Ab initio potential surface of oxidative addition of CH4 to coordinatively unsaturated PtC12 is presented. The electron correlation has a big effect on the transition state and activation energy.
The monofunctional substitution reactions between trans-[PtCl（H2O）（NH3）（pip）]＋,trans-[Pt（H2O）2（NH3）（pip）]2＋,trans-[PtCl（H2O）（pip）2]＋,trans-[Pt（H2O）2（pip）2]2＋ （pip = piperidine） and adenine/gu...The monofunctional substitution reactions between trans-[PtCl（H2O）（NH3）（pip）]＋,trans-[Pt（H2O）2（NH3）（pip）]2＋,trans-[PtCl（H2O）（pip）2]＋,trans-[Pt（H2O）2（pip）2]2＋ （pip = piperidine） and adenine/guanine nucleotides are explored by using B3LYP hybrid functional and IEF-PCM salvation models. For the trans-[Pt（H2O）2（NH3）（pip）]2＋ and trans-[PtCl（H2O）（NH3）（pip）]＋ complexes,the computed barrier heights in aqueous solution are 13.5/13.5 and 11.6/11.6 kcal/mol from trans-Pt-chloroaqua complex to trans/cis-monoadduct for adenine and guanine,and the corresponding values are 20.7/20.7 and 18.8/18.8 kcal/mol from trans-Pt-diaqua complex to trans/cis-monoadduct for adenine and guanine,respectively. For trans-[PtCl（H2O）（pip）2]＋ and trans-[Pt（H2O）2（pip）2]2＋,the corresponding values are 21.5/21.3 and 19.4/19.4 kcal/mol,and 26.0/26.0 and 20.7/20.8 kal/mol for adenine and guanine,respectively. Our calculations demonstrate that the barrier heights of chloroaqua are lower than the corresponding values of diaqua for adenine and guanine. In addition,the free energies of activation for guanine in aqueous solution are all smaller than that for adenine,which predicts a preference of 1.9 kcal/mol when trans-[PtCl（H2O）（NH3）（pip）]＋ and trans-[Pt（H2O）2（NH3）（pip）]2＋ are the active agents and ～1.9 and ～ 5.3 kcal/mol when trans-[PtCl（H2O）（pip）2]＋ and trans-[Pt（H2O）2（pip）2]2＋ are the active agents,respectively. For the reaction of trans-Pt-chloroaqua （or diaqua） to cis-monoadduct,we obtain the same transition-state structure as from the reaction of trans-Pt-chloroaqua （or diaqua） to trans-monoadduct,which seems that the trans-Pt-chloroaqua （or diaqua） complex can generate trans-or cis-monoadduct via the same transition-state.展开更多
A square wave voltammetry (DPV) method for trans-Pt[Cl2(Dimethylamine)(isopropylamine)] determination is developed. To this end, all the chemical and instrumental variables affecting the determination of trans-Pt[Cl2(...A square wave voltammetry (DPV) method for trans-Pt[Cl2(Dimethylamine)(isopropylamine)] determination is developed. To this end, all the chemical and instrumental variables affecting the determination of trans-Pt[Cl2(Dimethylamine) (isopropylamine)] are optimized. From studies of the mechanisms governing the electrochemical response of trans-Pt[Cl2(Dimethylamine)(isopropylamine)], it was concluded that it was an electrochemically reversible system with an adsorptive oxidation phenomenon. Under optimal conditions, the variation of analytical signal (Ip) with trans-Pt[Cl2(Dimethylamine)(isopropylamine)] concentration was linear in the 0.05 μg·mL-1 to 10 μg·mL-1 range, with a LOD 91 μg·mL-1 of and a LOQ of 303 μg·mL-1, a RSD 1.10% and Er 0.72%. The optimized method was applied to the determination of trans-Pt[Cl2(Dimethylamine)(isopropylamine)] in biological fluids, in human urine and synthetic urine.展开更多
目的探讨外周T细胞淋巴瘤(peripheral T cell lymphoma,PTCL)患者肿瘤组织中程序性细胞死亡受体1(programmed cell death-1,PD-1)和程序性细胞死亡受体1配体(programmed death ligand 1,PD-L1)蛋白的表达情况,分析其与患者预后的关系。...目的探讨外周T细胞淋巴瘤(peripheral T cell lymphoma,PTCL)患者肿瘤组织中程序性细胞死亡受体1(programmed cell death-1,PD-1)和程序性细胞死亡受体1配体(programmed death ligand 1,PD-L1)蛋白的表达情况,分析其与患者预后的关系。方法采用免疫组化法检测PTCL患者肿瘤组织中PD-1、PD-L1蛋白的表达,并分析其表达与患者临床分期、疗效及预后之间的关系。结果 PTCL患者肿瘤组织中PD-1蛋白的表达阳性率为35%,PD-L1蛋白的阳性率为70%,炎性淋巴结组织中未见PD-1、PD-L1表达,PD-1、PD-L1蛋白的表达与患者临床分期正相关,PD-1蛋白的表达与疗效负相关,PD-1与PD-L1蛋白双阳性的PTCL患者生存期明显缩短。结论PTCL患者淋巴瘤组织中PD-1和PD-L1蛋白表达阳性率高于炎性淋巴结组织,是预后不良的指标。展开更多
文摘Ab initio potential surface of oxidative addition of CH4 to coordinatively unsaturated PtC12 is presented. The electron correlation has a big effect on the transition state and activation energy.
基金supported from the National Natural Science Foundation of China (No. 20971056)
文摘The monofunctional substitution reactions between trans-[PtCl（H2O）（NH3）（pip）]＋,trans-[Pt（H2O）2（NH3）（pip）]2＋,trans-[PtCl（H2O）（pip）2]＋,trans-[Pt（H2O）2（pip）2]2＋ （pip = piperidine） and adenine/guanine nucleotides are explored by using B3LYP hybrid functional and IEF-PCM salvation models. For the trans-[Pt（H2O）2（NH3）（pip）]2＋ and trans-[PtCl（H2O）（NH3）（pip）]＋ complexes,the computed barrier heights in aqueous solution are 13.5/13.5 and 11.6/11.6 kcal/mol from trans-Pt-chloroaqua complex to trans/cis-monoadduct for adenine and guanine,and the corresponding values are 20.7/20.7 and 18.8/18.8 kcal/mol from trans-Pt-diaqua complex to trans/cis-monoadduct for adenine and guanine,respectively. For trans-[PtCl（H2O）（pip）2]＋ and trans-[Pt（H2O）2（pip）2]2＋,the corresponding values are 21.5/21.3 and 19.4/19.4 kcal/mol,and 26.0/26.0 and 20.7/20.8 kal/mol for adenine and guanine,respectively. Our calculations demonstrate that the barrier heights of chloroaqua are lower than the corresponding values of diaqua for adenine and guanine. In addition,the free energies of activation for guanine in aqueous solution are all smaller than that for adenine,which predicts a preference of 1.9 kcal/mol when trans-[PtCl（H2O）（NH3）（pip）]＋ and trans-[Pt（H2O）2（NH3）（pip）]2＋ are the active agents and ～1.9 and ～ 5.3 kcal/mol when trans-[PtCl（H2O）（pip）2]＋ and trans-[Pt（H2O）2（pip）2]2＋ are the active agents,respectively. For the reaction of trans-Pt-chloroaqua （or diaqua） to cis-monoadduct,we obtain the same transition-state structure as from the reaction of trans-Pt-chloroaqua （or diaqua） to trans-monoadduct,which seems that the trans-Pt-chloroaqua （or diaqua） complex can generate trans-or cis-monoadduct via the same transition-state.
文摘A square wave voltammetry (DPV) method for trans-Pt[Cl2(Dimethylamine)(isopropylamine)] determination is developed. To this end, all the chemical and instrumental variables affecting the determination of trans-Pt[Cl2(Dimethylamine) (isopropylamine)] are optimized. From studies of the mechanisms governing the electrochemical response of trans-Pt[Cl2(Dimethylamine)(isopropylamine)], it was concluded that it was an electrochemically reversible system with an adsorptive oxidation phenomenon. Under optimal conditions, the variation of analytical signal (Ip) with trans-Pt[Cl2(Dimethylamine)(isopropylamine)] concentration was linear in the 0.05 μg·mL-1 to 10 μg·mL-1 range, with a LOD 91 μg·mL-1 of and a LOQ of 303 μg·mL-1, a RSD 1.10% and Er 0.72%. The optimized method was applied to the determination of trans-Pt[Cl2(Dimethylamine)(isopropylamine)] in biological fluids, in human urine and synthetic urine.
文摘目的探讨外周T细胞淋巴瘤(peripheral T cell lymphoma,PTCL)患者肿瘤组织中程序性细胞死亡受体1(programmed cell death-1,PD-1)和程序性细胞死亡受体1配体(programmed death ligand 1,PD-L1)蛋白的表达情况,分析其与患者预后的关系。方法采用免疫组化法检测PTCL患者肿瘤组织中PD-1、PD-L1蛋白的表达,并分析其表达与患者临床分期、疗效及预后之间的关系。结果 PTCL患者肿瘤组织中PD-1蛋白的表达阳性率为35%,PD-L1蛋白的阳性率为70%,炎性淋巴结组织中未见PD-1、PD-L1表达,PD-1、PD-L1蛋白的表达与患者临床分期正相关,PD-1蛋白的表达与疗效负相关,PD-1与PD-L1蛋白双阳性的PTCL患者生存期明显缩短。结论PTCL患者淋巴瘤组织中PD-1和PD-L1蛋白表达阳性率高于炎性淋巴结组织,是预后不良的指标。
