Copper(II) Bromide–Catalyzed C-C/C-N Bond-Forming Reactions: Synthesis of Pyrrole-Incorporated Triarylmethanes

We have achieved a facile copper(II) bromide–catalyzed synthesis of 2,3,4-trisubtitued pyrrole incorporated into unsymmetrical triarylmethanes through direct replacement of hydroxyl group in the pyrrolyl phenyl methanol with electron-rich aromatic and heteroaromatic compounds. The newly developed method has been applied to a facile synthesis of a C2 symmetric bis-triarylmethane in which the two triarylmethanes were bridged through piperzine. The copper(II) bromide catalysis led to C-C bond formation at the C(5) position when the reacting partner was imidazole. In contrast, C-N bond formation took place with benzimdazole or 2-methylbenzimidazole.     

An efficient synthesis of β-ketoesters via transesterification and its application in Biginelli reaction under solvent-free,catalyst-free conditions

A simple and efficient transesterification process for the synthesis of β-ketoester derivatives has been achieved by the reaction of methyl β-ketoester with higher alcohols at 110 °C under solvent-free, catalyst-free conditions and its application in synthesis of 3,4-dihydropyrimidin-2(1H)-ones C-5 ester derivatives via Biginelli reaction has been described.     

Use of chromatographic pre-concentration for routine uranium bioassay analysis by ICP-MS

Routine monitoring of urine is an effective way to detect occupational intake of radioactive material. Historically, determinations of uranium isotopic ratios have been performed by radiochemical separation followed by alpha spectrometry. With recent advancements in technology, inductively coupled plasma-mass spectrometry (ICP-MS) has become widely available for the determination of trace metals as well as radioactive nuclides with long half-lives, such as ²³⁸U in urine. Furthermore, ICP-MS measurements of ²³⁸U do not require radiochemical separation since the number of atoms in the sample is determined instead of the number of alpha particles emitted. However, this method does not provide good sensitivity for the determination of ²³⁵U due to its shorter half-life. An improved procedure using pre-concentration of uranium and determination by ICP-MS decreases the detection limit by a factor of ten or greater with only slight increase in total analysis time. The method also has the capability of accurately determining the isotopic ratio of the sample, which is very important in cases where enriched or depleted uranium is involved.     

Liquid crystal parameters through image analysis

A technique which combines image analysis and polarising optical microscope (POM) is a useful tool for the physical investigation of discotic liquid crystals, such as hexabutoxytriphenylene and hexahexyloxytriphenylene. This investigation includes the phase transitions, optical properties and order parameter as a function of temperature. Textures of discotic liquid crystals are captured as a function of temperature using POM. These microscopic textures are analysed using MATLAB software to compute statistical parameters, Legendre moments, optical parameters and order parameters of discotic liquid crystal samples. Compared with other techniques in the literature, the proposed methodology is a reliable and very simple technique for the physical investigation of liquid crystals.     

Photoinduced phase transitions

Employing actinic light to alter/stabilise a particular thermodynamic phase via the photo-isomerisation of the constituent molecules is an interesting tool to investigate soft matter from a new dimension. This article focuses on our recent results on several aspects of these non-equilibrium phase transitions, which are isothermal in nature. We specifically discuss (i) the influence of different parameters, such as confinement, applied electric field, pressure etc., on the dynamics associated with both the photochemical transition driving the equilibrium nematic to the non-equilibrium isotropic phase and the thermal back relaxation recovering the nematic phase, (ii) unique light-driven disorder–order transition in a reentrant system, (iii) dynamic self-assembly of the smectic A phase, which is stabilised only in the presence of actinic light, (iv) novel temperature-intensity phase diagrams and an example of primary and secondary photo-ferroelectric effects in an antiferroelectric smectic C system. These results highlight the fact that the actinic light can be used as a new tool to study phase transitions and the associated critical phenomena that could also bring about effects that are not seen in equilibrium situations.     

Optical properties of a mesogen by image analysis

An image analysis technique in conjunction with polarising optical microscopy (POM) is proposed for assessment of the thermo-optical properties of homogeneously aligned chiral ester liquid crystals of the type ((S)-(-)-2-methylbutyl 4′-(4″-n-alkanoyloxybenzoyloxy) biphenyl-4-carboxylates, where n?=?16 or 18. Chiral ester textures are recorded as a function of temperature using POM provided with a hot-stage and a high-resolution colour camera. Temperature-dependent optical parameters, or thermo-optical properties such as optical transmission, degree of polarisation, absorption coefficient and birefringence are computed for chiral esters by analysing the texture of samples using MATLAB software. This is a simple experimental technique for observing how the optical parameters of liquid crystals change with temperature.     

Thermodynamic and Structural Trends in Hexavalent Actinyl Cations: Complexation of Dipicolinic Acid with NpO22+ and PuO22+ in Comparison with UO22+

The complexation of NpO₂²⁺ and PuO₂²⁺ with dipicolinic acid (DPA) has been investigated in 0.1 M NaClO₄ by spectrophotometry, microcalorimetry, and single crystal diffractometry. Formation of 1:1 and 1:2 (metal/ligand molar ratio) complexes of DPA with NpO₂²⁺ and PuO₂²⁺ were identified and the thermodynamic parameters were determined and compared with those of UO₂²⁺. All three hexavalent actinyl cations form strong 1:1 DPA complexes with slightly decreasing but comparable stability constants from UO₂²⁺ to PuO₂²⁺, whereas the stability constants of the 1:2 complexes (log β₂) decrease substantially along the series (16.3 for UO₂L₂^2?, 15.17 for NpO₂L₂^2?, and 14.17 for PuO₂L₂^2? at 25 °C). The enthalpies of complexation for the 1:2 complexes become less exothermic from UO₂L₂^2? (?28.9 kJ mol^?1), through NpO₂L₂^2? (?27.2 kJ mol^?1), and to PuO₂L₂^2? (?22.7 kJ mol^?1). The trends in the thermodynamic parameters are discussed in terms of the effective charge of the cations and the steric constraints in the structures of the complexes. In addition, the features of the absorption spectra, including the wavelength and intensity of the absorption bands, are related to the perturbation of the ligand field and the symmetry of the actinyl complexes.     

Ca(Ⅱ)、Mg(Ⅱ)和Zn(Ⅱ)与丙二醇-水混合体系中L-多巴的二元配合物的生成平衡

在303 K恒温条件下,以NaCl为电解质保持离子强度为0.16 mol·L^-1,用pH滴定法研究了M(Ⅱ)-Dopa(多巴)二元配合物在0～60%(V/V)的丙二醇(PG)-水体系中的生成平衡。在PG-水体系中,Ca(Ⅱ)和Mg(Ⅱ)的典型配合物为MLH,ML₂,ML₂H和ML₂H₂,而Zn(Ⅱ)的典型配合物为ML,MLH,ML₂,ML₂H和ML₂H₂。根据静电和非静电力解释了稳定常数随介质的介电常数而变化的倾向。还讨论了在不同组成的丙二醇(PG)-水体系中配合物物种随pH值变化的情况。     

The first stereoselective synthesis of dendrodolide A

The first stereoselective total synthesis of natural product, dendrodolide A (1) is described from readily available (R)-propylene oxide and 3-buten-1-ol as starting materials. The synthesis was achieved in 10 steps with an overall yield of 19.1%. The key steps involved in the synthesis are Jacobsen hydrolytic kinetic resolution, epoxide ring opening with 2-allyl-1, 3-dithiane, Yamaguchi esterification, and ring-closing metathesis (RCM).     

Influence of sputter power on structural and electrical properties of TiO2 films for Al/TiO2/Si gate capacitors

Titanium dioxide (TiO₂) thin films were deposited onto p‐Si substrates held at room temperature by reactive Direct Current (DC) magnetron sputtering at various sputter powers in the range 80–200 W. The as‐deposited TiO₂ films were annealed at a temperature of 1023 K. The post‐annealed films were characterized for crystallographic structure, chemical binding configuration, surface morphology and optical absorption. The electrical and dielectric properties of Al/TiO₂/p‐Si structure were determined from the capacitance–voltage and current–voltage characteristics. X‐ray diffraction studies confirmed that the as‐deposited films were amorphous in nature. After post‐annealing at 1023 K, the films formed at lower powers exhibited anatase phase, where as those deposited at sputter powers > 160 W showed the mixed anatase and rutile phases of TiO₂. The surface morphology of the films varied significantly with the increase of sputter power. The electrical and dielectric properties on the air‐annealed Al/TiO₂/p‐Si structures were studied. The effect of sputter power on the electrical and dielectric characteristics of the structure of Al/TiO₂/p‐Si (metal‐insulator‐semiconductor) was systematically investigated. Copyright © 2014 John Wiley & Sons, Ltd.