Alcohol Spectrum Research Articles

PYROLYTIC MASS-SPECTROMETRY OF THE OLIGOISOPRENE WITH OF TERMINAL HYDROXYL GROUPS

Pyrolytic mass spectrometry was used to evaluate the effect of terminal hydroxyl groups on the composition of thermal degradation products of oligoisoprene obtained using hydrogen peroxide as an initiator in the isopropyl alcohol solution. To interpret the mass spectra of the oligomer, the mass spectra of some low molecular weight alcohols were used. Oxygen-containing groups were found in the mass spectrum of the oligomer, confirming the presence of two types of hydroxyl groups. Peak m/z = 85 corresponds to the fragment from the terminal unit of isoprene directly connected with the primary hydroxyl group, and peak m/z = 127 does the same unit with the terminal fragment of isopropyl alcohol with the tertiary hydroxyl group. This conclusion is confirmed by the presence of peaks resulting from the transformations of the end groups of atoms in the oligomer, which are modeled by the corresponding low molecular weight alcohols.

Availability of nonbeverage alcohols in 50 Russian cities in 2015–2017

Introduction Nonbeverage alcohols (NAs) in Russia are manufactured alcohol containing liquids not intended for consumption instead of alcoholic beverages, not classed as alcoholic drinks, and not subject for legal regulation as alcoholic beverages, but which may be consumed for drinking. It has been found in a case-control study conducted in Urals in 2003–2005, that their consumption by working age Russian males was associated with a seven-fold increase in odds of death adjusted for smoking, education, and amount of ethanol consumed from alcoholic beverages. Legally produced NAs usually contain highly rectified concentrated ethanol (up to 95% by volume). In 2006 and later Russia implemented a range of legislative measures aimed at reduction of availability of illegal and nonbeverage alcohols. The most recent regulations were put in force at the end of December 2016 and in 2017 in response to deadly outbreak of mass alcohol poisoning with NA, containing methanol, which occurred in Siberian city of Irkutsk in December 2016 resulting in 76 deaths. Since 2007, no research was carried out to investigate the effectiveness of implemented regulations or to assess availability of NAs across the vast geography of Russia. Methods The availability survey was aimed: –to determine if NAs were still available in legal retail sale in cities of the Russian Federation in 2015–2017; –to provide characteristics of different types of NAs that were sold. Between July 2015 and December 2017 six field workers purchased samples of NAs in 50 Russian cities. NAs were defined as containing at least 60% ethanol by volume (as indicated on the label) and generally cost less than 40 rubles per bottle ($0.67, €0.59, £0.50). NAs were purchased in a variety of places, including pharmacies, shops, kiosks, individual persons and other types of retail outlets. Results In total, 2147 samples of NAs were purchased, which can be grouped into the following types: (1) perfumery and cosmetics spirituous liquids, (2) bath additives, (3) medicinal tinctures, (4) medicinal spirituous solutions for internal use, (5) antiseptics, (6) technical/medicinal ethanol, (7) spirituous liquids for oral or body hygiene, and (8) spirituous food flavour enhancers. Ethanol concentration in the vast majority of purchased NAs was above 60% by volume (min: 25%; max: 95%; median: 70%). Unit cost of ethanol in most samples was lower than in standard Russian vodka. The majority of purchased samples of NAs were of sorts, which were reported to be consumed for drinking in our simultaneously conducted in 2015–2017 survey of alcohol consumption among patients of narcology clinic in Kazan, Russia. In 2015 and 2016 we were able to purchase all types of nonbeverage alcohols specified above. However, in 2017 a range of NAs was no longer available in retail. This included specific types of perfumery and cosmetics spirituous liquids, such as cheap spirituous lotions, aftershaves and tonics; spirituous bath additives; and spirituous liquids for oral and body hygiene. However, medicinal tinctures in 25 mL, 40 mL, and 100 mL bottles, medicinal antiseptics, and cheap eau-de-colognes (e.g. Troynoy, Shirp) were still readily available in 2017. Conclusions The wide spectrum of nonbeverage alcohols, which were targeted by 2006 alcohol control regulations were readily available in 2015 and 2016. Regulations implemented at the end of 2016 and in 2017 in response to mass alcohol poisoning with NA were also not comprehensive, since they haven’t prevented production and sale of cheap sources of ethanol in the form of medicinal tinctures, antiseptics and not denatured eau-de-colognes. While these latest regulations banning sale of some sorts of NAs may indeed result in reduction of alcohol-attributable mortality in Russia in 2017, the stronger action is still required to prevent consumption of specific sorts of medicinal and perfumery nonbeverage alcohols, which are still available and affordable for those who may want to drink them.

The Effect of Chain Length on Mid-Infrared and Near-Infrared Spectra of Aliphatic 1-Alcohols.

Effect of the chain length on mid-infrared (MIR) and near-infrared (NIR) spectra of aliphatic 1-alcohols from methanol to 1-decanol was examined in detail. Of particular interest were the spectra-structure correlations in the NIR region and the correlation between MIR and NIR spectra of 1-alcohols. An application of two-dimensional correlation analysis (2D-COS) and chemometric methods provided comprehensive information on spectral changes in the data set. Principal component analysis (PCA) and cluster analysis evidenced that the spectra of methanol, ethanol, and 1-propanol are noticeably different from the spectra of higher 1-alcohols. The similarity between the spectra increases with an increase in the chain length. Hence, the most similar are the spectra of 1-nonanol and 1-decanol. Two-dimensional hetero-correlation analysis is very helpful for identification of the origin of bands and may guide selection of the best spectral ranges for the chemometric analysis. As shown, normalization of the spectra pronounces the intensity changes in various spectral regions and provides information not accessible from the raw data. The spectra of alcohols cannot be represented as a sum of the CH3, CH2, and OH group spectra since the OH group is involved in the hydrogen bonding. As a result, the spectral changes of this group are nonlinear and its spectral profile cannot be properly resolved. Finally, this work provides a lot of evidence that the degree of self-association of 1-alcohols decreases with the increase in chain length because of the growing meaning of the hydrophobic interactions. For butyl alcohol and higher 1-alcohols the hydrophobic interactions are more important than the OH OH interactions. Therefore, methanol, ethanol, and 1-propanol have unlimited miscibility with water, whereas 1-butanol and higher 1-alcohols have limited miscibility with water.

P-4 * THREE CASES OF ALCOHOLISM WITH AUTISM SPECTRUM DISORDER

Introduction. The relationship between alcoholism and autism spectrum disorder (ASD) has been the subject of much recent research. We report herein three patients with alcoholism and a history of ASD. Ethical considerations. Consent was directly obtained from Patients 1 and 2. Care was taken to protect the identities of all three patients. Case reports. Patient 1 was a 34-year-old man. From adolescence onwards,he had few friends and tended to isolate himself. At 21 years old, he began drinking alcohol due to the stress of interpersonal communication. At 29 years old, he was admitted with alcohol withdrawal symptoms. Post-discharge, no relapse has occurred. ASD was confirmed on psychological testing. Patient 2 was a 38-year-old man with a long-term history of anthropophobia. He entered employment at the age 19, but quit employment at age 30 due to the stress of interpersonal communication. After turning to alcohol in order to reduce anxiety, he became an alcoholic. He was admitted at 36 years old. Post-discharge, no relapse has occurred. ASD was confirmed on psychological testing. Patient 3 was a 28-year-old woman with a long-term history of stranger anxiety. She began drinking excessively in order to reduce the stress of interpersonal communication. At 26 years old, she was admitted for alcohol epilepsy. Post-discharge, no relapse has occurred. ASD was confirmed on psychological testing. Discussion. The following characteristics were common to all three patients: ASD; interpersonal communication disorder from a young age; development of alcoholism at a young age; and no difficulty maintaining abstinence after successfully quitting. In connection with alcohol consumption, ASD traits, including strong preferences, obsessive-compulsive behaviors, and stereotypies, reportedly result in early addiction, but also work favorably to enable maintained abstinence. These characteristics are consistent with the present patients. The identification of a history of ASD is important for the successful management of alcoholism.

Equilibrium Structures and Vibrational Assignments for Isoamyl Alcohol and tert-Amyl Alcohol: A Density Functional Study

We have calculated the vibrational spectra of isoamyl alcohol and of tert-amyl alcohol using Density Functional Theory (DFT) with the Becke-3 Lee Yang Parr (B3LYP) functional and a 6-311+G** atomic basis set. The energies of the conformers were also calculated with ab initio Perturbation Theory of second (MP2) and fourth order restricted to single, double and quadruple excitations (MP4 SDQ) with the same basis set. We found rather complicated equilibria of four conformations in each case, counting only those with appreciable abundancies. PED data were compared with GAUSSVIEW animations. The calculated wavenumbers agree rather well with the experimental ones when the gauche-trans conformer is assumed as the most important one for isoamyl alcohol, and the gauchegauche one for tert-amyl alcohol. However, some of the experimental bands had to be assigned also to other conformers, indicating their presence in the equilibrium mixture. Due to sterical reasons both the CO and the OH bonds appear to be weaker in the tertiary alcohol, considering the wavenumbers of the CO and OH bond stretching vibrations. The bond lengths point into the same direction, however, the OH bond in the tertiary alcohol is only slightly longer than that in the primary alcohol.

Effect of aluminum chloride on formation of a polyconjugated bond system in the initial stage of polyvinyl alcohol thermal decomposition

Fine-structure bands have been located in electronic absorption spectra of polyvinyl alcohol (PVA) films decomposed thermally in air at 80–150°C. Doping of the PVA film with aluminum chloride (thermolysis catalyst) was found both to enhance the degree of thermal decomposition and to reduce the starting temperature for formation of poly-π-conjugated chains although it had no effect on the spectral positions of the polyene-unit absorption bands. Values of the band gap of heat-treated PVA films were determined to be in the range 1.65–1.78 eV based on an analysis of the electronic spectra long-wavelength edge.

ChemInform Abstract: Microwave and Submillimeter-Wave Rotational Spectrum of Methyl Alcohol in the Ground Torsional State.

Abstract The frequencies of 440 transitions of the spectrum of the ground torsional-vibrational state of methyl alcohol have been measured in the microwave and submillimeter regions, 130 of these belonging to the main isotopomer CH 3 OH ( J ≤ 42, K ≤ 8), 190 to the isotopomer CD 3 OH ( J ≤ 37, K ≤ 10), and 120 to CD 3 OD ( J ≤ 27, K ≤ 5). For the first time, all the transitions were identified on the basis of directly calculated frequencies. These results were obtained through the use of a new effective torsional-rotational Hamiltonian. Its parameters were calculated based on the frequencies of all earlier known and new transitions of microwave and submillimeter-wave spectra of the ground torsional-vibrational state of methanol. The root-mean-square deviation is 710 kHz (800 lines) for the main isotopomer, 144 kHz (370 lines) for CD 3 OH, and 316 kHz (150 lines) for CD 3 OD.

Nanoscale molecular clusters and vibrational relaxation in simple alcohols

Our work is devoted to the determination of the structure peculiarities of such partially ordered substances as liquid monohydric alcohols. Quantum-chemical calculations of the nanoclusters forming the structure of liquid methanol and ethanol were made. Their optimal space geometry, forming energy and electrical parameters were calculated. The dynamical stability of the structure of liquid monohydric alcohols in the investigated temperature region was registered. The correlation analysis of the Raman spectra of ethyl alcohol was made. The time of vibrational relaxation was calculated. The broadening of the vibrational bands in the spectra of alcohols (vibrational dephasing) can be explained by the process of hydrogen bond dissociation.

Applications of Morphometric and Diffusion Tensor Magnetic Resonance Imaging to the Study of Brain Abnormalities in the Alcoholism Spectrum

Background: The International Conference on Applications of Neuroimaging to Alcoholism was held at Yale University in New Haven, CT, in January 2004. The following is a brief summary of the contributions of five speakers who presented their work during the magnetic resonance imaging (MRI) and diffusion tensor imaging (DTI) session. Methods: This session addressed how MRI and DTI are used to assess macro- and microstructural brain alterations in alcoholism. Structural MRI methods can address regional gray and white matter volumetric/morphometric abnormalities, and DTI methods can address microstructural disruptions of white matter tracts. These methods can be applied across the spectrum of alcoholism to elucidate distinct brain abnormalities underlying clinical subtypes, to disentangle brain volume deficits that precede, from those that follow, the onset of alcoholic drinking in chronic alcoholics, and to examine effects of prenatal alcohol exposures on brain development in children. The presentations highlighted recent scientific findings and methodological advances in these areas. Results: Disease-specific probabilistic atlases, designed to reflect the unique anatomy and physiology of particular clinical subpopulations, can be developed for alcoholism. Such an atlas can be used to identify efficiently patterns of altered structure or function in alcoholism and can guide algorithms for knowledge-based image analysis. DTI is sensitive to constraints on the random diffusion of water molecules in axons, allowing assessment of white matter tract integrity in neuropsychiatric diseases, including alcoholism. Recent MRI and DTI data were presented showing region-specific brain abnormalities at both macro- and microstructural levels that varied differentially according to sex, time of alcohol exposure in life, and alcoholism subtype. Conclusion: The International Conference on Applications of Neuroimaging to Alcoholism brought together leading experts in MRI and DTI techniques to discuss their applications to the study of alcoholism. The extant and new imaging technologies provide us with multiple modalities to study the brain in vivo. These noninvasive tools enable us to monitor the time course of alcohol effects on the brain and to characterize macro- and microstructural brain abnormalities across the full spectrum of alcoholism, including its precursors and its sequelae.

Supersonic Jet Spectroscopic Study of p-Methoxybenzyl Alcohol

Fluorescence and mass-resolved S1−S0 excitation spectra of p-methoxybenzyl alcohol in a supersonic jet are reported. The long vibrational progression bands are observed in both spectra and attribut...

Molecular and crystal structures of (S,S)-[o-(α-dimethylaminoethyl)phenyl]phenylarylcarbinols

The crystal structures of (S,S)-o-(α-dimethylaminoethyl)phenyl]phenyl-2,4-dimethylphenyl-carbinol (I) and (S,S)-o-(α-dimethylaminoethyl)phenyl]phenyl-2,4,5-trimethylphenylcarbinol (II) are determined by X-ray diffraction. The molecular and crystal structures of I and II are similar. The crystal structures of I and II are compared based on the analysis of the geometric characteristics of the Vorono\(\overset{\lower0.5em\hbox{$\smash{\scriptscriptstyle\smile}$}}{l} \)2-Dirichlet packing polyhedra. The circular dichroism spectra of amino alcohols I and II revealed a strong positive Cotton effect in the region of 230 nm, which correlates with the S-configuration of the chiral carbinol center.

ChemInform Abstract: Two‐Dimensional Infrared and Near‐Infrared Correlation Spectroscopy: Applications to Studies of Temperature‐Dependent Spectral Variations of Self‐Associated Molecules

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

Influence of pH, Ionic Strength, and Physical State on the Near-Infrared Spectra of Model Compounds

Abstract The accuracy of near-infrared spectroscopy (NIRS) when applied to high-moisture samples (i.e., silages) does not match that with dried materials. Previous work showed that the presence of water could cause shifts in the spectra of organic compounds, the degree of which depended on the material and the water concentration. For some solids, such as sugars, large spectral changes occur on dissolution. The objective of this study was to determine the effect of pH, ionic strength, and physical state on the NIR spectra of model compounds. The results show that pH has large effects on the spectra of amines and acids but little if any on the spectra of ketones, alcohols, and sugars. The spectra of peptides and proteins also were pH dependent, but that of cellulose was not. Ionic strength differences (deionized water vs saturated NaCI solution as the diluting media) had only minor or no effect on the spectra of the materials studied. The effect of physical state was far more complicated; the spectra of freeze-dried glucose and glycine were different from that of the crystalline forms, but the spectrum of serine was not. The spectra of molten compounds often appeared like those of solutions. These results, in agreement with earlier work, may explain the poorer performance of NIRS with wet materials compared with dry samples. They also have serious implications for the analysis of dried samples, if pH, ionic strength, or drying method varies among samples.

Use of Principal Component Analysis in a near Infrared Study of the Dissociation Process of Oleyl Alcohol

This paper demonstrates the usefulness of principal component analysis (PCA) in the study of the dissociation process of oleyl alcohol ( cis-9-octadecen-1-ol) as the pure liquid. Fourier transform near infrared (FT-NIR) spectra of the neat alcohol were measured over a temperature range of 6.5–90°C in the 11,500–6000 cm−1 region. The degree of dissociation of the alcohol was determined by the intensities of the first and second overtones of the OH stretching mode of the monomer. PCA on the obtained spectra were calculated over three different regions, the entire 11,500–6000 cm−1 region and the 11,500–9087 and 9087–6000 cm−1 regions. PCA clearly reveals that there exists a break point at around 45°C in the dissociation process of the alcohol.

Classification of alcoholism with reference to comorbidity.

Classification of individuals with alcoholism is currently limited. The purpose of this analysis was to determine whether antisocial personality disorder and other primary psychiatric syndromes identified subgroups of alcoholics with differing characteristics. Alcoholic probands (n = 224) with alcoholism were divided into those with primary alcoholism (n = 128), antisocial alcoholism (n = 50), and secondary alcoholism (n = 46). These groups were evaluated with regard to alcohol-related symptoms and upon a variety of psychiatric signs and symptoms. The secondary alcoholism. The antisocial alcoholic and primary alcoholic groups demonstrated many similarities, but overall, the antisocial alcoholic group appeared most severe. The antisocial alcoholic group additionally exhibited a dissociation between the subjectively reported and the observed behavior. These findings support the concept of heterogeneity within the alcoholism spectrum. Longitudinal data are needed to determine whether the observed cross-sectional differences predict outcome differences.

FUEL ETHANOL PRODUCTION FROM AGRICULTURAL L1GNOCELLULOSIC FEEDSTOCKS - A REVIEW

ABSTRACT Over the past three decades significant efforts have been made towards the conservation of fossil-based fuels and the exploration and exploitation of new renewable sources. The focus primarily has been on the outlook for alternatives to the petroleum products. In this spectrum alcohol manufacture from biomass has attracted a large attention all over the world which could be used as an alternative source to petrol or in blends with petrol The National Research Council (NRC) has substantially emphasized on the reduction of CO2 emissions and the other so-called green house gases. The NRC committee also recommends better evaluations of the processes for converting the biomass / lignocellulosic wastes to ethanol that will lessen the U.S. dependence on foreign oil. Among the factors behind the move to bio-based materials are the environmental concerns, the availability of abundant, renewable agricultural and forest resources that are both inexpensive and under-utilized.

ChemInform Abstract: Gas Phase IR Spectrum of syn‐Vinyl Alcohol Produced by Thermal Decomposition of Several Alcohol and Aldehydes

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

Ir spectra of the simplest stable proton solvates in methanol and ethanol

The spectra of (MeOH)2H+ and (EtOH)2H+ proton disolvates formed by strong symmetrical hydrogen bonding were separated from the multiple frustrated total internal reflection (MFTIR) IR spectra of solutions of HCl in methanol and ethanol. These spectra show a large number of rather narrow bands, exceeding the number of bands in the spectra of the pure alcohols and are in accord with a model, in which the generation of continuous absorption in solutions of strong acids is a consequence of the interaction of vibrations for protons in a strong, symmetrical hydrogen bond with the vibrations of other groups of proton disolvates.

Conformation of the piperidine ring in isomeric 1,2,5-trimethyl-4-phenyl(triorganosilyl)piperidin-4-ols from the PMR spectra

A full analysis of the PMR spectra of isomeric promedol alcohols was undertaken for the first time. It was shown that the conformational equilibrium must be taken into account only in the case of the Β isomer, where it is determined mainly by chair-chair interconversion. In the α isomers of 1,2,5-trimethyl-4-triorganosilylpiperidin-4-ols an equilibrium was found between the chair conformation and the two skew boat conformations, which are stabilized by an intramolecular hydrogen bond and by the large size of the triorganosilyl substituent.

Generalized Singular Value Decomposition And Discriminant Analysis

A fundamental and widely used approach to feature selection is the method of linear discriminant analysis. The standard formulation of the analysis requires knowledge of the total and pooled within-class scatter matrices. Estimates of these matrices are made from training sets. In spectral pattern recognition, one is usually faced with large numbers of highly correlated measurements and only a small number of representative spectra. The training sets are typically inadequate, and the resultant estimates of pooled within-class scatter matrices are ill conditioned or singular. This precludes the use of the standard formulation of discriminant analysis. By formulating the discriminant analysis in terms of generalized singular value decompositions of total and pooled within-class deviation matrices, the method can be applied in situations where the scatter matrices are ill conditioned or singular. The approach is illustrated with an example two-class problem of distinguishing between Fourier transform infrared (FTIR) spectra of aliphatic hydrocarbons and alcohols.