Radical formation of 5,10,15,20-tetra(4-sulfophenyl) porphinatopalladium(II)(4−) in the lowest excited triplet states

Excited 5,10,15,20-tetra(4-sulfopheny)porphinatopalladium(II) (PdTPPS⁴⁻) was studied by phosphorescence lifetime, phosphorescence quenching, delayed fluorescence, and transient absorption measurements in terms of the dimerization reaction. Lifetimes of monomer and dimer was determined as τ=360 and 270 μs, respectively. The self-association rates of PdTPPS⁴⁻ in the excited and ground states are the same. Transient absorption unveiled the radical formation resulted from the charge separation after photo excitation.     

One-electron reduction potentials of dietary carotenoid radical cations in aqueous micellar environments

The one-electron reduction potentials of the radical cations of five dietary carotenoids (β-carotene, canthaxanthin, zeaxanthin, astaxanthin and lycopene) in aqueous micellar environments have been obtained from a pulse radiolysis study of electron transfer between the carotenoids and tryptophan radical cations as a function of pH, and lie in the range of 980–1060 mV. These values are consistent with our observation that the carotenoid radical cations oxidise tyrosine and cysteine. The decays of the carotenoid radical cations in the absence of added reactants suggest a distribution of exponential lifetimes. The radicals persist for up to about 1 s, depending on the medium.     

C-C bond formation and cleavage in radical enzymes, a theoretical perspective

Quantum chemical methods are today a viable tool in the study of enzyme catalysis. The development of new density functional techniques and the enormous advancement in computer power have made it possible to accurately describe active sites of enzymes. This review gives a brief account of the methods and models used in this field. Three specific enzymes are discussed: pyruvate-formate lyase (PFL), spore photoproduct lyase (SPL), and benzylsuccinate synthase (BSS). What these enzymes have in common is that they use radical chemistry to catalyze C-C bond formation or cleavage reactions.     

Synthetic construction of sugar-amino acid hybrid polymers involving globotriaose or lactose and evaluation of their biological activities against Shiga toxins produced by Escherichia coli O157:H7

Synthetic assembly of sugar moieties and amino acids in order to create “sugar-amino acid hybrid polymers” was accomplished by means of simple radical polymerization of carbohydrate monomers having an amino acid-modified polymerizable aglycon. Amines derived from globotriaoside and lactoside as glycoepitopes were condensed with known carbobenzyloxy derivatives, including Z-Gly, Z-l-Ala and Z-β-Ala, which had appropriate spacer ability and a chiral center to afford fully protected sugar-amino acid hybrid compounds in good yields. After deprotection followed by acryloylation, the water-soluble glycomonomers were polymerized with or without acrylamide in the presence of a radical initiator in water to give corresponding copolymers and homopolymers, which were shown by SEC analysis to have high molecular weights. Evaluation of the biological activities of the glycopolymers against Shiga toxins (Stxs) was carried out, and the results suggested that glycopolymers having highly clustered globotriaosyl residues had high affinity against Stx2 (K_D?=?2.7～4.0?µM) even though other glycopolymers did not show any affinity or showed very weak binding affinity. When Stx1 was used for the same assay, all of the glycopolymers having globotriaosyl residues showed high affinity (K_D?=?0.30～1.74?µM). Interestingly, couple of glycopolymers having lactosyl moieties had weaker binding affinity against Stx1. In addition, when cytotoxicity assays were carried out for both Stxs, glycopolymers having highly clustered globotriaosyl residues showed higher affinity than that of the copolymers, and only highly clustered-type glycopolymers displayed neutralization potency against Stx2.     

保乳手术与改良根治术治疗Ⅰ-Ⅱ期乳腺癌患者的疗效及生存状况比较研究

目的:比较分析乳腺癌保乳手术和根治术的临床疗效及患者生存状况。方法:回顾性分析2012年6月至2015年6月在我院乳腺外科行手术治疗的乳腺癌患者92例的临床资料,其中行保乳手术患者24例(保乳组),行根治手术患者68例(根治组),两组患者术后均采用个性化综合治疗巩固疗效,对比观察两组疗效及预后状况;通过乳腺癌生命质量测定量表(FACT-B)检测对比两组患者术后1、2年的生存质量;并对比两组患者术后乳房美容效果。结果:保乳组患者手术时间、术中出血量、引流量以及引流时间均明显较根治组少,差异有统计学意义(P0.05),而淋巴结清扫数则无明显差异(P0.05);两组患者上肢水肿发生率无明显差异(P0.05),而保乳组切缘皮瓣缺血发生率低于根治组(P0.05);两组患者术后2年生存率、复发率以及远处转移率无统计学差异(P0.05)。保乳组患者术后1、2年生理状况、情感状况、社会状况、功能状况、其他因素及生活质量综合评分均显著高于根治组,差异有统计学意义(P0.05);保乳组术后乳房美容效果的优良率显著高于根治组,差异有统计学意义(P0.05)。结论:相比于根治术,保乳手术不仅具有创伤小、术后恢复快的优势,患者预后状况与根治术相当,同时可更好的改善患者生存质量,术后乳房美容效果较好,临床应用价值更高。     

肝癌乙型肝炎病毒感染患者术后恩替卡韦抗病毒治疗的临床疗效及安全性评价

目的:探讨肝癌乙型肝炎病毒(HBV)感染患者根治性切除术后采用恩替卡韦抗病毒治疗的临床疗效及安全性。方法:收集2015年1月-2017年8月在我院行根治性切除术的肝癌HBV感染患者279例为研究对象,以血清HBV-DNA载量10~5 copies/ml为界限,分为高病毒复制组128例,低病毒复制组151例,按照随机数字表法将高病毒复制组分为高-治疗组64例、高-对照组64例,将低病毒复制组分为低-治疗组76例、低-对照组75例。高-治疗组和低-治疗组术后给予恩替卡韦0.5 mg/d,高-对照组和低-对照组未行抗病毒治疗。比较手术前、术后7 d各组的血清HBV-DNA水平,血清白蛋白(ALB)、谷丙转氨酶(ALT)、前白蛋白(PA),以及术后并发症的发生情况。结果:高-治疗组、高-对照组、低-治疗组、低-对照组术后血清ALB、PA均较治疗前降低,血清ALT均较治疗前升高,且高-治疗组或低-治疗组术后血清ALB、PA均高于高-对照组或低-对照组,血清ALT水平均低于高-对照组或低-对照组,差异均有统计学意义(P0.05);高-治疗组或低-治疗组术后血清HBV-DNA水平均低于治疗前,且均低于同期高-对照组或低-对照组,差异均有统计学意义(P0.05)。高-治疗组与高-对照组、低-治疗组与低-对照组患者术后并发症发生率均无统计学差异(P0.05)。结论:恩替卡韦能显著改善肝癌HBV感染患者术后的血清HBV-DNA载量水平和肝功能,安全性高,值得临床推广。     

肾脏部分切除手术对T1a期肾癌患者炎性因子与肝肾功能的影响

目的:探讨肾脏部分切除手术对T_(1a)期肾癌患者炎性因子与肝肾功能的影响。方法:回顾性分析我院2013年6月至2016年12月收治的91例T_(1a)期肾癌患者的临床资料,按治疗方式不同分为对照组与试验组,对照组48例接受后腹腔镜根治性肾癌切除术治疗,试验组43例接受后腹腔镜肾脏部分切除手术治疗。比较两组的手术指标、治疗前后血清炎性因子、肝肾功能的变化及并发症发生情况。结果:对照组的手术时间、术中出血量均少于试验组(P0.05)。治疗后,试验组血清IL-1变化值低于对照组[(-19.47±-2.57)μg/L比(-41.61±-6.38)μg/L]、IL-6变化值低于对照组[(-8.71±-1.05)ng/L比(-18.96±-3.10)ng/L]、CRP变化值低于对照组[(-12.72±-1.54)mg/L比(-17.46±-2.64)mg/L]、TNF-α变化值低于对照组[(-5.66±-0.15)ng/L比(-14.33±-2.04)ng/L]、BUN变化值低于对照组[(-1.53±-0.19)mmol/L比(-3.01±-0.79)mmol/L]、AST变化值低于对照组[(-15.29±-2.46)U/L比(-33.70±-3.78)U/L]、ALT变化值低于对照组[(-19.46±-2.27)U/L比(-34.02±-5.51)U/L],试验组Ccr变化值低于对照组[(19.78±2.94)mL/min比(28.26±3.52)mL/min]、GFR变化值低于对照组[(14.45±1.48)mL/min比(29.36±1.91)mL/min],除CRP和GFR外,其余指标差异均有统计学意义(P0.05)。对照组和试验组并发症发生率分别为16.67%(8/48)和9.30%(4/43),两组比较差异无统计学意义(P0.05)。结论:后腹腔镜肾脏部分切除手术治疗T_(1a)期肾癌患者的临床效果优于后腹腔镜根治性肾癌切除术治疗,其对患者炎性因子及肝肾功能的影响较小,安全性更高。     

Degradation of Hyaluronic Acid by Photosensitized Riboflavin In Vitro. Modulation of the Effect by Transition Metals, Radical Quenchers, and Metal Chelators

The effect of photoexcited riboflavin (RF) on the viscosity of hyaluronic acid (HA) solutions has been investigated. UV irradiation of RF causes under aerobic conditions fragmentation of HA and a decrease in the viscosity of its solutions. A decrease of HA viscosity occurs in PO₄-buffered solutions and is accelerated by high pH, Fe²⁺ (but much less so by Fe³⁺), certain metal chelators, and horseradish peroxidase (HRP); it is partially inhibited by catalase and less so by superoxide dismutase (SOD). The reactivity of the system was completely blocked by Tris, ethanol, aspirin, d-manitol, dimethylthiourea (DMTU), dimethylsulfoxide (DMSO), and sodium azide. These results indicate that the most likely chemical species involved in the reaction is the hydroxyl radical. Singlet oxygen (¹0₂) generation is suggested by the ability of NaN₃ and DMSO to completely inhibit the reactivity of the system. These two agents, however, may also interact with OH^√ radical, as well and suppress the reactivity of the system. H₂O₂ and seem also to be produced in significant amounts, because catalase and SOD partially block the reactivity of the system. The effect of HRP may be due to hydrogen subtraction from HA and H₂O₂ reduction to water. Photoexcitation of RF may potentially occur in vitro and in vivo in the organs and tissues that are permeable to light, such as the eye or skin, and damage HA and other cell-matrix components causing inflammation and accelerating aging.  © 1997 Elsevier Science Inc.     

Effect of Brønsted acids on the thiophenol-mediated radical addition–translocation–cyclization process for the preparation of pyrrolidine derivatives

Abstract

A thiophenol-mediated method for the conversion of propargylamines to pyrrolidines under acidic conditions is described. This cascade reaction involves addition of a thiyl radical to the terminal alkyne followed by a 1,5-hydrogen transfer (radical translocation) and a rapid cyclization affording the pyrrolidine ring. Our studies reveal that complete protonation of the tertiary amine with 10 equivalents of trifluoroacetic acid avoids undesired hydrogen atom abstractions by the thiyl radicals.