Interpretation of the vibrational spectra of glassy polymers using coarse-grained simulations

The structure and vibrational density of states (VDOS) of polymer glasses are investigated using numerical simulations based on the classical Kremer-Grest bead-spring model. We focus on the roles of chain length and bending stiffness, the latter being set by imposing three-body angular potentials along chain backbones. Upon increasing the chain length and bending stiffness, structural reorganisation leads to volumetric expansion of the material and build-up of internal stresses. The VDOS has two dominant bands: a low frequency one corresponding to inter- and intra-chain non-bonding interactions and a high frequency one corresponding principally to vibrations of bonded beads that constitute skeletal chain backbones. Upon increasing the steepness of the angular potential, vibrational modes associated with chain bending gradually move from the low-frequency to the high-frequency band. This redistribution of modes is reflected in a reduction of the so-called Boson peak upon increasing chain stiffness. Remarkably, the finer structure and the peaks of the high-frequency band, and their variations with stiffness, can, for short chains, be explained using an analytical solution derived for a model triatomic molecule. For longer chains, the qualitative evolution of the VDOS with chain stiffness is similar, although the distinct peaks observed for short chains become increasingly smoothed-out. Our findings can be used to guide a systematic approach to interpretation of Brillouin and Raman scattering spectra of glassy polymers in future work, with applications in polymer processing diagnostics.Comment: To appear in Macromolecule

In silico rationalisation of selectivity and reactivity in Pd-catalysed C-H activation reactions.

A computational approach has been developed to automatically generate and analyse the structures of the intermediates of palladium-catalysed carbon-hydrogen (C-H) activation reactions as well as to predict the final products. Implemented as a high-performance computing cluster tool, it has been shown to correctly choose the mechanism and rationalise regioselectivity of chosen examples from open literature reports. The developed methodology is capable of predicting reactivity of various substrates by differentiation between two major mechanisms - proton abstraction and electrophilic aromatic substitution. An attempt has been made to predict new C-H activation reactions. This methodology can also be used for the automated reaction planning, as well as a starting point for microkinetic modelling.EPSRC grant EP/K009494/1 (MK and SL) and the National Research Foundation, Prime Minister’s Office, Singapore under its CREATE programme, project “Cambridge Centre for Carbon Reduction in Chemical Technology” (LC and AL)

Puberty vs age: on the issue of a warning sign of a victim of non-violent intercourse with a minor

The purpose of the study was to identify the most optimal sign of a victim of non-violent sexual intercourse with a minor based on the analysis of approaches to the definition of such a sign in the criminal legislation of different countries, as well as the doctrinal provisions of medicine and jurisprudence.Метою дослідження було виявлення найбільш оптимальної ознаки потерпілого від ненасильницьких статевих зносин с неповнолітнім на основі аналізу підходів до визначення такої ознаки у кримінальному законодавстві різних країн, а також доктринальних положень медицини і юриспруденції.Целью исследования явилось выявление наиболее оптимального признака потерпевшего от ненасильственного полового сношения с несовершеннолетним на основании анализа подходов к определению такого признака в уголовном законодательстве разных стран, а также доктринальных положений медицины и юриспруденции

Puberty vs age: on the issue of a warning sign of a victim of non-violent intercourse with a minor

The purpose of the study was to identify the most optimal sign of a victim of non-violent sexual intercourse with a minor based on the analysis of approaches to the definition of such a sign in the criminal legislation of different countries, as well as the doctrinal provisions of medicine and jurisprudence.Метою дослідження було виявлення найбільш оптимальної ознаки потерпілого від ненасильницьких статевих зносин с неповнолітнім на основі аналізу підходів до визначення такої ознаки у кримінальному законодавстві різних країн, а також доктринальних положень медицини і юриспруденції.Целью исследования явилось выявление наиболее оптимального признака потерпевшего от ненасильственного полового сношения с несовершеннолетним на основании анализа подходов к определению такого признака в уголовном законодательстве разных стран, а также доктринальных положений медицины и юриспруденции

Continuous Flow Metathesis for Direct Valorization of Food Waste: An Example of Cocoa Butter Triglyceride.

The direct chemical conversion of cocoa butter triglycerides, a material available as a postmanufacture waste stream from the food industry, to 1-decene by way of ethenolysis is reported. The conversion of the raw waste material was made possible by use of 1 mol % of the [RuCl2(iBu-phoban)2(3-phenylindenyl)] catalyst. The process has been investigated in both batch and flow conditions, where the latter approach employs a Teflon AF-2400 tube-in-tube gas-liquid membrane contactor to deliver ethylene to the reaction system. These preliminary studies culminate in a continuous processing system, which maintained a constant output over a 150 min period tested.The ERC (Advanced Investigator Award-FUNCAT to S.P.N.) and EPSRC are gratefully acknowledged for support (S.V.L., D.L.B., Award No. EP/K009494/1). Umicore AG is acknowledged for their generous gift of materials. S.P.N. is a Royal Society Wolfson Research Merit Award holder.This is the final version of the article. It first appeared from ACS via http://dx.doi.org/10.1021/acssuschemeng.5b00397

Pd/C catalysts based on synthetic carbons with bi- and tri-modal pore-size distribution: Applications in flow chemistry

Synthetic carbons with hierarchical mesopores are promising for developing new catalysts for intensified continuous-flow catalysis in structured reactors.Financial support from the Engineering and Physical Sciences Research Council (Engineering Functional Materials, EP/C519736/1), the Overseas Research Students Awards Scheme and the University of Bath Research Studentship is gratefully acknowledged. The assistance of Dr Martin Jennings Dr. Chris Muryn (School of Chemistry, The University of Manchester) on ICP-OES and XPS analyses is acknowledged. KW acknowledges the Royal Society for the award of an Industry Fellowship.This is the author accepted manuscript. The final version is available from RSC via http://dx.doi.org/10.1039/C5CY01401

Pd/C catalysts based on synthetic carbons with bi- and tri-modal pore-size distribution: applications in flow chemistry

Two new types of phenolic resin-derived synthetic carbons with bi-modal and tri-modal pore-size distributions were used as supports for Pd catalysts. The catalysts were tested in chemoselective hydrogenation and hydrodehalogenation reactions in a compact multichannel flow reactor. Bi-modal and tri-modal micro-mesoporous structures of the synthetic carbons were characterised by N2 adsorption. HR-TEM, PXRD and XPS analyses were performed for characterising the synthesised catalysts. N2 adsorption revealed that tri-modal synthetic carbon possesses a well-developed hierarchical mesoporous structure (with 6.5 nm and 42 nm pores), contributing to a larger mesopore volume than the bi-modal carbon (1.57 cm3 g–1 versus 1.23 cm3 g–1). It was found that the tri-modal carbon promotes a better size distribution of Pd nanoparticles than the bi-modal carbon due to presence of hierarchical mesopore limitting the growth of Pd nanoparticles. For all the model reactions investigated, the Pd catalyst based on tri-modal synthetic carbon (Pd/triC) show high activity as well as high stability and reproducibility. The trend in reactivities of different functional groups over the Pd/triC catalyst follows a general order alkyne >> nitro > bromo >> aldehyde.Financial support from the Engineering and Physical Sciences Research Council (Engineering Functional Materials, EP/C519736/1), the Overseas Research Students Awards Scheme and the University of Bath Research Studentship is gratefully acknowledged. The assistance of Dr Martin Jennings Dr. Chris Muryn (School of Chemistry, The University of Manchester) on ICP-OES and XPS analyses is acknowledged. KW acknowledges the Royal Society for the award of an Industry Fellowship.This is the author accepted manuscript. The final version is available from RSC via http://dx.doi.org/10.1039/C5CY01401

Is it possible to enhance immune response after vaccination? The role of a probiotic with a proven positive effect on all components of the immune system

Preventive vaccination is currently the most affordable and economical way to reduce morbidity and mortality from many infections, improve quality and human life expectancy with an almost ideal balance of benefits and risks among all medical procedures. The article deals with the reasons for variability of the immune response caused by vaccines, between individuals and between populations, which is of fundamental importance for human health. The authors have presented data indicating a key role of the gut microbiota in the control of the immune response to vaccination. Particular attention is paid to the microbial diversity in different loci of the body. The role of microorganisms in the proper functioning of the body and the formation of a number of pathological conditions is described. Most modern vaccines are live-attenuated, killed / inactivated or subunit (recombinant) vaccines, and they are designed for the parenteral route of administration. Most of these vaccines elicit a weak immune response, especially in the mucous membranes, due to the route of administration and are associated with weak cell-mediated immunity. Therefore, mechanisms that can enhance virus-specific vaccine immunity in infants and children are required, such as the use of more potent or selective immunity-enhancing adjuvants. Some probiotic strains may be considered as promising vaccine adjuvants. This article evaluates the recent clinical studies of probiotics used to enhance vaccine-specific immunity in adults and infants. The present-day knowledge on the role of the probiotic strain Lactobacillus rhamnosus GG with the aim of activating immunity after vaccination are presented

Infant colic: from theory to practice

Infant colic is one of the most common, yet least studied, functional disorders of the gastrointestinal tract. Until now, there is no certainty both in the understanding of the nature of this condition and in the approaches to its correction. At the same time, infant crying is of concern to parents, forcing them to seek professional help and incur considerable medical expenses and to resort, sometimes unreasonably, to dietary and medical corrections. This article provides information on the etiology, pathogenesis and management of infantile colic from an evidence-based perspective, based on a review of the current literature. Various preconditions for the occurrence and development of infantile colic are analysed in detail, none of which can affect all occurrences. Evidence for the proven efficacy of including Lactobacillus reuteri in the treatment of intestinal colic in infants is presented. Effects on the gastrointestinal tract microbiome can be of undeniable benefit. Lactobacillus reuteri is one of the most studied and scientifically documented probiotics. 203 completed clinical trials involving 17,200 participants, including 67 trials involving 8,200 participants between 0 and 3 years of age. Numerous placebo-controlled studies have shown that taking Lactobacillus reuteri DSM 17938 can significantly reduce crying time in infants with colic, and in these studies, rates of 50% or more reduction in crying time were 2.3 times higher compared to controls