and source of much of its economic well-being … the Alhambra.
In the early years of the 19th century, the city was taken by Napoleon's troops during the course of the Peninsular War (or War of Independence to Spaniards). The French not only stationed their soldiers in the Alhambra, but also kept prisoners and stored dynamite in the buildings. Upon retreat, they blew up some of the Moorish towers but fortunately were unsuccessful in destroying the palace complex.
What is clear from travelers' reports at this time is that Granadinos themselves were indifferent to the beauty of the Alhambra. It was populated by gypsies and the penniless, and served as a prison and military hospital.
Richard Ford, traveling in Spain in the 1830s, is caustic about the neglected state of the Alhambra. Granadinos, he says, "despise the Alhambra as a "casa de ratones," or rat's hole, which indeed they have made it… They resent almost as heretical the preference shown by foreigners to the works of infidels rather than to those of good Catholics."
It was a foreigner, the American diplomat and scholar Washington Irving, who more than anyone else brought the Alhambra to the popular imagination. While staying in the Alhambra in 1829 he began writing the book for which he is best known: Tales of the Alhambra, a combination of romantic legend and descriptions of the place and the people living there. At a time when Romanticism was in the air and the exotic was in vogue, the tales of Medieval Muslim Spain were particularly attractive. Irving's book sold widely and put Granada on the tourist map.
Modern Granada.
Granada entered the 20th century on the back of its tourist appeal. Although Andalusia at this time was subject to frequent anarchist outbursts from impoverished peasants ("campesinos"), Granada was solidly conservative. Its backbone was the military and the church, and a middle class that was inward looking and unadventurous.
Richard Ford had described the society of Granada in the 1830s as "dull" and "ignorant." Over 100 years later, the poet Federico García Lorca –one of Spain's greatest poets and dramatists, and native of Granada– reproached Granadinos as "the worst bourgeoisie in Spain today."
Lorca himself was shot soon after in Granada, an early victim of the Civil War (1936-39) in which Granada –after a brief and bloody purge of anyone with liberal sympathies– quickly sided with the Franco rebels against the central government.
Since the death of Franco (1975), Granada has transformed itself into a prosperous, bustling city. Its student life is reputed to be the liveliest in Spain, and night life goes on to the early hours of the morning. A magnificent interactive Science Park was opened in the city in May 1995, its ultramodern architecture a symbol of confidence in the city's future.
The high rise buildings that have invaded the plain (vega), and the congested traffic are the scourge of modern urban sprawl. Modern Granada is a cacophony of blaring car horns and the high pitched buzz of mopeds that weave suicidally between traffic.
Granada: the Albaicín and the Return of Islam.
Standing above the noise on their respective hills overlooking the modern city, the Albaicín (or Albayzín) and the Alhambra restore a balance of sanity. True, there are lots of tourists but there is always a hidden corner, an unexpected discovery to be made.
Albaicín. San Nicolás church to the left. The new mosque's minaret can be made out in the middle top.
This is especially so in the Albaicín, with its hilly, narrow, winding streets and intimate squares. It is to the Plaza de San Nicolás that many tourists go for a distant view of the Alhambra, across the gorge that divides the two hills. At dusk, the breathtaking sight of the reddish-coloured Palace against the backdrop of the snow-covered Sierra Nevada is one of the most memorable images they will take with them.
It is views like this that prompted the 20th-century Mexican poet and diplomat, Francisco Alarcón de Icaza, to exclaim: dale limosna mujer/ que no hay en la vida nada/ como la pena de ser ciego en Granada ("Give him alms lady, for there is nothing in life as wretched as being blind in Granada"). These lines can now be found in several spots in the city.
The Alhambra from the Plaza de San Nicolás in the Albaicín
A feature of the Albaicín is the carmen, a Moorish-style house set in gardens with flowers, fruit trees, plants, fountains, and slender, vivid green cypresses, all enclosed by high walls. The cármenes are to old Granada what the patios are to old Córdoba, private spaces, a kind of inner paradise meant for the pleasure of the family.
Another much more recent feature of the Albaicín is the presence of Muslims, many of whom are converts to Islam. In the streets of the Albaicín now you can find tea houses serving mint tea, coffee, juices accompanied by Arabic music and Arab news reports on the radio.
There are halal butcher shops, and bakeries selling baklava and kenafa (a soft cheese), and shops that sell leather goods, sandals, incense, spices etc. During the holy month of Ramadan some shops display signs in their windows wishing passersby Feliz Ramadan.
Nevertheless, the major Muslim attraction in the Albaicín is the new mosque sitting next to a convent close to the Plaza San Nicolás.
Granada's new mosque.
The mosque opened in July 2003, the culmination of 22 years of effort to overcome the various objections raised by city leaders and by neighbourhood resistance. The opening was attended by various Muslim and non-Muslim dignitaries, including the mayor of Granada, a member of the then ruling right-wing Partido Popular party.
It is the first mosque built in Granada in over 500 years (the Muslims of Granada earlier met in makeshift centres) and carries with it significant symbolic value, not always interpreted in the same way by Muslims in Spain.
Native-born Muslims, who make up most of the congregation, are anxious not to arouse fears of an Islamic reconquest of Andalusia. They want to promote a tolerant and democratic Islam which is able to live with its Catholic neighbours, not an easy task when al-Andalus was frequently evoked by Osama bin Laden and his followers as territory to be reclaimed for Islam.
Beyond the Albaicín, on the edge of the town, is the gypsy cave district of Sacromonte, the most popular place to go to for flamenco dancing. There's a lot of debate about the quality of the shows, but it can be a fun if somewhat more expensive experience than bargained for. Be cautious is the advice usually given to visitors, especially at night.
Fletcher, Richard Moorish Spain London, 1994
Fletcher, Richard The Cross and the Crescent London, 2003
Ford, Richard A Hand Book for Travellers in Spain London, 1845
Gilmour, David Cities of Spain London, 1994
Jacobs, Michael A Guide to Andalusia London: Viking 1990
An interesting article on the building of the new mosque in Granada can be read in: http://www.guardian.co.uk/world/2003/dec/06/spain.gilestremlett


text:
Neurosurgical Focus
An Ethical Framework for Deep Brain Stimulation in Children
Benjamin Davidson, MD; Lior M. Elkaim; Nir Lipsman, MD, PhD; George M. Ibrahim, MD, PhD
Neurosurg Focus. 2018;45(3):e11
Abstract and Introduction
The Population: Ethical Challenges in Vulnerable Patients
The Procedure: Known and Unknown Risks of Surgical Innovation
The Element of Time: Interaction Between Disease Course and the Child's Development
The Technical Nuances: Ethical Challenges Introduced by Technical Considerations
The Evidence: Translating From Adult to Pediatric Populations
Ethical Framework for Pediatric DBS
DEEP brain stimulation (DBS) is increasingly considered for the treatment of refractory neurodevelopmental conditions affecting children.[25] In 1999, Coubes and colleagues were among the first to report on the use of pediatric DBS for primary dystonia.[9] Since then, pediatric DBS has gained considerable traction, with several case series reported.[25,29] Although dystonia remains the most common indication for pediatric DBS, the technology has also been applied to treat epilepsy[44] and Tourette syndrome.[38] More recently, DBS of the nucleus accumbens and amygdala have been reported for self-injurious behaviors.[34,41]
The majority of the evidence for DBS in children has been derived from the adult literature, in which the procedure has been shown to be safe and effective for an increasing number of indications.[37] However, pediatric DBS has many substantial differences, with important bioethical, social, and legal considerations. First, patients and their caregivers represent a uniquely vulnerable population. Second, given biological differences between adults and children, the procedure in pediatric populations can be considered a surgical innovation and is still investigational for all indications. Third, the natural history of a disease within the context of a child's neuromuscular and cognitive development must be factored into treatment decisions. Furthermore, the surgical risks and technical nuances of DBS differ from those in adults. Thus, evidence from the adult DBS literature may not be readily translatable to pediatric populations.
With the exception of DYT1 dystonia (for which there is level II-2 evidence[45]), all indications for DBS in pediatric patients are in the early stages of investigation; thus, the procedure represents a surgical innovation, i.e., a procedure that "departs in a significant way from standard or accepted practice."[11] Surgical innovations are characterized by evolving techniques, outcome measures, and patient selection.[31] Three systematic reviews and meta-analyses (two manuscripts currently under review and one paper in press[10]) have described the conduct of DBS in pediatric populations (Table 1), all emphasizing significant heterogeneity and the need for prospective studies to guide patient selection. The framework we describe here is intended to be applied to DBS in children in all settings, most of which are presently experimental or under the realm of surgical innovation. Ultimately, the most basic ethical principles protecting research subjects flow from the Nuremberg Code (1948), the Declaration of Helsinki (1964), and the Belmont Report (1979); however, in children with a medically complex condition who may benefit from novel investigational treatments, a more targeted framework is needed.[11,14,43]
Herein we expand on differences in the conduct of DBS between adults and children and the unique ethical challenges they pose. First, we describe ethical issues raised by the vulnerability of the patient population, the novelty of the application of DBS for expanding indications in children, and the conduct of the procedure in children despite limited evidence. We then propose a bioethical framework for the evaluation of children for DBS. Although ethical issues may figure more or less prominently depending on the individual patient and the indication, the framework we put forth may be generalized to shape personal, institutional, and social policies regarding DBS in children. It is not our intention to prescribe the steps and thought process for carrying out pediatric DBS, but rather to advance dialogue regarding the ethical underpinnings of this promising technique in children.
Neurosurg Focus. 2018;45(3):e11 © 2018 American Association of Neurological Surgeons
Table 1. Systematic reviews and meta-analyses of DBS in exclusively pediatric populations
Indication No. of Subjects (total no. of studies)
Elkaim et al., 2018* Primary & secondary dystonia Primary: 173; secondary: 139; myoclonus: 9 (72)
Coulombe et al., 2018 (in press) Tourette's syndrome 58 (21)
Yan et al., 2018* Epilepsy 40 (21)
*Manuscripts currently under review.
Table 2. Guidelines for the ethical conduct of DBS in children
Research design & conduct in the child's best interest
Hypotheses, outcomes, & procedures viewed in a developmentally relevant context
Realistic discussion of what is known & what is unknown regarding the risk profile in pediatric DBS; weighing the decision to proceed with & the timing of DBS vs other treatments with better known efficacy & risk profiles
Cautious application of adult data to the design of pediatric clinical trials
Diligently report methods & results to the neurosurgical community in the spirit of collaboration
Benjamin Davidson, MD1, Lior M. Elkaim2, Nir Lipsman, MD, PhD1,3 and George M. Ibrahim, MD, PhD1,4
1Division of Neurosurgery, Department of Surgery, University of Toronto, Ontario; 2Faculty of Medicine, Université de Montréal, Québec; 3Division of Neurosurgery, Sunnybrook Health Sciences Centre, University of Toronto, Ontario; and 4Division of Neurosurgery, Hospital for Sick Children, Program in Neuroscience and Mental Health, Hospital for Sick Children Research Institute, University of Toronto, Ontario, Canada
George M. Ibrahim: george.ibrahim@sickkids.ca.
The authors report no conflict of interest.
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2001http://www.medscape.com/features/year-in-medicine/public/2014
The Year In Medicine 2014 Special Collection


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It's been known for thousands of years that our main abdominal organs also process certain of our thoughts. In my new book, I've described our immune system as also having mental functions, just as the other organs have; and I've given examples of the types of thoughts our immune system produces in us.
I was recently ill. It seemed my body had already successfully adjusted to Autumn, but then on the equinox I came down with a one day "bug". There was no initial sneezing, no congestion. I simply felt extremely weak; too weak to stand for long, so I spent most of the day sitting or lying. I felt nausea, had no appetite, and slightly achy joints. All my pulses were full (which is the opposite of their normal states in me) and there was a thick tongue coating, mostly in the stomach region, indicating the presence of a strong pathogen.
During this one day, when clearly my immune system was working hard, I felt a great dislike for almost all external stimuli, such as TV programmes, music, and I felt even more dislike than usual for "personality" factors; you could say I simply felt a dislike for any mental quality emanating from other people. I just wanted to sit in silence and not even look at anything; I even found the sight of my normal surroundings distasteful. At the time, my observation was that I was made extremely sensitive by the illness, even more sensitive than I was normally. But then afterwards, it occurred to me that this may have been the effect of my overactive immune system processing my thoughts and rejecting almost everything.
It's true that when you're ill, most of your senses can be affected; your sense of taste, smell, sight, hearing. This can be understood as being due to the physical affect of the illness on our body. But why would our thoughts be affected, and be affected in a way that resembles the action of our immune system?
Our immune system protects us from damaging external "pathogens". In our normal state, when our immune system is just "ticking over", it also appears to continuously processes our thoughts, just as all our other organs do, and it may recognise certain thoughts as harmful (the idea of a particular person's conduct, which our immune system recognises as alien in some way, distasteful, damaging to us, "infectious" and to be avoided; or any of our thoughts related to other things), causing us to reject that idea, person, or thing. But when my immune system was operating at its peak, at the moment of its greatest battle against this invading pathogen, its normal presence in my thoughts would also have been similarly amplified, which may have caused me to reject all the stimuli that I normally found either pleasing or simply neutral. And the following day, once I'd returned to normal, and my immune system had calmed down, I no longer found all these thoughts distasteful, and could enjoy them again.
Another factor that may be involved here is the mental function of our lungs. This is to discern quality in all the ethereal things around us (just at the physical lung function is to extract something precious from the air around us). And when ill in this way, our lungs are under attack. They are the first line of defence against such pathogens. Because my lungs were under this heavy attack and were weakened, my ability to appreciate quality in the things around me would also have been diminished, and this factor may have been partly responsible for me being unable to find pleasure in such things as media, sights, sounds, and so on. But then, the elements of our immune system that are present in our lungs could be considered an integral part of the lung function; the two are so intimately related that it may not be possible to separate them, when considering some of these mental functions.
The lungs extract something precious from the air around us (identify quality); and our immune system rejects pathogens (something harmful to us), which is another way of saying "something of poor quality". What's the difference between the inability to identify quality, and an exaggerated tendency to reject things as being of poor quality (harmful to us)? There is an obvious overlap here. One actively seeks quality; the other actively rejects poor quality. But what can be said is that when our lung function is weakened, so that we cannot appreciate quality, and our immune system is working hard, so that many of our thoughts may be rejected as possibly being harmful to us, then just about everything we encounter will seem unpleasant or distasteful to us.


text:
Girls Lacrosse: Martin, Sasso launch Freehold Township past Holmdel in SCT quarterfinals
Sherlon Christie
@sherlonapp
FREEHOLD TOWNSHIP – The Freehold Township girls lacrosse team has a knack for making Shore Conference observers take notice of the Patriots this season.
First, it was an 11-game winning streak to start the season that featured a win over fourth-ranked Manasquan on April 1.
Now, the Patriots have seized the spotlight again with a 10-5 win over sixth-ranked Holmdel in a Shore Conference Tournament quarterfinal game on Wednesday afternoon.
And it all started with the No. 3 seed Patriots' ability to take and win the draw against the No. 6 seed Hornets.
"Every girl (you take the draw against) is different. Literally every single one. The first girl I was taking the draw against it was a lot easier (against her) and then they (Holmdel) put someone else in and it made it hard for me for a couple times," said Freehold Township senior Nicole Sasso, who takes the draws for the Patriots. "I just had to adjust to it and I have Cai (Martin) and usually Kirsten (Murphy) or Madison (Hoskins) on the circle. It is a total effort from all three of us."
On several occasions, the Patriots (15-1) won the draw and immediately raced down the field and scored a goal. After Holmdel senior Chelsea Covino (one goal) scored with 14:33 left left in the second half and cut Freehold Township's lead to 5-4, the Patriots had a swift answer.
This time it was junior Cai Martin getting control of the draw and drawing opponents to her and then she quickly got rid of the ball to an awaiting junior Michelle Pascrell for the goal just nine seconds later.
"That's how Michelle (Pascrell) and I practice all the time. We've been playing together since the fourth or fifth grade. So, we are very comfortable with each other," Martin said. "So, I know if I draw two girls to me, she's going to be open every single time and I trust her to get the ball in the back of the net."
Girls Lacrosse: 2017 SCT First Round Recap
Girls Lacrosse: 2017 SCT Seeds, Schedule, Results
Girls Lacrosse: It's time for the SCT-themed version of the rankings for May 4
The Martin to Pascrell combination worked once again in the second half for a 7-4 lead with 12:09 left. The duo then ignited a game-breaking five-goal run that saw Freehold Township's lead swell from 5-4 to 10-4 with 7:11 left in the game. Naturally, Martin started and finished off that five-goal run with an assist, the last assist went to Sasso for that six-goal lead.
"We knew that Holmdel was gunning for us from the beginning and not many people expected us to win this game. So, we knew that possession was going to be key," Martin said. "We knew we had to keep time on our side and play our game, which is coming out and getting a big lead and holding onto it the whole game."
And the Patriots did just that against the Hornets (10-5) as they jumped out to a 4-0 lead with 6:54 left in the first half and never relinquished control to Holmdel.
Overall, Pascrell (four goals), Martin (three goals, four assists) and Sasso (two goals, two assists) and junior Lindsay Smith (five saves) powered the Patriots to their fourth win in a row. Now, Freehold Township has a showdown with No. 2 seed Red Bank Catholic in Friday's 7 p.m. SCT semifinal game at Ocean Township High School.
Meanwhile, senior Margie Quintana and sophomore Kinsey Clark each finished with two goals and senior Sarah Farag made four saves as the Hornets had their four-game winning streak snapped.
In other SCT quarterfinals
Red Bank Catholic 13, Red Bank 3: Olivia Farrington (five goals, one assist), Erin Mattone (four goals), Mackenzie Boyle (two goals, two assists) and Emily Kirman (13 saves) paced the No. 2 seed Caseys (16-2) to victory for the third time this season against the No. 7 seed Bucs (11-5), who were led by Maggie Davis (one goal), Meghan Murray (one goal), Mary Vilardi (one goal) and Hannah Noglows (four saves).
Rumson-Fair Haven 17, Ocean 5: Elizabeth Scarrone accounted for 10 points (six goals, four assists) as the No. 1 seed Bulldogs (14-2) toppled the No. 8 seed Spartans (13-7) to advance to Friday night's 5 p.m. SCT semifinal against No. 4 seed Manasquan. Brittany Bruno added five goals and one assist, Kyra Weiner had three goals and one assist and Sophia Bocklage made four saves. Meanwhile, Ocean's Morgan Bartlett had two goals, Taylor Herr added one goal and one assist and Shannon Ross made six saves.
Manasquan 17, Shore 15: The No. 4 seed Warriors (11-4) jumped out to a 9-7 halftime lead and held off the No. 5 seed Blue Devils (11-6) in the second half as Bella Feldmann finished with six goals and two assists. Janie Cowley facilitated the offense with three goals (including the 100th goal of her career) and six assists while Logan Harms added four goals and Jenna Harms recorded three goals and two assists. Manasquan goalie Jackie Kurtz made seven saves. Shore's Mary Kate George finished with a team-high six goals while Allie Reiser added four goals and Erin Rogers had one goal and one assist. Shore's Molly Santi made six saves.
Shore Conference Tournament
(2) Red Bank Catholic 13, (7) Red Bank 3
(4) Manasquan 17, (5) Shore 15
(3) Freehold Township 10, (6) Holmdel 5
(1) Rumson-Fair Haven 17, (8) Ocean 5
Staff Writer Sherlon Christie: schristie@gannettnj.com
Follow him on Twitter at https://twitter.com/sherlonapp
Follow him on Facebook at https://www.facebook.com/sherlonapp