(−)‐Englerin A is a Potent and Selective Activator of TRPC4 and TRPC5 Calcium Channels

Current therapies for common types of cancer such as renal cell cancer are often ineffective and unspecific, and novel pharmacological targets and approaches are in high demand. Here we show the unexpected possibility for the rapid and selective killing of renal cancer cells through activation of calcium‐permeable nonselective transient receptor potential canonical (TRPC) calcium channels by the sesquiterpene (?)‐englerin A. This compound was found to be a highly efficient, fast‐acting, potent, selective, and direct stimulator of TRPC4 and TRPC5 channels. TRPC4/5 activation through a high‐affinity extracellular (?)‐englerin A binding site may open up novel opportunities for drug discovery aimed at renal cancer.     

Out of the blue: semiconductor laser pumped visible rare‐earth doped lasers

The rise of semiconductor‐based pump sources such as In_xGa_1‐xN‐laser diodes or frequency‐doubled optically pumped semiconductor lasers with emission wavelengths in the blue encourages a revisitation of the rare‐earth ions Pr³⁺, Sm³⁺, Tb³⁺, Dy³⁺, Ho³⁺ and Er³⁺ with respect to their properties as active ions in crystalline solid‐state laser materials with direct emission in the visible spectral range. Nowadays, some of these blue‐pumped visible lasers compete with Nd³⁺‐lasers in terms of efficiency and direct lasing at various colors from the cyan‐blue to the deep red can be addressed in very simple and compact laser setups. This paper highlights the spectroscopic properties of suitable rare‐earth ions for visible lasing and reviews the latest progress in the field of blue‐pumped visible rare‐earth doped solid‐state lasers.

     

Crystal Structures of Hydrazinium(II) Salts of [SbF6]– and [Sb2F11]–

N₂H₆(Sb₂F₁₁)₂ was synthesized by the reaction of N₂H₆F₂ with excess of SbF₅ in anhydrous hydrogen fluoride (aHF). It crystallizes in the triclinic space group P$\bar{1}$ (No. 2) with a = 6.6467(3) Å, b = 8.3039(4) Å, c = 8.3600(5) Å, α = 76.394(5) ^o, β = 70.161(5) ^o, γ = 70.797(5) ^o, V = 405.90(4) ų at 150 K, Z = 2. When it is redissolved in aHF, it solvolysis with the release of SbF₅ yielding N₂H₆(SbF₆)₂ which crystallizes in the monoclinic C2/c space group (No. 15) with a = 7.3805(3) Å, b = 12.3248(5) Å, c = 10.4992(4) Å, β = 92.218(4) ^o, V = 954.33(7) ų at 150 K, and Z = 8. No other phases were observed in crystallization products when different molar ratios of N₂H₆F₂/SbF₅ (1:1,2:3,1:3) in aHF were used as starting materials.     

Effect of Y2O3 on microstructural characteristics and wear resistance of cobalt‐based composite coatings produced on TA15 titanium alloy surface by laser cladding

The effects of Y₂O₃ on the microstructure, phase composition of the coatings, microhardness and wear resistance of cobalt‐based composite coatings prepared by laser cladding were investigated. The TA15 titanium alloy was selected as substrate which the cobalt‐based composite powder with different content of Y₂O₃ was cladded on. The microstructure of the coatings was observed by scanning electron microscope (SEM) and metallurgical microscope. The phase structure of the coatings was determined by X‐ray diffraction (XRD), and the microhardness and wear resistance of the coatings were measured by hardness tester and wear testing machine. The results show that the rare earth oxide Y₂O₃ can refine and purify the microstructure of the coatings, reduce the porosities and cracks and improve compactness of the coatings. Moreover the addition of Y₂O₃ improves the microhardness of the coatings and reduces the friction coefficient, thus improving the wear property of the coatings. And the wear resistance of the coating with Y₂O₃ has improved about 50 times; the highest value of microhardness in the coating is HV1181.1. And 0.8 wt% content of Y₂O₃ in the coating is the best choice for improving the microhardness and wear resistance of the coating. It is feasible to improve the microstructure and tribological properties of laser cladding coatings by adding of Y₂O₃. Copyright © 2014 John Wiley & Sons, Ltd.     

Enhanced conformational sampling method for proteins based on the TaBoo SeArch algorithm: Application to the folding of a mini‐protein,chignolin

The conformational samplings are indispensible for obtaining reliable canonical ensembles, which provide statistical averages of physical quantities such as free energies. However, the samplings of vast conformational space of biomacromolecules by conventional molecular dynamics (MD) simulations might be insufficient, due to their inadequate accessible time‐scales for investigating biological functions. Therefore, the development of methodologies for enhancing the conformational sampling of biomacromolecules still remains as a challenging issue in computational biology. To tackle this problem, we newly propose an efficient conformational search method, which is referred as TaBoo SeArch (TBSA) algorithm. In TBSA, an inverse energy histogram is used to select seeds for the conformational resampling so that states with high frequencies are inhibited, while states with low frequencies are efficiently sampled to explore the unvisited conformational space. As a demonstration, TBSA was applied to the folding of a mini‐protein, chignolin, and automatically sampled the native structure (C_α root mean square deviation < 1.0 Å) with nanosecond order computational costs started from a completely extended structure, although a long‐time 1‐µs normal MD simulation failed to sample the native structure. Furthermore, a multiscale free energy landscape method based on the conformational sampling of TBSA were quantitatively evaluated through free energy calculations with both implicit and explicit solvent models, which enable us to find several metastable states on the folding landscape. © 2015 Wiley Periodicals, Inc.     

Double-ion imprinted polymer @magnetic nanoparticles modified screen printed carbon electrode for simultaneous analysis of cerium and gadolinium ions

A typical, reproducible, and rugged screen printed carbon electrode, modified with dual-ion imprinted beads, was fabricated employing the “surface grafting from” approach. For this, the acyl chloride functionalized magnetic nanoparticles were first immobilized and chemically attached with a typical functional monomer (but-2-enedioic acid bis-[(2-amino-ethyl)-amide]) on the electrode surface. This was subsequently subjected to the thermal polymerization in the presence of template ions (Ce(IV) and Gd(III)), cross-linker (ethylene glycol dimethacrylate), initiator (AIBN), and multiwalled carbon nanotubes. The modified sensor was used for the simultaneous analysis of both template ions in aqueous, blood serum, and waste-water samples, using differential pulse anodic stripping voltammetry which revealed two oxidation peaks for respective templates with resolution as much as 950 mV, without any cross reactivity, interferences and false-positives. The detection limits realized by the proposed sensor, under optimized conditions, were found to be as low as 0.07 ng mL⁻¹ for Ce(IV) and 0.19 ng mL⁻¹ for Gd(III) (S/N = 3) that could eventually be helpful for lanthanide estimation at stringent levels.     

A circular dichroism sensor for Ni and Co based on l-cysteine capped cadmium sulfide quantum dots

A new circular dichroism sensor for detecting Ni²⁺ and Co²⁺ was proposed for the first time using chiral chelating quantum dots. The detection principle was based on changing of circular dichroism signals of the chiral quantum dots when forming a chiral complex with Ni²⁺ or Co²⁺. l-Cysteine capped cadmium sulfide quantum dots (l-Cyst-CdS QDs) were proposed as a chiral probe. The CD spectrum of l-Cyst-CdS QDs was significantly changed in the presence of Ni²⁺ and Co²⁺. On the other hand, other studied cations did not alter the original CD spectrum. Moreover, when increasing the concentration of Ni²⁺ or Co²⁺, the intensity of the CD spectrum linearly increased as a function of concentration and could be useful for the quantitative analysis. The proposed CD sensor showed linear working concentration ranges of 10–60 μM and 4–80 μM with low detection limits of 7.33 μМ and 1.13 μM for the detection of Ni²⁺ and Co²⁺, respectively. Parameters possibly affected the detection sensitivity such as solution pH and incubation time were studied and optimized. The proposed sensor was applied to detect Ni²⁺ and Co²⁺ in real water samples, and the results agreed well with the analysis using the standard ICP-OES.     

Highly selective and sensitive paper-based colorimetric sensor using thiosulfate catalytic etching of silver nanoplates for trace determination of copper ions

A novel, highly selective and sensitive paper-based colorimetric sensor for trace determination of copper (Cu²⁺) ions was developed. The measurement is based on the catalytic etching of silver nanoplates (AgNPls) by thiosulfate (S₂O₃²⁻). Upon the addition of Cu²⁺ to the ammonium buffer at pH 11, the absorption peak intensity of AuNPls/S₂O₃²⁻ at 522 nm decreased and the pinkish violet AuNPls became clear in color as visible to the naked eye. This assay provides highly sensitive and selective detection of Cu²⁺ over other metal ions (K⁺, Cr³⁺, Cd²⁺, Zn²⁺, As³⁺, Mn²⁺, Co²⁺, Pb²⁺, Al³⁺, Ni²⁺, Fe³⁺, Mg²⁺, Hg²⁺ and Bi³⁺). A paper-based colorimetric sensor was then developed for the simple and rapid determination of Cu²⁺ using the catalytic etching of AgNPls. Under optimized conditions, the modified AgNPls coated at the test zone of the devices immediately changes in color in the presence of Cu²⁺. The limit of detection (LOD) was found to be 1.0 ng mL⁻¹ by visual detection. For semi-quantitative measurement with image processing, the method detected Cu²⁺ in the range of 0.5–200 ng mL⁻¹(R² = 0.9974) with an LOD of 0.3 ng mL⁻¹. The proposed method was successfully applied to detect Cu²⁺ in the wide range of real samples including water, food, and blood. The results were in good agreement according to a paired t-test with results from inductively coupled plasma-optical emission spectrometry (ICP-OES).     

C3对称性含膦三足体衍生物及其Eu(Ⅲ)配合物的合成以及与DNA相互作用的研究

设计合成了一种新的C3对称性含膦三足体衍生物N',N',N'-三(亚磷酸三乙酯)缩氨三乙酸(L)及其Eu(Ⅲ)配合物.用1H NMR、13C NMR、红外光谱、元素分析、差热-热重及紫外光谱对其组成和结构进行分析和表征.结果表明,三足体衍生物与稀土苦味酸盐(Eu(pic)3·6H2O)形成了1:1配合物Eu(pic)3L.综合运用紫外-可见吸收光谱法、荧光光谱法和循环伏安法研究了Eu(pic)3L与小牛胸腺DNA之间的结合模式,结果表明,配合物Eu(pic)3L与DNA之间以嵌插形式发生相互作用.将该配合物作为杂交探针,对其在DNA电化学传感器方面的应用进行了探讨.结果发现,该配合物在修饰单链DNA的电极检测作用下,无明显的电化学信号响应,而当将其用于检测杂交双链DNA时,出现了明显信号,并且该配合物的DNA传感器对互补序列、错配序列及非互补序列都有良好的选择作用.     

Metal‐Chelating N,N′‐Bis(4‐dimethylaminophenyl)acetamidinyl Radical: A New Chromophore for the Near‐Infrared Region

A new non‐innocent ligand redox system, N,N′‐bis(4‐dimethylaminophenyl) substituted acetamidinato/acetamidinyl, has been designed and described by example of structurally and spectroscopically characterized ruthenium complexes. The hitherto unreported ligand is responsible for rather intense and narrow absorptions in the near‐infrared region of the one‐ and two‐electron oxidized forms. The spectroscopic, computational, and first structural characterization of an amidinyl radical complex adds to the list of established N‐based radical ligands.