Azolium-based systems: application of an anion exchange resin (A- form) method and 1H NMR analysis of the charged-assisted (CH)+·anion hydrogen bonds

The counteranion exchange of quaternary 1,2,3-triazolium salts was examined using a simple method that permitted halide ions to be swap for a variety of anions using an anion exchange resin (A¯ form). The method was applied to 1,2,3-triazolium-based ionic liquids and the iodideto- anion exchange proceeded in excellent to quantitative yields, concomitantly removing halide impurities. Additionally, an anion exchange resin (N3¯ form) was used to obtain the benzyl azide from benzyl halide under mild reaction. Likewise, following a similar protocol, bis(azidomethyl)arenes were also synthesized in excellent yields. The results of a proton NMR spectroscopic study of simple azolium-based ion pairs are discussed, with attention focused on the significance of the charged-assisted (CH)+···anion hydrogen bonds of simple azolium systems such as 1-butyl-3-methylimidazolium and 1-benzyl-3-methyl-1,2,3-triazolium salts.

Chemical constituents from Tabernaemontana catharinensis root bark: a brief NMR review of indole alkaloids and in vitro cytotoxicity

This work describes the isolation and structural determination of pharmacological compounds present in the bark of roots of Tabernaemontana catharinensis (Apocynaceae). Among the 27 substances detected 12 were identified as terpenoid-indole alkaloids, 2 steroids and 13 pentacyclic triterpenes. Structures were outlined based on HMQC, COSY, DEPT, 13C, and ¹H NMR data and MS. Spectral data of indole alkaloids were reviewed. An in vitro screening of the extracts and isolated compounds was carried out. Compounds ibogamine (5), 3-oxo-coronaridine (9) and 12-methoxy-4-methylvoachalotine (MMV) demonstrated effective cytotoxicity towards SKBR-3 breast adenocarcinoma and C-8161 human melanoma tumor cell lines.

RESSONÂNCIA MAGNÉTICA NUCLEAR DE SUBSTÂNCIAS ORGANOFLUORADAS: UM DESAFIO NO ENSINO DE ESPECTROSCOPIA

Nuclear magnetic resonance is a technique that is widely used for elucidating and characterizing organic substances. Organofluorine substances have applications in many areas from drugs to liquid crystals, but their NMR spectra are often challenging due to fluoride coupling with other nuclei. For this reason, NMR spectra of this class of substances are not commonly covered in undergraduate and graduate chemistry courses and related fields. Thus, the aim of this work was the presentation and discussion of 1H, 13C, and 19F NMR spectra of eleven organofluorine substances which, in the case of 1H and 13C nuclei, showed classic patterns of first-order coupling and the effects of the fluorine nucleus in different chemical and magnetic environments. In addition, the observation of long distance coupling constants was possible through the use of apodization functions in the processing of the spectra. It is expected that the examples presented herein can be utilized and discussed in undergraduate and graduate NMR spectroscopy disciplines and thus improve the teaching and future research of organofluorine compounds.

NMR studies of the exchange reactions of CH3CN.BX3 with excess CH3CN /|nJoseph Fogelman. -- 260 St. Catharines, Ont. : [s. n.],

Exchange reactions between molecular complexes and excess acid or base are well known and have been extensively surveyed in the literature(l). Since the exchange mechanism will, in some way involve the breaking of the labile donor-acceptor bond, it follows that a discussion of the factors relating to bonding in molecular complexes will be relevant. In general, a strong Lewis base and a strong Lewis acid form a stable adduct provided that certain stereochemical requirements are met. A strong Lewis base has the following characteristics (1),(2) (i) high electron density at the donor site. (ii) a non-bonded electron pair which has a low ionization potential (iii) electron donating substituents at the donor atom site. (iv) facile approach of the site of the Lewis base to the acceptor site as dictated by the steric hindrance of the substituents. Examples of typical Lewis bases are ethers, nitriles, ketones, alcohols, amines and phosphines. For a strong Lewis acid, the following properties are important:( i) low electron density at the acceptor site. (ii) electron withdrawing substituents. (iii) substituents which do not interfere with the close approach of the Lewis base. (iv) availability of a vacant orbital capable of accepting the lone electron pair of the donor atom. Examples of Lewis acids are the group III and IV halides such (M=B, AI, Ga, In) and MX4 - (M=Si, Ge, Sn, Pb). The relative bond strengths of molecular complexes have been investigated by:- (i) (ii) (iii) (iv) (v] (vi) dipole moment measurements (3). shifts of the carbonyl peaks in the IIIR. (4) ,(5), (6) .. NMR chemical shift data (4),(7),(8),(9). D.V. and visible spectrophotometric shifts (10),(11). equilibrium constant data (12), (13). heats of dissociation and heats of reactions (l~), (16), (17), (18), (19). Many experiments have bben carried out on boron trihalides in order to determine their relative acid strengths. Using pyridine, nitrobenzene, acetonitrile and trimethylamine as reference Lewis bases, it was found that the acid strength varied in order:RBx3 > BC1 3 >BF 3 • For the acetonitrile-boron trihalide and trimethylamine boron trihalide complexes in nitrobenzene, an-NMR study (7) showed that the shift to lower field was. greatest for the BB~3 adduct ~n~ smallest for the BF 3 which is in agreement with the acid strengths. If electronegativities of the substituents were the only important effect, and since c~ Br ,one would expect the electron density at the boron nucleus to vary as BF3

Letter - E.C. Schmon to Arthur A. Schmon, 13 July 1917

The letter describes a party with family at the Pell Tree Inn where they had dinner and dancing. She also mentions that Arthur was made an instructor of topography and may soon do his examinations for second lieutenant.

Letter - E.C. Schmon to Arthur A. Schmon, 13 May 1919

The letter describes a day Eleanore Celeste spent downtown and many friends she ran into during her outing. She then mentions an article she read that states most troops will be out of France by July 1st. This letter is labelled number 278.

Letter - E.C. Schmon to Arthur A. Schmon, 13 April 1916

The letter states that they will see one another on the nineteenth and Eleanore Celeste is excited for the date to arrive. She also mentions some volunteer work "tagging" for donations for the "benefit of war sufferers". She also attends a concert of Columbia University given at Carnegie Hall.

Letter - E.C. Schmon to Arthur A. Schmon, 13 November 1919

Eleanore Celeste is on her way to Mother Schmon's. She has been shopping and to see friends. She will leave for Shelter Bay in a month or so. The letter is labelled number 33 & 34.

Letter - E.C. Schmon to Arthur A. Schmon, 13 November 1918

Eleanore Celeste is teaching at Lafayette Street School. She states that she likes "this school better than any I've substituted in." She writes about a boy who could not attend school because he had no shoes and the family was living in terrible conditions with barely anything to eat. She has also read some articles about men returning from France and she is hoping that Arthur will return soon. The letter is labelled number 189.

Letter - E.C. Schmon to Arthur A. Schmon, 13 July 1918

Eleanore Celeste discusses going to the theatre alone and remarks "these war times are making girls independent". She also mentions her studies and how much she enjoys learning. She has enclosed an article titled "Heroes of our Army Parade in Paris". The letter is labelled number 127.

Letter - E.C. Schmon to Arthur A. Schmon, 13 April 1917

Eleanore Celeste mentions she went to see the film "The Matrimaniac" starring Douglas Fairbanks. She hopes to travel to Princeton in a week or so to visit Arthur. He is studying for exams.

Effects of hypothermia on brain glucose metabolism in acute liver failure: a H/C-nuclear magnetic resonance study.

Mild hypothermia has a protective effect on brain edema and encephalopathy in both experimental and human acute liver failure. The goals of the present study were to examine the effects of mild hypothermia (35°C) on brain metabolic pathways using combined 1H and 13C-Nuclear Magnetic Resonance (NMR) spectroscopy, a technique which allows the study not only of metabolite concentrations but also their de novo synthesis via cell-specific pathways in the brain. :1H and 13C NMR spectroscopy using [1-13C] glucose was performed on extracts of frontal cortex obtained from groups of rats with acute liver failure induced by hepatic devascularization whose body temperature was maintained either at 37°C (normothermic) or 35°C (hypothermic), and appropriate sham-operated controls. At coma stages of encephalopathy in the normothermic acute liver failure animals, glutamine concentrations in frontal cortex increased 3.5-fold compared to sham-operated controls (P < 0.001). Comparable increases of brain glutamine were observed in hypothermic animals despite the absence of severe encephalopathy (coma). Brain glutamate and aspartate concentrations were respectively decreased to 60.9% ± 7.7% and 42.2% ± 5.9% (P < 0.01) in normothermic animals with acute liver failure compared to control and were restored to normal values by mild hypothermia. Concentrations of lactate and alanine in frontal cortex were increased to 169.2% ± 15.6% and 267.3% ± 34.0% (P < 0.01) respectively in normothermic rats compared to controls. Furthermore, de novo synthesis of lactate and alanine increased to 446.5% ± 48.7% and 707.9% ± 65.7% (P < 0.001), of control respectively, resulting in increased fractional 13C-enrichments in these cytosolic metabolites. Again, these changes of lactate and alanine concentrations were prevented by mild hypothermia. Mild hypothermia (35°C) prevents the encephalopathy and brain edema resulting from hepatic devascularization, selectively normalizes lactate and alanine synthesis from glucose, and prevents the impairment of oxidative metabolism associated with this model of ALF, but has no significant effect on brain glutamine. These findings suggest that a deficit in brain glucose metabolism rather than glutamine accumulation is the major cause of the cerebral complications of acute liver failure.

Traducción de la Sentencia de la Corte Internacional de Justicia sobre el diferendo relativo a la aplicación del Acuerdo Provisional del 13 de septiembre de 1995 (Ex - República Yugoslava de Macedonia c. Grecia) Decisión sobre el fondo

Se presenta a continuación una traducción no oficial al idioma español del texto de la sentencia proferida por la Corte Internacional de Justicia el 5 de diciembre de 2011, relativa al fondo del Diferendo relativo a la aplicación del Acuerdo Provisional del 13 de septiembre de 1995 (ex - República Yugoslava de Macedonia c. Grecia).

Derecho penal y la obligación de investigar y sancionar graves violaciones de derechos humanos y el derecho internacional humanitario -especial referencia a la sentencia de la corte constitucional colombiana c-579/13-

En el presente trabajo se analiza la obligación de investigar graves violaciones de Derechos Humanos y Derecho Internacional Humanitario, a la luz de la sentencia de la Corte Constitucional Colombiana referente a la constitucionalidad del Marco Jurídico para la paz. De la aparente remisión que hace la Corte Constitucional a la Corte Interamericana de Derechos Humanos sobre el deber de investigar graves violaciones de Derechos Humanos y de Derecho Internacional Humanitario se concluye que la Corte Constitucional propone como premisa mayor una obligación que surge de una interpretación extensiva de la Convención Interamericana. De la misma forma, se estudia el tratamiento indebido del derecho aplicable a las amnistías e indultos, que se relaciona con la necesidad de evitar cualquier tipo de impunidad, cuyo concepto sirve para esclarecer cuáles son los estándares que se quiere proteger. Por último, se analiza el contexto al que se pretende aplicar dicha obligación, es decir, la justicia transicional, proponiendo un modelo interpretativo de los fines de la pena, y su aplicación por medio de la favorabilidad penal, para la justicia transicional, que sea acorde a la interpretación de la Convención Interamericana.