Platinum(II) Complexes Bearing Triphenylphosphine and Chelating Oximes: Antiproliferative Effect and Biological Profile in Resistant Cells

Platinum(II) complexes of the type [Pt(Cl)(PPh₃){(κ²-N,O)-(1{C(R)=N(OH)-2(O)C₆H₄})}] with R=Me, H, ( 1 and 2 ) were synthesized and characterized. Single-crystal X-ray diffraction confirmed the proposed (SP4-3) configuration for 1 . Study of the antiproliferative activity, performed on a panel of human tumor cell lines and on mesothelial cells, highlighted complex 2 as the more effective. In particular, it showed a remarkable cytotoxicity in ovarian carcinoma cells (A2780) and interestingly, a significant antiproliferative effect on cisplatin resistant cells (A2780cis). Investigation into the intracellular mechanism of action demonstrated that 2 had a lower ability to platinate DNA than did cisplatin, which was taken as reference, and a notably higher uptake in resistant cells. A significant accumulation in mitochondria, along with the ability to induce concentration-dependent mitochondrial membrane depolarization and intracellular reactive oxygen species production, allowed us to propose a mitochondrion-mediated pathway as responsible for the interesting cytotoxic profile of complex 2 .     

Effect of a halophilic aromatic yeast together with Aspergillus oryzae in koji making on the volatile compounds and quality of soy sauce moromi

Koji making is an essential step in the production of high‐quality soy sauce. In this study, we inoculated koji with a halophilic aromatic yeast (Zygosaccharomyces rouxii) and Aspergillus oryzae and investigated the effects on the volatile compounds and quality of soy sauce moromi. Our results suggest that the optimal yeast inoculation was approximately 1.5 × 10⁶ yeast per gram of koji, and excessive yeast greatly decreased A. oryzae enzyme activity. In comparison with the control group, there were no significant changes in the concentrations of amino nitrogen, total titratable acids, total soluble nitrogen and reducing sugar by extending the fermentation time during the first fermentation month, whereas the concentration of glutamate in the yeast‐inoculated sample increased by 46.16% and the arginine concentration decreased by 61.07%. After the second fermentation month, 17, 38 and 38 volatile components were identified by GC–MS in C1, C2 and C5, respectively. Moreover, a large number of volatile components, such as 2‐Methoxy‐4‐vinylphenol, ethyl acetate and 1‐Octen‐3‐ol were found in C2 and C5. And the total contents of volatile compounds in C2 were obviously higher than C5. This work furthers our understanding of the traditional multistrain koji making and provides a new method for enhancing the quality and flavour of soy sauce.     

定子扇形片复合模设计

分析零件自身的特点和成形难点,针对成形难点制定相应的解决对策,结合类似模具在以往设计、加工、组装、使用和维护过程中遇到的问题,对定子扇形片复合模设计难点的解决方法及相关注意事项分别进行了介绍,模具经多次调试已顺利投入生产,对类似零件的模具设计具有一定的参考作用。     

Copper–4,4′-dipyridyl coordination compound as solid reagent for spectrophotometric determination of reducing sugar employing a multicommutation approach

In this work a multicommuted flow system employing copper–4,4′- dipyridyl coordination compound as the solid-phase reagent for the spectrophotometric determination of reducing sugar was developed. The coordination compound was synthesized through a reaction of the 4,4′-dipyridyl and copper (II) nitrate, under hydrothermal conditions. The complex was characterized by infrared spectroscopy (FTIR), power X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive spectrometer (EDS) and thermogravimetric analysis (TGA). Based on the characterization, a multicommuted spectrophotometric procedure for the determination of reducing sugar using copper (II) complex as solid reagent is proposed. The proposed method was based on the redox reaction between a monosaccharide, such as fructose and glucose (reducing sugar) and Cu(II). This reaction, mediated in an alkaline medium, produces a yellow compound that can be determined by absorption electronic spectroscopy (λ_ABS = 420 nm). Under optimum experimental conditions, a linear response ranging from 1.0 to 20.0 g L⁻¹ (R = 0.9978 and n = 5), a detection (3σ criterion) and quantification (10σ criterion) limit estimated at 0.23 and 0.75 g L⁻¹, respectively, a standard deviation relative of 4.7% (n = 7), for a reference solution of 10.0 g L⁻¹ reducing sugar, and a sampling rate of 75 determinations per hour were achieved. The proposed system was applied to the determination of reducing sugars in coconut water and juices. The analysis of ten samples and the application of the t-test to the results found, and those obtained using reference procedures (AOAC), provided no significant differences at a 95% confidence level. This system enabled the analysis of reducing sugar with ease and simplicity, providing a significant economy of the solid reagent (600 μg per determination) and reducing effluent generation.     

Computational studies on the radiative and nonradiative processes of luminescent N-heteroleptic platinum(II) complexes

Three N-heteroleptic Pt(II) complexes, [Pt(C^C)(O^O)] [O^O = acetylacetonate, C^C = 1-phenyl-1,2,4-triazol-5-ylidene (1), C^C = 4-phenyl-1,2,4-triazol-5-ylidene (2), C^C = 2-phenylpyrazine (3)] have been investigated with density functional theory (DFT) and time-dependent density functional theory (TDDFT). The radiative decay rate constants of complexes 1–3 have been discussed with the oscillator strength (f_n), the strength of spin–orbit coupling (SOC) interaction between the lowest energy triplet excited state (T₁) and singlet excited states (S_n), and the energy gaps between E(T₁) and E(S_n). To illustrate the nonradiative decay processes, the transition states between triplet metal-centered (³MC) and T₁ states have been optimized and were verified with the calculations of vibrational frequencies and intrinsic reaction coordinate (IRC). In addition, the minimum energy crossing points (MECPs) between ³MC and ground states (S₀) were optimized. At last, the potential energy curves relevant to the nonradiative decay pathways are simulated. The results show that complex 3 has the biggest photoluminescence quantum yield because the complex 3 has the biggest radiative decay rate constant and the smallest nonradiative decay rate constant in complexes 1–3.     

Casting methods for the production of rotationally symmetric copper bimetals

ABSTRACT

Multiple-material products are characterised by a complex property profile which is achieved by combining the particular advantages of at least two different materials. Bimetal casting is an energy- and material-efficient technology for the production of multi-metallic objects. This paper describes the development of a semi-continuous casting process for the formation of a rotationally symmetric bimetal with a cohesive bonding character at the interface of a copper–tin alloy (CuSn6) and pure copper (Cu99.5). Initial experiments are conducted by static casting to evaluate the thermal process window. Based on the results of the initial experiments, a vertical semi-continuous compound casting process is developed. A stable cohesive bond between the joining partners is accomplished by forming a solid solution at the interface.

This paper is part of a Thematic Issue on Copper and its Alloys.     

通孔式钛合金层强韧化Ti2AlC/TiAl基叠层复合板材

以通孔式结构TC4钛合金箔为增韧层,以TiC-Ti-Al混合粉末为反应体系,采用放电等离子烧结技术(SPS)制备TC4/Ti2AlC-TiAl基叠层结构复合板材。借助XRD、SEM等分析相组成和组织结构,并测量室温弯曲强度和断裂韧性。结果表明,叠层结构复合板材的力学性能呈各向异性;当Ti2AlC含量(质量分数)为15%时,断裂韧性在加载方向垂直于叠层方向时达到最大值18.81 MPa·m1/2,远高于无Ti2AlC的复合板材的断裂韧性。通孔叠层结构设计以及复合化手段构建了复杂的裂纹扩展路径,且钛合金韧化层可以吸收断裂能,对改善韧性具有重要作用,为金属复合板材研究提供了一种全新的设计思路。     

Observation of table-like magnetocaloric effect and large refrigerant capacity in Nd6Fe13Pd1–xCux compounds

The table-like magnetocaloric effect is significant for the magnetic refrigeration applications above 20 K based on the Ericsson cycle. Herein, we prepared a series of Nd₆Fe₁₃Pd_1–xCu_x (x = 0.05, 0.1, 0.15) compounds by the arc-melting method. These compounds show the single crystalline phase in the tetragonal Nd₆Fe₁₃Si-type structure with the space group I4/mcm. A magnetic phase transition from ferromagnetism to antiferromagnetism and a metamagnetic transition from the antiferromagnetic state to the ferromagnetic state are observed in each of the compounds. The compounds exhibit table-like magnetocaloric effects with large refrigerant capacities. A constant ΔS_M in a temperature span of 40 K in the Nd₆Fe₁₃Pd_0.85Cu_0.15 compound are observed. For a field change of 0–5 T, the peak values of –ΔS_M for the Nd₆Fe₁₃Pd_0.95Cu_0.05, Nd₆Fe₁₃Pd_0.90Cu_0.10, and Nd₆Fe₁₃Pd_0.85Cu_0.15 compounds are estimated to be 4.8, 4.6 and 4.4 J/(kg·K) with corresponding refrigerant capacity values of 323, 331 and 316 J/kg, respectively. The obtained table-like magnetocaloric effects with large refrigerant capacities as well as fairly small thermal and magnetic hysteresis deem these series of compounds good candidates for single-phase magnetic refrigeration based on the Ericsson cycle.