Graphene-modified Monolithic Capillary Column for the Microextraction of Trace Benzodiazepines in Biological Samples

A graphene monolithic column was fabricated in a capillary using π-electron-rich poly(N-vinylcarbazole-divinylbenzene) as the supporter through in situ one-step polymerization for the enrichment of trace benzodiazepines in biological samples. This new three-dimensional monolith showed uniformity and a continuous column bed; more importantly, it retained the unique properties of graphene that are typically associated with individual graphene sheets. Based on the large delocalized π-electron system, graphene forms π–π stacking interactions with benzodiazepines and benzene rings of poly(N-vinylcarbazole-divinylbenzene), which not only enhance the extraction performance for benzodiazepines compared to the neat polymer but also provide chemical stability of the graphene monolith. Moreover, several factors likely to affect the extraction, including ionic strength, sample pH, sample volume, and eluant volume were studied in detail. The optimized method gave a linear range of 0.005–1?ng?mL^?1, and detection limits of 1.12–2.35?ng?L^?1. Finally, the graphene monolith was successfully applied to the separation and enrichment of benzodiazepines from urine and hair samples coupled with high-performance liquid chromatography–mass spectrometry. The recoveries were in the range of 78.6–85.6% for urine and 87.2–94.3% for hair with relative standard deviations of 3.4–6.9 and 2.9–8.3%, respectively.     

Computational studies on optoelectronic and charge transfer properties of some perylene‐based donor‐π‐acceptor systems for dye sensitized solar cell applications

We report DFT studies on some perylene‐based dyes for their electron transfer properties in solar cell applications. The study involves modeling of different donor‐π‐acceptor type sensitizers, with perylene as the donor, furan/pyrrole/thiophene as the π‐bridge and cyanoacrylic group as the acceptor. The effect of different π‐bridges and various substituents on the perylene donor was evaluated in terms of opto‐electronic and photovoltaic parameters such as HOMO‐LUMO energy gap, λ_max, light harvesting efficiency(LHE), electron injection efficiency (Ø_inject), excited state dye potential (E^dye*), reorganization energy(λ), and free energy of dye regeneration (). The effect of various substituents on the dye–I₂ interaction and hence recombination process was also evaluated. We found that the furan‐based dimethylamine derivative exhibits a better balance of the various optical and photovoltaic properties. Finally, we evaluated the overall opto‐electronic and transport parameters of the TiO₂‐dye assembly after anchoring the dyes on the model TiO₂ cluster assembly.     

The self‐consistent charge density functional tight‐binding theory study of carbon adatoms using tuned Hubbard U parameters

The self‐consistent charge density functional tight‐binding (DFTB) theory is a useful tool for realizing the electronic structures of large molecular complex systems. In this study, the electronic structure of C₆₁ formed by fullerene C₆₀ with a carbon adatom is analyzed, using the fully localized limit and pseudo self‐interaction correction methods of DFTB to adjust the Hubbard U parameter (DFTB + U). The results show that both the methods used to adjust U can significantly reduce the molecular orbital energy of occupied states localized on the defect carbon atom and improve the gap between highest occupied molecular orbital(HOMO) and lowest unoccupied molecular orbital(LUMO) of C₆₁. This work will provide a methodological reference point for future DFTB calculations of the electronic structures of carbon materials.     

Characterization of Sixteenth to Nineteenth Century Ottoman Silk Brocades by Scanning Electron Microscopy–Energy Dispersive X-Ray Spectroscopy and High-Performance Liquid Chromatography

Historical textiles in the Topkap? Museum, which are called silk kaftans and brocades by art historians from the sixteenth and nineteenth were characterized by scanning electron microscopy–energy dispersive X-ray spectroscopy (SEM–EDX) and high-performance liquid chromatography with diode array detection for identification of metal threads and dyestuffs. In the most Ottoman textiles, metal threads, especially belonging to the sultans, were used as the gold gild. Although the chemical composition of the samples on the surface may easily be obtained by SEM–EDX, the thickness of the thin gold layer on metal threads cannot be obtained directly. Hence, the goal of this project is to describe whether metal threads are gilded or not and to measure coating thickness. A new method was developed for measuring the thickness of gold layer, and the modeling was reformed. The SEM–EDX results were interpreted in accordance with the theoretical models. The coating thickness of metal threads was subsequently measured in ancient textiles. The thickness, depth, and valuable metal composition in the threads of the artistic objects were obtained by this approach. Dye analysis was used to characterize the presence of indigotin, carminic acid, ellagic acid, and luteolin in the historical textiles.     

Ultrafine grain formation and coating mechanism arising from a blast coating process: A transmission electron microscopy analysis

This article examines the substrate/coating interface of a coating deposited onto mild steel and stainless steel substrates using an ambient temperature blast coating technique known as CoBlast. The process uses a coincident stream of an abrasive blast medium and coating medium particles to modify the substrate surface. The hypothesis for the high bond strength is that the abrasive medium roughens the surface while simultaneously disrupting the passivating oxide layer of the substrate, thereby exposing the reactive metal that then reacts with the coating medium. The aim of this study is to provide greater insight into the coating/substrate bonding mechanism by analysing the interface between a hydroxyapatite coating on both mild and stainless steel substrates. The coating adhesion was measured via a tensile test, and bond strengths of approximately 45 MPa were measured. The substrate/coating interface was examined using transmission electron microscopy and selected area diffraction. The analysis of the substrate/coating interface revealed the presence of ultrafine grains in both the coating and substrate at interface associated with deformation at the interface caused by particle impaction during deposition. The chemical reactivity resulting from the creation of these ultrafine grains is proposed to explain the high adhesive strength of CoBlast coatings.     

Viscoelastic behaviour of silica filled natural rubber composites – Correlation of shear with elongational testing

Dynamic mechanical behaviour of natural rubber-silica composites was studied by a frequency sweep method at different temperatures (40 °C,70 °C and 100 °C) using a dynamic mechanical analyzer and a rotorless rheometer, RPA, in an attempt to establish a correlation between the two. The composites with silica content up to 40 phr were studied. It was found that the dependence of dynamic modulus on the frequency as obtained from both the instruments followed a similar trend. This suggests that the dynamic mechanical properties of rubber compounds can be determined even during curing. A correlation could be arrived at between the two sets of data, making it possible to predict one set knowing the other. The impact of silane coupling agent, bis (3-triethoxysilylpropyl tetrasulphide), TESPT, on viscoelasticity was also investigated. The mechanical properties were improved in the presence of TESPT. Additionally, an increase in thermal stability was also observed in the presence of TESPT. Scanning electron micrographs showed the better filler dispersion in the case of silane-coupled silica composites.     

A full‐pivoting algorithm for the Cholesky decomposition of two‐electron repulsion and spin‐orbit coupling integrals

A significant reduction in the computational effort for the evaluation of the electronic repulsion integrals (ERI) in ab initio quantum chemistry calculations is obtained by using Cholesky decomposition (CD), a numerical procedure that can remove the zero or small eigenvalues of the ERI positive (semi)definite matrix, while avoiding the calculation of the entire matrix. Conversely, due to its antisymmetric character, CD cannot be directly applied to the matrix representation of the spatial part of the two‐electron spin‐orbit coupling (2e‐SOC) integrals. Here, we present a computational strategy to achieve a Cholesky representation of the spatial part of the 2e‐SOC integrals, and propose a new efficient CD algorithm for both ERI and 2e‐SOC integrals. The proposed algorithm differs from previous CD implementations by the extensive use of a full‐pivoting design, which allows a univocal definition of the Cholesky basis, once the CD δ threshold is made explicit. We show that is the upper limit for the errors affecting the reconstructed 2e‐SOC integrals. The proposed strategy was implemented in the ab initio program Computational Emulator of Rare Earth Systems (CERES), and tested for computational performance on both the ERI and 2e‐SOC integrals evaluation. © 2017 Wiley Periodicals, Inc.     

受电子束辐照的硬铝靶的喷射冲量耦合系数随能通量的变化规律

采用通光式传感法和直接测量特定时间间隔的探头原理，在闪光２号装置上进行了电子束辐照硬铝靶产生的喷射冲量耦合系数与能通量关系的研究。结果表明:在能通量为１１５～２４０Ｊ／ｃｍ２范围内，喷射冲量和亏损质量面密度都随能通量近似线性变化，而喷射冲量耦合系数随能通量增大而缓慢递增，并趋于一渐近值；硬铝产生喷射冲量的能通量阈值为４０Ｊ／ｃｍ２左右；喷射冲量值为８１～２１８Ｐａｓ，亏损质量面密度为３．１ １０－２～８．６１０－２ｇ／ｃｍ２，喷射冲量耦合系数为０．７０～０．９８Ｐａｓ／（Ｊ／ｃｍ　２）。     

Theoretical Studies on the Halogen Bond between Propargyl Radical and Dihalogen Molecules

MP2/aug‐cc‐pVDZ calculations are carried out on the geometries, vibrational frequencies, interaction energies and topological properties for the π‐type halogen‐bonded complexes between propargyl radical and dihalogen molecules ClF, BrF and BrCl. There are two kinds of geometries: complex ( a ) involves the interaction between the X (X=Cl, Br) atom and the midpoint of C(1) –C(2) bond, complex ( b ) involves the interaction between the X atom and C(3) atom. The lengths of the halogen bond, the frequencies of the halogen bond, the elongation extent of the X–Y (XY=ClF, BrF, BrCl) bond, topological parameters at the BCPs of the halogen bond and X–Y bond are all well consistent with the interaction energies. The interaction of complex ( a ) is stronger than that of complex ( b ); the interaction of propargyl···BrF is stronger than that of propargyl···ClF and propargyl···BrCl. For the complexes ( a ) and ( b ), the charge transfer is observed from propargyl radical to XY, the atomic energy, the dipolar polarization, and the volume of the halogen atom X decrease upon complex formation.