Unusual mode of reactivity of 2-alkylidene-4-oxothiazolidine S-oxides under the Pummerer reaction conditions

The reactivity of 2-alkylidene-4-oxothiazolidine S-oxides under the Pummerer reaction conditions, using Ac₂O, TFAA, SOCl₂ and SOBr₂ as initiators, has been examined. Almost all reactions proceeded with absolute regioselectivity yielding α-substituted sulfides or vinyl-chloro derivatives. The mechanism for the formation of the latter products was postulated and proved experimentally.     

Fabrication of Pascal-triangle Lattice of Proteins by Inducing Ligand Strategy

A protein Pascal triangle has been constructed as new type of supramolecular architecture by using the inducing ligand strategy that we previously developed for protein assemblies. Although mathematical studies on this famous geometry have a long history, no work on such Pascal triangles fabricated from native proteins has been reported so far due to their structural complexity. In this work, by carefully tuning the specific interactions between the native protein building block WGA and the inducing ligand R-SL , a 2D Pascal-triangle lattice with three types of triangular voids has been assembled. Moreover, a 3D crystal structure was obtained based on the 2D Pascal triangles. The distinctive carbohydrate binding sites of WGA and the intralayer as well as interlayer dimerization of RhB was the key to facilitate nanofabrication in solution. This strategy may be applied to prepare and explore various sophisticated assemblies based on native proteins.     

High regioselectivity in the heterocyclization of β-oxonitriles to 4-oxothiazolidines: X-ray structure proof

Base-catalyzed reactions of β-oxonitriles 1 with diethyl mercaptosuccinate favour heterocyclization to afford 2-alkylidene-4-oxothiazolidines 3, rather than 2-alkylidene-4-oxo-1,3-thiazinanes 4. The observed regioselectivity is based on spectroscopic and experimental evidence, including a single-crystal X-ray structure determination.     

The Generalized Cross Entropy Method, with Applications to Probability Density Estimation

Nonparametric density estimation aims to determine the sparsest model that explains a given set of empirical data and which uses as few assumptions as possible. Many of the currently existing methods do not provide a sparse solution to the problem and rely on asymptotic approximations. In this paper we describe a framework for density estimation which uses information-theoretic measures of model complexity with the aim of constructing a sparse density estimator that does not rely on large sample approximations. The effectiveness of the approach is demonstrated through an application to some well-known density estimation test cases.     

Modeling of aortic valve dynamics in a lumped parameter model of left ventricular-arterial coupling

A lumped parameter model of the sub-system of left ventricle, aortic valve, systemic arteries, systemic capillaries and systemic veins was considered during systole. A model of aortic valve dynamics based solely on geometrical and kinematical consideration is defined. The model is described by two geometrical parameters of aortic valve and a few kinematical relationships. The proposed model mimics the incisures in the aortic flow and aortic pressure very well. We showed that the dicrotic notch could be explained by aortic valve closing in terms of a lumped parameter model, without a need for any wave reflection theory. According to the proposed model the effects of aortic valve dynamics on the aortic flow and pressure are mainly limited to the valve opening and closing periods. The model offers a new paradigm for defining a more realistic left ventricle model.      

Highly Dispersible Hexagonal Carbon–MoS2–Carbon Nanoplates with Hollow Sandwich Structures for Supercapacitors

MoS₂, a typical layered transition-metal dichalcogenide, is promising as an electrode material in supercapacitors. However, its low electrical conductivity could lead to limited capacitance if applied in electrochemical devices. Herein, a new nanostructure composed of hollow carbon–MoS₂–carbon was successfully synthesized through an l -cysteine-assisted hydrothermal method by using gibbsite as a template and polydopamine as a carbon precursor. After calcination and etching of the gibbsite template, uniform hollow platelets, which were made of a sandwich-like assembly of partial graphitic carbon and two-dimensional layered MoS₂ flakes, were obtained. The platelets showed excellent dispersibility and stability in water, and good electrical conductivity due to carbon provided by the calcination of polydopamine coatings. The hollow nanoplate morphology of the material provided a high specific surface area of 543 m² g⁻¹, a total pore volume of 0.677 cm³ g⁻¹, and fairly small mesopores (≈5.3 nm). The material was applied in a symmetric supercapacitor and exhibited a specific capacitance of 248 F g⁻¹ (0.12 F cm⁻²) at a constant current density of 0.1 A g⁻¹; thus suggesting that hollow carbon–MoS₂–carbon nanoplates are promising candidate materials for supercapacitors.     

An extraction system for low-energy hydrogen ions formed by electron impact

A system has been developed for extracting near-zero kinetic energy H⁻ and D⁻ ions formed by dissociative electron attachment. It is the essential part of a new set-up for vibrational spectroscopy of hydrogen molecules. A magnetic field is used to collimate the probing electron beam. Ions produced by electron collision with the target molecules are collected by the combined action of this field and an electrostatic field penetrating into the interaction region. Highly effective extraction is achieved by taking into account the correct out-of plane displacement of ion trajectories which is usually neglected in similar arrangements. The extraction conditions are mass dependent so that by proper tuning, mass selection of detected ions is achieved. The new system is also used for detecting positive ions created by electron collisions with hydrogen atoms and molecules.     

Self-assembly Mechanism and Chiral Transfer in CuO Superstructures

Chiral inorganic superstructures have received considerable interest due to the chiral communication between inorganic compounds and chiral organic additives. However, the demanding fabrication and complex multilevel structure seriously hinder the understanding of chiral transfer and self-assembly mechanisms. Herein, we use chiral CuO superstructures as a model system to study the formation process of hierarchical chiral structures. Based on a simple and mild synthesis route, the time-resolved morphology and the in situ chirality evolution could be easily followed. The morphology evolution of the chiral superstructure involves hierarchical assembly, including primary nanoparticles, intermediate bundles, and superstructure at different growth stages. Successive redshifts and enhancements of the CD signal support chiral transfer from the surface penicillamine to the inorganic superstructure. Full-field electro-dynamical simulations reproduced the structural chirality and allowed us to predict its modulation. This work opens the door to a large family of chiral inorganic materials where chiral molecule-guided self-assembly can be specifically designed to follow a bottom-up chiral transfer pathway.     

Presmectic wetting and supercritical-like phase behavior of octylcyanobiphenyl liquid crystal confined to controlled-pore glass matrices

The influence of controlled-pore glass (CPG) confinement on the phase behavior of octylcyanobiphenyl liquid crystal (LC) is studied by means of x-ray scattering and high precision calorimetry. For CPG samples with pore diameter 2R>24 nm, the smectic order parameter temperature dependence eta(T) reveals apparent presmectic ordering far above the bulk smectic A-nematic (SmA-N) phase transition for both nontreated and silane-treated CPG matrices. The behavior of eta(T) is qualitatively similar in all samples, well obeying the mean field approach (MFA) in which the surface wetting tendency plays the dominant role. In contrast, the critical fluctuations remain important in the specific heat data, which cannot be described within the MFA. We show experimentally that randomness and surface wetting become dominant over finite-size effects for 2R approximately<10 nm, in agreement with theoretical analysis. In nontreated samples, the noncritical character of the static disorder and the interfacial LC-CPG coupling almost completely suppress the quasi-SmA-N and nematic-isotropic phase transitions at 2R approximately 15.1 and approximately 7.5 nm, respectively.     

High-resolution calorimetric study of pb(mg_{1/3}nb_{2/3})o_{3} single crystal

Motivated by the long-standing unresolved enigma of the relaxor ferroelectric ground state, we performed a high-resolution heat capacity and polarization study of the field-induced phase transition in the relaxor ferroelectric single crystal Pb(Mg_{1/3}Nb_{2/3})O_{3} (PMN) oriented along the [110] direction. We show that the discontinuous evolution of polarization as a function of the electric field or temperature is a consequence of a true first order transition from a glassy to ferroelectric state, which is accompanied by an excess heat capacity anomaly and released latent heat. We also find that in a zero field there is no ferroelectric phase transition in bulk PMN at any temperature, indicating that the nonergodic dipolar glass phase persists down to the lowest temperatures.