One‐Pot Process to Carborano‐Coumarin via Catalytic CascadeDehydrogenative Cross‐Coupling

Ir‐catalyzed cascade dehydrogenative CH/BH and BH/OH cross‐coupling of carboranyl carboxylic acid with readily available benzoic acid has been achieved, leading to the facile synthesis of previously unavailable carborano‐coumarin in a simple one‐pot process. Two cage B—H, one aryl C—H and one O—H bonds are activated to construct efficiently new B—C and B—O bonds. The cascade cyclization can stop at the first B—H/C—H cross‐coupling step by tuning the reaction conditions, resulting in a series of α‐carboranyl benzoic acid and aryl carborane derivatives. Control experiments indicate that B—H/C—H dehydrocoupling proceeds preferentially over B—H/O—H dehydrocoupling, and both directing groups and oxidants are crucial for this reaction. An iridium(V) intermediate is proposed to be involved in the catalytic cycle.     

Synthesis,cytotoxicity, and interaction with DNA of platinum(II) complexes of (1R,2R)-N1-2-amyl-1,2-diaminocyclohexane

(1R,2R)-N¹-2-amyl-1,2-diaminocyclohexane, which has an amyl substituent as compared with 1,2-diaminocyclohexane, was used as the carrier group to construct three platinum(II) complexes. MTT assay revealed that the complexes showed decent cytotoxicity against all of the four tested tumor cell lines with the IC₅₀ values ranging from 1.08 to 253.36 μM. Particularly, the IC₅₀ values of 2 against A549 and HCT-116 reached 3.32 and 1.08 μM, respectively, which were much lower than those of cisplatin and oxaliplatin. Flow cytometry demonstrated that 2 inhibited HepG2 cells proliferation and caused cytotoxicity by inducing apoptosis and arresting cells in the G2 phase. Furthermore, agarose gel electrophoresis showed that 2 had the ability to interact with DNA in a manner different from cisplatin and oxaliplatin, indicating the carrier ligand with an alkyl moiety had an influence on the action mode of the complex.     

基于优化后流动敏感黑血序列的豆纹动脉3 T磁共振成像

豆纹动脉是大脑内部的重要动脉,其阻塞往往会导致腔隙性脑梗死.现在在临床上主要利用数字减影血管造影(Digital Subtraction Angiography,DSA)技术实现豆纹动脉成像,然而DSA的有创性是其重要的限制因素.有研究表明,在高场磁共振系统(7 T)下,时间飞跃法(Time-Of-Flight,TOF)已经能够得到较好的豆纹动脉影像,但是在临床使用的1.5 T或3 T磁共振系统下,由于豆纹动脉的管腔直径非常小(大约为0.3~0.7 mm)、血流速度比较慢,对其成像仍然是个挑战.该文主要研究了在3 T磁共振系统下使用流动敏感黑血(Flow-Sensitive Black-Blood,FSBB)序列对豆纹动脉进行成像的方法,并对该成像序列中流动敏感梯度的设计进行了优化,使其在扫描时间和图像分辨率、对比度、信噪比等方面都能够基本满足临床使用的要求.     

Sorption of La(III) and Ce(III) by oxidized carbon nanotubes

The ion-exchange sorption of La(III) and Ce(III) from nitrate solutions using oxidized carbon nanotubes with a solubility of 4.2 g/L is studied at metal concentration С = 5–160 mg/L, рН 2.5–6.0, ratio S: L = 0.002–0.06, and room temperature. At С = 35 mg/L, the equilibrium capacity is shown to grow dramatically with рН rising from 3.0 to 4.0–4.5 and reaching 840 mg/g in La and 950 mg/g in Се when S: L < 0.006 and рН > 4.0–4.5. The introduction of ionic salts is found to reduce the capacity (at рН > 4 and concentrations of 0.01 М and 0.1 М NaCl, the Се capacity is reduced to ~500 and ~200 mg/g). It is concluded that the sorption equilibrium is better described by the Langmuir equation, while the process kinetics, by pseudo-first and pseudo-second order equations.     

Sorption of inorganic salts on carbon nanomaterials and magnetite

Magnetic composites based on graphene oxides and functionalized carbon nanotubes containing magnetite nanoparticles are synthesized. The dispersing ability of these composites in water at different pH values is studied. It is shown that the solubility of Fe₃O₄ composites is constant in the рН range of 3.5–10, though these composites are unstable at both lower and higher pH values. Magnetic sorbents for extracting Се(NO₃)₃ and La(NO₃)₃ from solutions are tested. Dependences of the volume on the sorbent’s composition, pH value, and salt concentration in the solution are found. Maximum sorption capacity in relation to Се³⁺ and La³⁺ at рН 7.5 and 8.5 are found to be 1040 and 920 mg/g respectively.     

Principal component analysis and response surface methodology: optimization for H2 evolution from water catalyzed adopting V–Bi under visible light

Energy generation by photocatalytic water splitting with semiconductors under visible light is an effective method for generating pollution-free energy. In this work, a highly efficient vanadium pentoxide (V₂O₅)-based composite photocatalyst was prepared by hydrothermal calcination. The preparation conditions were optimized using single factor experiments, factor analysis (FA), principal component analysis (PCA), and response surface method (Design Expert). The results showed that the optimal preparation conditions were 6% Bi₂S₃ loading, 10 h hydrothermal time, 175.0°C hydrothermal temperature, 4.0 h calcination time, and a calcination temperature of 400.0°C. The results of FA and PCA analysis showed that the hydrothermal temperature, calcination time, and calcination temperature were the three main influencing factors. According to the optimization analysis using the response surface method, the highest hydrogen production rate (590.151 μmol/(g?h)) was obtained at a hydrothermal temperature of 168.74°C, a calcination time of 3.97 h, and a calcination temperature of 390.15°C. The quantum yield of the catalyst was 27.71%.     

Numerical investigation on thermodynamic performance of CO2-based mixed refrigerants applied in transcritical system

Journal of Thermal Analysis and Calorimetry - The CO2-based mixed refrigerants R744/R152a and R744/R161 are proposed to enhance the thermodynamic performance of pure CO2 refrigerant. The basic...     

Developmental validation of the Microreader Group Y Direct ID System: A novel six-dye typing system with 54 Y-chromosomal loci for forensic application

Y-chromosome, as a gender-determined biological marker, is inherited only between fathers and sons. The Y-chromosome short tandem repeats (Y-STRs) play an essential role in paternity lineage tracing as well as sexual assault cases. The Microreader Group Y Direct ID System as a six-dye multiplex amplification kit, including 53 Y-STR and one Y-Indel locus, would improve performance and aid in obtaining more information through a greater number of loci with high polymorphism. In the present study, to verify the accuracy and efficiency of the kit, developmental validation was conducted by investigating sensitivity, species specificity, PCR inhibition, male–male and male–female mixtures, and reproducibility. The kit was tested using 311 male samples from Han and Qiang populations in Sichuan Province. The results showed that this kit had fairly high power for forensic discrimination (Han: haplotype diversity [HD] = 1, Qiang: HD = 0.999944). Additionally, 44 confirmed father–son pairs were also genotyped, among which 69 distinct haplotypes could be obtained. These father–son pairs cannot be distinguished by commonly used Y-STR panels, indicating that adding these extra Y-STRs to a single panel can achieve better discrimination performance. Collectively, the Microreader Group Y Direct ID System is robust and informative for forensic applications.     

Organic pH Buffer for Dendrite-Free and Shuttle-Free Zn-I2 Batteries

Aqueous Zn-Iodine (I₂) batteries are attractive for large-scale energy storage. However, drawbacks include, Zn dendrites, hydrogen evolution reaction (HER), corrosion and, cathode “shuttle” of polyiodines. Here we report a class of N-containing heterocyclic compounds as organic pH buffers to obviate these. We evidence that addition of pyridine /imidazole regulates electrolyte pH, and inhibits HER and anode corrosion. In addition, pyridine and imidazole preferentially absorb on Zn metal, regulating non-dendritic Zn plating /stripping, and achieving a high Coulombic efficiency of 99.6 % and long-term cycling stability of 3200 h at 2 mA cm⁻², 2 mAh cm⁻². It is also confirmed that pyridine inhibits polyiodines shuttling and boosts conversion kinetics for I⁻/I₂. As a result, the Zn-I₂ full battery exhibits long cycle stability of >25 000 cycles and high specific capacity of 105.5 mAh g⁻¹ at 10 A g⁻¹. We conclude organic pH buffer engineering is practical for dendrite-free and shuttle-free Zn-I₂ batteries.     

Molecular third-harmonic-generation microscopy through resonance enhancement with absorbing dye

This paper reports a facile and effortless method to realize three-dimensional (3D) molecular third-harmonic-generation (THG) microscopy through the technique of resonance enhancement with absorbing dye. Hematoxylin, a popular absorbing stain, is applied as an example to verify the multiphoton resonant enhancement based on the 1230 nm excitation light and can selectively enhance THG yield at cell nuclear sites in the studied specimens, serving as a cell nucleus contrast agent. It is concluded that combining THG microscopy with the mature staining technique can readily achieve 3D molecular imaging without using fluorescence.