scholarly journals HR-DOSY and sulfoxide enantiomeric discrimination by cyclodextrin

2000 ◽  
Vol 14 (4) ◽  
pp. 203-213 ◽  
Author(s):  
Ricardo Batista Borges ◽  
Antonio Laverde Jr. ◽  
André Luiz Meleiro Porto ◽  
Anita Jocelyne Marsaioli
Keyword(s):  
Chiral Recognition ◽  
Chemical Shifts ◽  
Binding Constants ◽  
Chiral Selector ◽  
Point Of View ◽  
The Other ◽  
Stoichiometric Ratio ◽  
Enantiomeric Resolution ◽  
Rp Hplc ◽  
C Nmr

Racemic and chiral ethyl-phenylsulfoxide (solute) andβ-cyclodextrin (chiral selector) were used to compare two NMR methodologies to predict RP-HPLC enantiomeric resolution efficiency. One of them based on the classical approach involving apparent binding constants and complexation‒induced chemical shifts at saturation and the other based on13C NMR signal splittings (solute and chiral selector in stoichiometric ratio) and HR-DOSY of the same solution. We have concluded that the latter methodology is rather efficient and though more elaborate from the NMR point of view, the results are promising and constitute an alternative method to investigate chiral recognition and other supramolecular phenomena.

17O and 13C NMR spectra of some geminal diacetates

1988 ◽  
Vol 53 (3) ◽  
pp. 588-592 ◽  
Author(s):  
Antonín Lyčka ◽  
Josef Jirman ◽  
Jaroslav Holeček
Keyword(s):  
13C Nmr ◽  
Nmr Spectra ◽  
Chemical Shifts ◽  
The Other ◽  
13C Nmr Spectra ◽  
Other Hand ◽  
Carboxylic Esters ◽  
C Nmr ◽  
Oxygen Atoms

The 17O and 13C NMR spectra of eight geminal diacetates RCH(O(CO)CH3)2 derived from simple aldehydes have been measured. In contrast to the dicarboxylates R1R2E(O(CO)R3)2, where E = Si, Ge, or Sn, whose 17O NMR spectra only contain a single signal, and, on the other hand, in accordance with organic carboxylic esters, the 17O NMR spectra of the compound group studied always exhibit two well-resolved signals with the chemical shifts δ(17O) in the regions of 183-219 ppm and 369-381 ppm for the oxygen atoms in the groups C-O and C=O, respectively.

scholarly journals Bridge effect of the C=C, C=N and N=N bonds on the long distance electronic charge transfer ofpara‒substituted stilbenoid compounds

2000 ◽  
Vol 14 (4) ◽  
pp. 259-267 ◽  
Author(s):  
Manuel A. Leiva ◽  
Raul G. E. Morales
Keyword(s):  
Charge Transfer ◽  
Double Bond ◽  
Molecular System ◽  
Chemical Shifts ◽  
Phenyl Group ◽  
Point Of View ◽  
Electronic Charge ◽  
Orbital Theory ◽  
Long Distance ◽  
C Nmr

By means of13C‒NMR spectroscopy and ab initio molecular orbital theory calculations, we have analyzed the bridge effect of the C=C, C=N and N=N bonds on the long distance charge transfer of4‒dimethylamino‒4'‒nitrostilbenoid compounds in the ground electronic state.After a complete spectral assignment of the13C‒NMR signals in these molecular compounds, we have characterized the effect of the nitrogen centres on the molecular bridge by means of the chemical shifts of the carbon centres, the theoretical charge densities and the dipolar moments.From an electronic molecular point of view, our results describe two main properties of the double bond bridge. The first is related to the local charge accumulation capacity given by the type of the atomic centres and the structural orientation of the double bond bridge, and the second property is related to the modulation of the electronic charge distribution through the molecular system by the electrical polarization of the bridge.Other complementary experimental evidences have permit us to establish new local molecular domains of the bridge effect in these stilbenoid compounds by means of linear correlations between13C‒NMR chemical shifts of the aromatic carbon centres of the acceptor‒phenyl group and the molecular polarity of the species under study.

The structures and reactions of stannylene acetals from carbohydrate-derived trans-diols. Part I. In the absence of added nucleophiles

1990 ◽  
Vol 68 (7) ◽  
pp. 1007-1019 ◽  
Author(s):  
T. Bruce Grindley ◽  
Rasiah Thangarasa
Keyword(s):  
Nuclear Magnetic Resonance ◽  
Nmr Spectroscopy ◽  
Magnetic Resonance ◽  
Magnetic Resonance Spectroscopy ◽  
Chemical Shifts ◽  
The Other ◽  
Resonance Spectroscopy ◽  
Pyranose Ring ◽  
Regioselective Reactions ◽  
C Nmr

Di-n-butylstannylene acetals of benzyl 4,6-O-benzylidene-α- and -β-D-glucopyranoside and galactopyranoside have been prepared and studied in solution by 1H, 13C, and 119Sn nuclear magnetic resonance spectroscopy. The species present in solution have been identified from the 119Sn nmr spectral data, by comparison of the 13C nmr chemical shifts of the stannylene acetals and their precursor diols and also by analysis of the products of reactions performed without added nucleophiles. The orientations of the two substituents on the carbons in the pyranose ring attached to the carbons in the stannylene ring determine the structures adopted by the stannylene acetal in solution. If one substituent is axial and the other equatorial, the stannylene acetal exists as a single symmetrical dimer in which the two oxygen atoms in the two 1,3,2-dioxastannolane rings adjacent to the axial substituents are dicoordinate. A stannylene acetal with two adjacent equatorial substituents exists as a non-interconverting mixture of dimers; one with two adjacent axial substituents is present as a rapidly interconverting mixture of dimers, trimers, and tetramers. Benzoylation and benzylation of the latter two types of stannylene acetals have been performed and have been shown to be only slightly regioselective in contrast to the known highly regioselective reactions of the first type. Only when single dimers are present are regiospecific or highly regioselective reactions obtained. The causes of the variation in the species present and of the reaction regioselectivity for different stannylene acetals are discussed. Keywords: stannylene acetals, 1,3,2-dioxastannolanes, 119Sn NMR spectroscopy, regioselective reactions, carbohydrates.

Chemometrical analysis of substituent effects on 13C and 15N NMR chemical shifts in 1-aroyl-3-substituted thioureas

1989 ◽  
Vol 54 (9) ◽  
pp. 2399-2407 ◽  
Author(s):  
Oldřich Pytela ◽  
Josef Jirman ◽  
Antonín Lyčka
Keyword(s):  
Latent Variables ◽  
Chemical Shifts ◽  
Substituent Effects ◽  
The Other ◽  
15N Nmr ◽  
Nmr Chemical Shifts ◽  
Additional Constant ◽  
Substituent Constants ◽  
Derivatives Of ◽  
C Nmr

The methods of conjugated deviations and regression analysis have been used to study the substituent effects on 13C and 15N NMR chemical shifts of 12 derivatives of 1-aroyl-3-phenylthiourea and 1-aroyl-3-methylthiourea. The 13C NMR chemical shifts can be described by two latent variables, one univocally correlated with the Hammett substituent constants (r = 0.993) and the other reflecting the increased shielding of the nuclei due to overlap of the adjacent bond electrons as a consequence of electron-donor or electron-acceptor character of the substituents.This effect is less pronounced with the 15N nuclei. Application of dual substituent constants σR, σF with the additional constant σα describing the polarization has failed in giving sufficiently close correlations and explanation of the substituent effect found.

A study of the observable axial- and equatorial-2,4-dimethyl-2-adamantyl cations. Further examples of equilibrating nonclassical structures in "ordinary" tertiary carbocations

1990 ◽  
Vol 68 (10) ◽  
pp. 1889-1893 ◽  
Author(s):  
D. J. Buffam ◽  
T. S. Sorensen ◽  
S. M. Whitworth
Keyword(s):  
Chemical Shifts ◽  
The Other ◽  
Temperature Dependent ◽  
Lower Field ◽  
Tertiary Alcohols ◽  
Cation System ◽  
Different Temperatures ◽  
The Face ◽  
Opposite Face ◽  
C Nmr

The title cations have been prepared insitu from the corresponding tertiary alcohols, using three different superacid systems. The 13C NMR spectra were measured at a number of different temperatures, using the structurally related 13C peaks of internal 2-methyl-2-adamantyl cation as a reference. Using this protocol, one finds that the 13C chemical shifts of the four β carbons are quite temperature dependent, two of them shifting to higher field and the other two on the opposite face shifting to lower field, or vice versa, as the temperature is increased or decreased. This behavior is uniquely ascribed to a rapid equilibration between two "structures" for each cation system. The two structures in question involve selective C–C hyperconjugative delocalization on one face or the other of the 2-adamantyl skeleton. In the case of the 4-equatorial-methyl isomer, a structure with C–C hyperconjugation on the methyl-substituted face is most stable, while for the 4-axial-methyl cation, the structure with delocalization from the face opposite the substituent is favored. The former preference is regarded as stereoelectronic in origin while the latter is ascribed to steric effects. Keywords: non-planar carbocations, temperature dependent NMR shifts, stereoelectronic effects.

scholarly journals Binding Constants Determination of Ofloxacin and Ornidazole Enantiomers with Sulfated β-Cyclodextrin as Single Ligand by Capillary Electrophoresis using Three Different Linear Plotting Methods

2021 ◽  
Vol 33 (7) ◽  
pp. 1663-1670
Author(s):  
Khaldun M. Al Azzam
Keyword(s):  
Capillary Electrophoresis ◽  
Background Electrolyte ◽  
Binding Constants ◽  
Chiral Selector ◽  
The Other ◽  
Binding Parameters ◽  
Guest Binding ◽  
Different Temperatures ◽  
Temperature Ranges

The aim of this research is to use capillary electrophoresis to establish/determine the binding constants for ofloxacin and ornidazole enantiomers with the negatively charged chiral selector sulfated-β-cyclodextrin (S-β-CD). Using electrophoretic mobility values of ofloxacin and ornidazole enantiomers at various concentrations of S-β-CD used in the context of background electrolyte (BGE), binding constants were calculated using three separate linearization plots, namely double-reciprocal, X-reciprocal and Y-reciprocal. The R-ofloxacin enantiomer-S-β-CD complex had the highest inclusion affinity of the ofloxacin and ornidazole enantiomers, which matched with previously reported estimation. Every enantiomer-S-β-CD complex’s binding constants, as well as thermodynamic binding parameters, were calculated at different temperatures. The host-guest binding constants using double reciprocal fit showed greater linearity (R2 > 0.99) at all temperature ranges measured (15-30 ºC) as compared to the other two fit approaches. The thermodynamic complexation parameters were found to be dependent on the temperature of the enantiomers, as seen by the linear van’t Hoff (15-30 ºC) plot.

scholarly journals Nitrogen NMR shieldings of 2-amino-5-nitro-6-methylpyridines

1997 ◽  
Vol 13 (4) ◽  
pp. 251-256 ◽  
Author(s):  
B. Palasek ◽  
A. Puszko ◽  
Z. Biedrzycka ◽  
W. Sicinska ◽  
M. Witanowski
Keyword(s):  
Nitro Group ◽  
Aromatic Ring ◽  
Steric Hindrance ◽  
Chemical Shifts ◽  
Amino Nitrogen ◽  
Point Of View ◽  
The Other ◽  
Amino Group ◽  
Alkyl Aryl ◽  
Pyridine Nitrogen

Nitrogen NMR shieldings (chemical shifts) of 2-amino-5-nitro-6-methylpyridine derivatives are assessed from the point of view of substituent-induced effects under conditions where alkyl, aryl, nitro, and nitroso moieties are substituents at the amino nitrogen. The nitro nitrogen shielding reveals only little variation upon varying the substituents, and this seems to indicate that steric hindrance which is likely to force the nitro group out of the plane of the aromatic ring reduces theπ-electron conjugation with the latter, and with the amino group as well. On the other side, the pyridine nitrogen shielding shows large effects of substituents at the amino moiety, which suggests a significant conjugation between the ring and the amino group. The latter effects produce a remarkable deshielding of the pyridine nitrogen in the case of nitro and nitroso substituents at the amino group.

Can the Academic Self-Concept be Positive and Realistic?

2005 ◽  
Vol 19 (3) ◽  
pp. 129-132 ◽  
Author(s):  
Reimer Kornmann
Keyword(s):  
Academic Performance ◽  
Opposite Effect ◽  
Self Esteem ◽  
Point Of View ◽  
The Other ◽  
Self Concept ◽  
High Ability ◽  
Self Image ◽  
Other Hand

Summary: My comment is basically restricted to the situation in which less-able students find themselves and refers only to literature in German. From this point of view I am basically able to confirm Marsh's results. It must, however, be said that with less-able pupils the opposite effect can be found: Levels of self-esteem in these pupils are raised, at least temporarily, by separate instruction, academic performance however drops; combined instruction, on the other hand, leads to improved academic performance, while levels of self-esteem drop. Apparently, the positive self-image of less-able pupils who receive separate instruction does not bring about the potential enhancement of academic performance one might expect from high-ability pupils receiving separate instruction. To resolve the dilemma, it is proposed that individual progress in learning be accentuated, and that comparisons with others be dispensed with. This fosters a self-image that can in equal measure be realistic and optimistic.

RHYNCHOLITES AND THE PROBLEM OF NARROW AND BROAD CONCEPTION OF TAXONS

2018 ◽  
pp. 12-17 ◽  
Author(s):  
I. R. Khuzina ◽  
V. N. Komarov
Keyword(s):  
Sexual Dimorphism ◽  
Morphological Characteristics ◽  
Mass Scale ◽  
Individual Variability ◽  
Point Of View ◽  
The Other ◽  
New Taxon ◽  
Artificial System ◽  
Broad Understanding

The paper considers a point of view, based on the conception of the broad understanding of taxons. According to this point of view, rhyncholites of the subgenus Dentatobeccus and Microbeccus are accepted to be synonymous with the genus Rhynchoteuthis, and subgenus Romanovichella is considered to be synonymous with the genus Palaeoteuthis. The criteria, exercising influence on the different approaches to the classification of rhyncholites, have been analyzed (such as age and individual variability, sexual dimorphism, pathological and teratological features, degree of disintegration of material), underestimation of which can lead to inaccuracy. Divestment of the subgenuses Dentatobeccus, Microbeccus and Romanovichella, possessing very bright morphological characteristics, to have an independent status and denomination to their synonyms, has been noted to be unjustified. An artificial system (any suggested variant) with all its minuses is a single probable system for rhyncholites. The main criteria, minimizing its negative sides and proving the separation of the new taxon, is an available mass-scale material. The narrow understanding of the genus, used in sensible limits, has been underlined to simplify the problem of the passing the view about the genus to the other investigators and recognition of rhyncholites for the practical tasks.

Birlikte Yaşama Kültürü Çerçevesinde Avrupa Birliği ve Türkiye Politikaları: Suriyelilere Yönelik Tutumun Sultanbeyli Örneği Üzerinden Değerlendirilmesi

2017 ◽  
Vol 4 (1) ◽  
pp. 41-61
Author(s):  
Pelin Sönmez ◽  
Abulfaz Süleymanov
Keyword(s):  
Civil Wars ◽  
Large Scale ◽  
Social Acceptance ◽  
Point Of View ◽  
The Other ◽  
Syrian Refugees ◽  
The European Union ◽  
International Protection ◽  
Legal Structure ◽  
Turkish People

Türkiye, Cumhuriyet tarihinin en yoğun zorunlu göç dalgasını 2011 yılından bu yana süren Suriye Savaşı ile yaşamaktadır. Suriye vatandaşlarının geçici koruma statüsü altında Türkiye toplumuna her açıdan entegrasyonları günümüzün ve geleceğin politika öncelikleri arasında düşünülmelidir. Öte yandan ülkeye kabul edilen sığınmacıların kendi kültürel kimliğini kaybetmeden içinde yaşadığı ev sahibi topluma uyumu, ortak yaşam kültürünün gelişmesi açısından önem arz etmektedir. Bu makalede, "misafir" olarak kabul edilen Suriyeli vatandaşların Türk toplumunca kabul edilmeleri ve dışlanma risklerinin azaltılmasına yönelik devlet politikaları ortaya konularak, üye ve aday ülkelere göçmenlerin dışlanmasını önlemek için Avrupa Birliği (AB) tarafından sunulan hukuki yapı ve kamu hizmeti inisiyatifleri incelenmekte, birlikte yaşam kültürü çerçevesinde Suriyeli vatandaşlara yönelik  toplumsal kabul düzeyleri ele alınmaktadır. Çalışma iki ana bölümden oluşmaktadır: göçmen ve sığınmacılara karşı toplumsal dışlanmayı engellemek için benimsenen yasa ve uygulamaların etkisi ve İstanbul-Sultanbeyli bölgesinde Suriyeli sığınmacılarla ilgili toplumsal algı çalışmasının sonuçları. Bölgede ikamet eden Suriyelilere yönelik toplumsal kabul düzeyinin yüksek olduğu görülürken, halkın Suriyelileri kendilerine  kültürel ve dini olarak yakın hissetmesi toplumsal kabul düzeyini olumlu etkilemektedir. ABSTRACT IN ENGLISHAn evaluation of the European Union and Turkish policies regarding the culture of living togetherThis article aims to determine the level of social acceptance towards Syrians within the context of cohabitation culture by evaluating EU’s legal structure and public service initiatives in order to prevent Syrian refugees from being excluded in member and candidate countries and by revealing government policies on acceptance of Syrians as “guest” by Turkish society and minimizing the exclusion risks of them. This article consists of two main parts, one of which is based on the effects of law and practices preventing refugees and asylum seekers from social exclusion, and the other is on the results of social perception on Syrians in Sultanbeyli district of Istanbul. At the end of 5-years taking in Syrian War, it is obvious that most of more than 3 million Syrian with unregistered ones in Turkey are “here to stay”. From this point of view, the primary scope of policies should be specified in order to remove side effects of refugee phenomenon seen as weighty matter by bottoming out the exclusion towards those people. To avoid possible large-scale conflicts or civil wars in the future, the struggle with exclusion phenomenon plays a crucial role regarding Turkey’s sociological situation and developing policies. In the meaning of forming a model for Turkey, a subtitle in this article is about public services for European-wide legal acquis and practices carried out since 1970s in order to prevent any exclusion from the society. On the other hand, other subtitles are about legal infrastructure and practices like Common European Asylum and Immigration Policies presented in 2005, and Law on Foreigners and International Protection introduced in 2013. In the last part of the article, the results of a field survey carried out in a district of Istanbul were used to analyze the exclusion towards refugees in Turkey. A face-to-face survey was randomly conducted with 200 settled refugees in Sultanbeyli district of Istanbul, and their perceptions towards Syrian people under temporary protection were evaluated. According to the results, the level of acceptance for Syrians living in this district seems relatively high. The fact that Turkish people living in the same district feel close to Syrian refugees culturally and religiously affect their perception in a positive way: however, it is strikingly seen and understood that local residents cop an attitude on the refugees’ becoming Turkish citizens.

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