Iron carbonyl thioboronyls: effect of substitution of sulfur for oxygen in the viability of binuclear complexes toward dissociation reactions

The recent discovery of boronyl complexes of the type (R₃P)₂Pt(BO)X (R = cyclohexyl; X = halogen) makes of interest the chemistry of complexes of the related thioboronyl (BS) ligand. In this connection, the binuclear iron carbonyl complex Fe₂(BS)₂(CO)₈ is predicted by density functional theory to have a symmetrical unbridged structure similar to the valence isoelectronic Mn₂(CO)₁₀. Higher-energy unsymmetrical (OC)₅Fe → Fe(BS)₂(CO)₃ structures are also found as well as a doubly bridged Fe₂(BS)₂(CO)₆(µ-CO)₂ structure. The complex Fe₂(BS)₂(CO)₈ is predicted to be viable toward symmetrical dissociation into Fe(BS)(CO)₄ fragments. However, the unsymmetrical dissociation of Fe₂(BS)₂(CO)₈ into Fe(CO)₅ + Fe(BS)₂(CO)₃ is predicted to be exothermic by ~9 kcal mol^?1. The low-energy structures of the mononuclear Fe(BS)₂(CO)₃ include structures in which the two BS ligands have coupled to form a B₂S₂ ligand through B–B bond formation.     

Facile synthesis of Pd-decorated ZnO nanoparticles for acetone sensors with enhanced performance

ZnO and Pd nanoparticles (NPs) with average diameter of 38 and 10 nm were prepared in advance through a chemical solution method. Pd-functionalized ZnO nanoparticles (Pd@ZnO) were simply synthesized by adding ethanol solution of Pd NPs into ZnO powder, and annealing in argon atmosphere at 500 °C for 1 h after grinding for 30 min. The morphology and structure of the materials were systemically analyzed using Brunauer–Emmett–Teller (BET), X-ray diffraction (XRD), field-emission scanning electron microscopy (FESEM), and transmission electron microscopy (TEM) techniques. A weak peak in the XRD pattern of Pd@ZnO belonging to the (111) plane of elemental Pd indicated successfully loading of Pd. EDS and TEM results further confirmed successfully coating of Pd NPs onto the surface of ZnO. Sensors using ZnO NPs decorated with Pd (1 wt%) on the surface of exhibited highly elevated sensitivity of 76 in comparing with the response of 36 when based on pure ZnO NPs. In addition, such modification also resulted in a decrease in the operating temperature from 370 to 340 °C for 100 ppm acetone vapor. The sensing mechanism of the sensor based on Pd@ZnO NPs is discussed. Addition of Pd NPs can play an important role in improving the performance of gas sensors, including high sensitivity, good selectivity, and short response/recovery times.     

Lone-Pair Enhanced Birefringence in an Alkaline-Earth Metal Tin(II) Phosphate BaSn2(PO4)2

The first alkaline-earth metal tin(II) phosphate, BaSn₂(PO₄)₂, has been discovered, which consists of layered structures constructed from strictly alternating [SnO₃]⁴⁻ and [PO₄]³⁻ moieties. This compound is expected to have a large birefringence with Δn≈0.071 at 1064 nm, owing to the presence of stereochemically active lone pair metal cations.     

Silica microbeads capture fetal nucleated red blood cells for noninvasive prenatal testing of fetal ABO genotype

ABO hemolytic disease of the newborn (ABO-HDN), which may cause neonatal jaundice and polycythemia, or even stillbirth or neonatal death, is widespread in China. Prenatal testing for the fetal ABO blood group can reduce unnecessary concerns or ensure prompt treatment. Herein, we presented a method to employ high-density silica microbeads (SiO₂ MBs) for capturing fetal nucleated red blood cells (fnRBCs) in maternal peripheral blood, and we detected the ABO genotype of the fetus using these captured cells. We evaluated 52 patients using the SiO₂ MBs. Among 26 pregnant women with type O blood, 8 (30.8%) of the fetuses had type A blood, 5 (19.2%) had type B blood, and 13 (50%) had type O blood. SRY genes were detected in all 27 male fetuses. This study represents a simple and effective method for noninvasive prenatal detection of the fetal ABO genotype. We believe that this method has great potential for noninvasive prenatal testing of the fetal Rh blood group and other fetal diseases as well.     

The Core/Shell Structure P Doped MoS2@Ni3S2 Nanorods Array for High Current Density Hydrogen Evolution in Alkaline and Acidic Electrolyte

Electrocatalysis is the most promising strategy to generate clean energy H₂, and the development of catalysts with excellent hydrogen evolution reaction (HER) performance at high current density that can resist strong alkaline and acidic electrolyte environment is of great significance for practical industrial application. Therefore, a P doped MoS₂@Ni₃S₂ nanorods array (named P-NiMoS) was successfully synthesized through successive sulfuration and phosphorization. P-NiMoS presents a core/shell structure with a heterojunction between MoS₂ (shell) and Ni₃S₂ (core). Furthermore, the doping of P modulates the electronic structure of the P-NiMoS; the electrons transfer from the t_2g orbital of Ni element to the e_g empty orbital of Mo element through the Ni−S−Mo bond at the Ni₃S₂ and MoS₂ heterojunction, facilitating the hydrogen evolution reaction. As a result, P-NiMoS exhibits excellent HER activity; the overpotential is 290 mV at high current density of 250 mA cm⁻² in alkaline electrolyte, which is close to Pt/C (282 mV@250 mA cm⁻²), and P-NiMoS can stably evolve hydrogen for 48 h.     

Molecular structure and properties of click hydrogels with controlled dangling end defect

In this study, controlled amount of dangling ends is introduced to the two series of poly(ethylene glycol)‐based hydrogel networks with three and four crosslinking functionality by using click chemistry. The structure of the gels with regulated defect percentage is confirmed by comparing the results of low‐field NMR characterization and Monte Carlo simulation. The mechanical properties of these gels were characterized by tensile stress–strain behaviors of the gels, and the results are analyzed by Gent model and Mooney–Rivlin model. The shear modulus of the swollen gels is found to be dependent on the functionality of the network, and decreases with the defect percentage. Furthermore, the value of shear modulus well obeys the Phantom model for all the gels with varied percentage of the defects. The maximum extension ratio, obtained from the fitting of Gent model, is also found to be dependent on the functionality of the network, and does not change with the defect percentage, except at very high defect percentage. The value of the maximum extension ratio is between that predicted from Phantom model and the Affine model. This indicates that at the large deformation, the fluctuation of the crosslinking points is suppressed for some extend but still exists. Polymer volume fractions at various defect percentages obtained from prediction of Flory–Rehner model are found to be in well agreement with the swelling experiment. All these results indicate that click chemistry is a powerful method to regulate the network structure and mechanical properties of the gels. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 1227–1236     

1,4-二烯和醛的烯丙基碳氢不对称烷基化反应

利用钯配合物、有机胺和手性布朗斯特酸三元催化剂体系实现了α-取代丙醛参与的1,4-二烯烃的烯丙基碳氢不对称烷基化反应,以良好的产率、优良的区域选择性和立体选择性得到了结构多样的手性α-羰基化合物.此外发现非手性膦配体对钯配合物的催化活性和反应的选择性有十分显著的影响,为后续相关研究提供了新的思路.     

ZnIn2S4 flowerlike microspheres embedded with carbon quantum dots for efficient photocatalytic reduction of Cr(VI)

Development of efficient heterostructured photocatalysts that respond to visible light remains a considerable challenge. We herein show the synthesis of ZnIn₂S₄/carbon quantum dot hybrid photocatalysts with flowerlike microspheres via a facile solvothermal method. The ZnIn₂S₄/carbon quantum dot flowerlike microspheres display enhanced photocatalytic and photoelectrochemical activity compared with that of pure ZnIn₂S₄. With a content of only 0.5 wt % carbon quantum dots, 93% of Cr(VI) is reduced under visible-light irradiation at 40 min. As a co-catalyst, the carbon quantum dots improve the light absorption and lengthen the lifetime of charge carriers, consequently enhancing the photocatalytic and photoelectrochemical activity.