Building up PtII−Thiosemicarbazone−Lysine−sC18 Conjugates

Three chiral tridentate N^N^S coordinating pyridine-carbaldehyde (S)-N4-(α-methylbenzyl)thiosemicarbazones (HTSCmB) were synthesised along with lysine-modified derivatives. One of them was selected and covalently conjugated to the cell-penetrating peptide sC18 by solid-phase peptide synthesis. The HTSCmB model ligands, the HTSCLp derivatives and the peptide conjugate rapidly and quantitatively form very stable Pt^II chlorido complexes [Pt(TSC)Cl] when treated with K₂PtCl₄ in solution. The Pt(CN) derivatives were obtained from one TSCmB model complex and the peptide conjugate complex through Cl⁻→CN⁻ exchange. Ligands and complexes were characterised by NMR, IR spectroscopy, HR-ESI-MS and single-crystal XRD. Intriguingly, no decrease in cell viability was observed when testing the biological activity of the lysine-tagged HdpyTSCLp, its sC18 conjugate HdpyTSCL-sC18 or the PtCl and Pt(CN) conjugate complexes in three different cell lines. Thus, given the facile and effective preparation of such Pt-TSC-peptide conjugates, these systems might pave the way for future use in late-stage labelling with Pt radionuclides and application in nuclear medicine.     

电感耦合等离子体原子发射光谱法测定辛酸铑催化剂中铂钯铅铁铜铝镍

准确测定辛酸铑催化剂中杂质元素含量,是判定产品是否合格的重要指标之一。以往常采用直流电弧发射光谱法(摄谱法)进行检测,但测定周期长,且重复性较差。用电感耦合等离子体原子发射光谱法(ICP-AES)测定辛酸铑催化剂中微量杂质元素时,辛酸铑催化剂样品中含有的大量有机组分和铑基体会对测定有严重干扰。实验采用反复滴加硝酸消解样品中有机组分,再用王水溶解盐类,选用合适背景点扣除的方式消除铑基体的干扰,建立了使用ICP-AES测定辛酸铑催化剂中0.001%~0.1%(质量分数)Pt、Pd、Pb、Fe、Cu、Al、Ni等7种微量杂质元素的方法。各元素在0.10~10.00μg/mL范围内与其发射强度呈线性关系,相关系数均大于0.9999;方法检出限(μg/mL)为0.075(Pt)、0.0033(Pd)、0.015(Pb)、0.0036(Fe)、0.010(Cu)、0.001(Al)、0.012(Ni)。实验方法用于测定辛酸铑催化剂样品中Pt、Pd、Pb、Fe、Cu、Al、Ni,结果的相对标准偏差为(RSD,n=7)为1.4%~9.6%。按照实验方法测定辛酸铑催化剂中Pt、Pd、Pb、Fe、Cu、Al、Ni,并与直流电弧发射光谱法的测定结果进行比对,结果相一致。     

Pt-WC/Mnt三元纳米复合材料的制备及其电催化性能

以剥离后的蒙脱石(Mnt)片层为载体、六氯化钨(WCl6)为钨源,通过浸渍负载及原位还原碳化获得了碳化钨(WC)与蒙脱石(Mnt)纳米复合材料,然后将氯铂酸(H2PtCl6)通过浸渍负载于复合材料上,并在氢气(H2)中还原得到Pt-WC/Mnt三元纳米复合催化材料。采用X射线粉末衍射和透射电子显微镜对三元纳米复合催化材料的物相、形貌和结构进行表征,采用三电极体系和循环伏安法测试了样品的电催化性能。结果表明:样品物相主要为WO3和WC,蒙脱石片层结构明显,铂(Pt)纳米粒子均匀分布于WC/Mnt复合材料的外表面。Pt-WC/Mnt三元纳米复合材料对甲醇电催化氧化具有较高的催化活性,并且在酸碱体系中均具有良好的稳定性。     

电子行业用高纯钯的制备研究

高纯钯在电子行业等领域应用广泛，需求迫切。以氯化钯为原料，提出采用氯化铵沉淀-氨水配合联合工艺净化钯溶液，水合肼还原纯净钯溶液制备高纯钯。结果表明，固体氯化钯溶解后，在合适的条件下，该钯溶液经过氧化-氯化铵沉淀、氨水配合有效去除杂质元素，获得纯净二氯四氨合钯溶液，再经水合肼还原后，获得纯度99.999%高纯钯，其碳、氧、氮等杂质元素总含量小于355×10^-6。     

薄膜铂电阻元件稳定性测试与分析

高端军事应用环境对测温传感器提出了小结构、高精度、良好的长期稳定性等要求,采用溅射方式制备的薄膜铂电阻元件成为了首选。通过分析薄膜铂电阻元件的结构、工艺,探讨影响稳定性的主要因素,包括薄膜缺陷、杂质、电迁移、结构封装应用与温度应力等。选择薄膜铂电阻在水三相点下的电阻值作为稳定性的比较基准,设计了一款不大于3mK的高精度测试系统。通过对薄膜铂电阻元件进行高温电寿命试验和温度冲击试验,评估得出薄膜铂电阻元件长期稳定性达到10mK,满足设计需求。     

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 .     

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.     

中国商用车领域的铂族金属需求依然强劲

2020年以来中国商用车市场发生了很多变化，近期卡车销量从疫情萧条中大幅反弹，物流、基建以及排放标准升级共同推动了2020年商用车市场需求，对铂族金属的需求更加有利，对铂金需求的预期增长似乎比对钯金需求更有保障。     

铂钯精矿中氯化银的浸出预处理研究

铜阳极泥分铜液所得铂钯精矿中的银主要以氯化银(AgCl)形态存在，可用氨水或亚硫酸钠作为浸出剂去除银。绘制了Ag⁺与NH3、SO2- 3配体组分图，结合电位-pH图分析表明，氨浸的pH值范围为7.7~13.5，亚硫酸钠浸出宜在中性或碱性条件下进行。优化条件实验结果表明，银的氨浸浸出率为95.3%，碲浸出率为14.9%，有微量铂、钯浸出；以亚硫酸钠为浸出剂，银的浸出率为97.3%，碲浸出率为11.5%，金、铂和钯均不被浸出。亚硫酸钠更适于作为铂钯精矿预处理除银的浸出剂。