胃癌与七种元素关系的分析

57例胃癌癌灶内锌值为(13.740±4.150)×10~(-6),低于癌边缘组织(15.677±4.567)×10~(-6)(P<0.01),亦低于正常组织(15.897±3.580)×10~(-6)(P<0.01)。癌灶铜值为(7.91±6.19)×10~(-6),高于正常组织(5.62±12.01)×10~(-6)(P<0.05),癌灶铜/锌比值亦高于正常组织(P<0.01),但与边缘组织无显著性差异。分化较好的胃腺癌与未分化癌间七种微量元素含量均无显著性差异。这些结果提示,胃癌组织中锌值的降低与铜/锌比值的升高可作为胃癌的辅助诊断指标,而且锌值的检测更具意义。但与分化程度无关。     

微量元素对胎儿发育影响的临床研究

为了解小于胎龄儿的血锌、铜、铅的变化 ,对 3 8例小于胎龄儿 (其中 1 2例有先天缺陷 )进行了血锌、铜、铅三种微量元素检测 ,并与 3 1例健康足月适于胎龄儿比较。结果表明 ,3 8例小于胎龄儿血锌、铜、铅结果分别为 49 4± 1 9 88μmol/L、 1 0 7± 3 3 μmol/L、 1 5± 0 83 μmol/L ;与正常对照组 (分别为 62 3 9± 1 5 2 9μmol/L、 1 1 0 2± 1 73 μmol/L、 0 82± 0 3 9μmol/L)比较 ,血锌明显低于正常组 ,t=-2 88,P <0 0 1 ;血铅明显高于对照组 ,t =4 6,P <0 0 1 ,有显著性差异。两组血铜无明显差异。小于胎龄儿血锌降低 ,血铅增高 ,而且其先天性缺陷者占3 5 .5 8% ,证明胎儿的低锌高铅状态对其生长发育有重要影响。     

补肾调肝方对特发性少弱精症患者精液锌影响的临床观察

临床观察了60例特发性少弱精症患者使用补肾调肝方治疗后精液质量、精液微量元素锌的改变。60例患者精液密度、精液活力在治疗前后分别为(59.40±54.95)×10~6/mL、(85.48±75.58)×10~6/mL(P<0.05);(38.78±28.11)％、(47.10±28.74)％(P<0.05)。治疗前后精液锌含量分别为(1.79±1.20)mmol·L~(-1)、(1.96±1.07)mmol·L~(-1)。经计算,t值等于2.397,大于t_(0.05)(60),即P<0.05,治疗前后锌元素的差异有显著性意义。     

儿童易疲劳与血清中微量元素含量的相关性研究

测定了1562名儿童(其中包括153名易疲劳儿童)血清中Zn、Fe、Cu、Ca、Mn和Pb的含量。研究发现,易疲劳儿血清Ca含量(84.4±12.5μg/mL)显著低于对照组儿童(88.5 4±13.4μg/mL),P<0.05;Fe含量(1.094±0.22μg/mL)显著高于对照组儿童(1.07 4±0.22μg/mL),P<0.05;Mn含量(0.040 4±0.035μg/mL)非常显著高于对照组儿童(0.035 4±0.013μg/mL),P<0.001。     

复方金蒲片对原发性肝癌的血硒水平及免疫功能影响的观察

为探讨肝癌患者服含硒复方金蒲片前后血硒水平的变化及对细胞免疫、体液免疫功能的影响,将肝癌病例随机分为经肝动脉介入栓塞治疗联合服用复方金蒲片的治疗组(n =3 2 )与单纯介入栓塞治疗的对照组(n =3 0 ) ,正常对照组选择本市体检健康者(n=3 0 ) ,比较治疗前、后检测血硒及免疫指标。结果表明,肝癌患者全血中硒含量0 1 75 μg/g ,比正常对照组硒均值( 0 2 2 0±0 0 83 ) μg/g低。治疗组病人治后1个月血硒均值( 0 2 5 1±0 1 0 6) μg/g,明显高于治疗前( 0 1 75±0 0 3 4) μg/g,P <0 0 0 5 ,有非常显著性意义。治疗组服药后免疫指标IgG、IgA、IgM以及CD3+ 、CD4 + 、n(CD4 + ) /n(CD8+ )比值均有提高,治疗组治疗前后比较,差异均有显著性意义。结论是复方金蒲片能提高肝癌病人血硒水平和增强免疫功能作用     

微量元素影响幼儿智力发育多因素分析

研究了3609名1～岁儿童头发中微量元素与儿童智力发育不全的关系.结果表明,智力发育不全(IQ值55～69)儿童的发Zn为(68.24±16.56)×10-6、Pb为(14.73±8.68)×10-6;高智商(IQ值109～131)儿童的发Zn为(98.62±20.47)×10-6、Pb为(7.92±6.31)×10-6.正常儿童头发中Zn含量[(83.16±19.35)×10-6]显著高于智力发育不全儿童[(80.08±18.47×10)-6,P＜0.05].而正常儿童头发中Pb含量[(12.67±7.48)×10-6则明显低于智力发育不全儿童[(13.25±7.57)×10-6,P＜0.05].正常女童发Zn明显高于智力发育不全儿童的发Zn(P＜0.05).正常女童发Mn、Pb明显低于智力发育不全儿童的发Mn(P＜0.05)、Pb(P＜0.05).正常男童的发Zn、Cu明显高于智力发育不全儿童的发Zn(P＜0.05)、Cu(P＜0.05).正常男童的发Pb明显低于智力发育不全儿童的发Pb(P＜0.05).低锌高铅可能是儿童智力发育不全的重要致病原因.     

铝(Ⅲ)与脱铁伴清蛋白结合的紫外差光谱研究

在 pH7.4、 0.1mol· L~(－1)N-2-羟乙基哌嗪- N′-2-乙磺酸（ Hepes）及室温条件下,使用紫外吸收差光谱进行了铝(Ⅲ)对脱铁伴清蛋白的滴定。结果表明铝(Ⅲ)与脱铁伴清蛋白结合后其紫外差光谱在 238nm和 291nm处出现吸收峰。在 238nm处铝(Ⅲ)-脱铁伴清蛋白配合物的摩尔吸光系数是 (1.52± 0.04)× 10~4cm~(－1)· mol~(－1)· L。铝(Ⅲ)可占据脱铁伴清蛋白的两个金属离子结合部位,条件稳定常数是 lgK_N=11.21± 0.12,lgKC=9.53± 0.24。 N-端单铁伴清蛋白的紫外差光谱滴定表明,铝 ?优先占据脱铁伴清蛋白的 N端结合部位。     

32例反复呼吸道感染患儿发铅研究

研究了铅对儿童免疫系统的影响。选择了32例反复呼吸道感染患儿作为研究对象,38例健康儿童为对照。结果表明,患儿发铅含量(26.7±14.1)×10~(-6),高于对照组发铅含量(19.4±9.1)×10~(-6),经统计学处理,两者有显著性差异,t=2.59,P<0.05。证实铅对人体免疫力具有抑制作用,可增加小儿对致病微生物的敏感性。     

硒锌氨基酸治疗儿童锌缺乏症疗效分析

为观察硒锌氨基酸治疗儿童锌缺乏的疗效,将98例锌缺乏儿童随机分为硒锌氨基酸治疗组及对照组,测定治疗前后血锌增加值,并比较治疗效果。结果表明,治疗组血锌平均增加值为(16.37±4.89)μmol/L,对照组为(12.39±5.01)μmol/L,P<0.01,差异有高度显著性;治疗组50例中,显效36例,有效10例,无效4例,对照组48例中显效24例,有效12例,无效12例,χ2=4.12,P<0.05,差异有显著性。可见硒锌氨基酸治疗儿童锌缺乏症取得显著疗效。     

高分辨MRI 3D黑血技术诊断颈动脉斑块的研究

本研究探讨高分辨磁共振成像(MRI)3D黑血技术判断颈动脉斑块位置及预测脑卒中的应用价值。选取缺血性脑卒中患者68例(观察组),同时选取健康体检者50例作为对照组,给予高分辨MRI 3D黑血技术检查,分析两组黑血技术参数差异,同时采用ROC曲线分析参数预测脑卒中的价值。共检出颈动脉粥样硬化斑块82处;高分辨MRI 3D黑血技术颈动脉斑块检出率为95.12%;观察组颈动脉血管总面积(TVA)、管壁面积(WA)及管壁标准化指数(NWI)明显高于对照组(P<0.05);观察组缺血侧TVA明显高于非缺血侧(P<0.05);TVA、WA及NWI预测脑卒中的ROC曲线下面积分别为0.801、0.825和0.842(P<0.05)。高分辨MRI 3D黑血技术判断颈动脉斑块位置有较好的价值,颈动脉定量指标在脑卒中预测中有一定应用价值。     

二氧化碳和丙烯直接合成甲基丙烯酸的NiPMo/TiO2催化剂的研究

用溶胶-凝胶法以磷钼酸(MPA)的镍盐溶液水解钛酸四丁酯制备了NiPMo/TiO2催化剂.使用ICP、 XRD、 TG-DTA、 IR、 TPD-MS和微反应技术研究了催化剂的化学组成、热稳定性、化学吸附性质和催化反应性能.杂多钼酸盐与TiO2通过O2-在TiO2表面发生了键合.在623 K下,杂多阴离子仍保持原有的Keggin结构.CO2在Lewis酸位Ni(Ⅱ)和Lewis碱位Ni-O-Mo的桥氧协同作用下生成CO2卧式吸附态Ni(Ⅱ)←O-(CO)←(O--Ni).丙烯有多种吸附态在催化剂上吸附.在563 K、 1 MPa和空速1500 h-1的反应条件下,丙烯的摩尔转化率为3.2%,产物MAA选择性为95%.     

Synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives

Different approaches for the synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives from simple amino acids have been investigated. A library of 33 precursors for the preparation of N-hydroxy pyrazinones was obtained in moderate to good yields.     

α-Amino acid derived enaminones and their application in the synthesis of N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates and other heterocycles

A new and simple synthesis of novel N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates, which exist in equilibrium with their 4-oxo tautomers, has been developed in two steps starting from N-protected α-amino acids. The key intermediates are enaminones, which can also be isolated, characterized, and used for the construction of other functionalized heterocycles, before they spontaneously decompose to pyrrole products. 4-Hydroxypyrroles are prone to partial aerial oxidation but can be efficiently alkylated or reduced to stable polysubstituted pyrrolidine derivatives.     

Specific intramolecular aromatic CH insertion of diazosulfonamides

The chemoselectivity in the intramolecular CH insertion of various diazosulfonamides has been experimentally studied. The results reveal that the aliphatic 1,4-, 1,5-, or 1,6-C(sp³)?H insertions of diazosulfonamides are not accessible, while the aromatic 1,5-C(sp²)?H insertion can be realized specifically by adjusting the diazo-adjacent group. In addition, the general chemoselectivities in the intramolecular CH insertions of diazosulfonyl compounds are summarized. Generally, diazosulfones undergo both aromatic 1,5-C(sp²)?H and aliphatic 1,5- and 1,6-C(sp³)?H insertions, while diazosulfonates undergo aliphatic 1,5- and 1,6-C(sp³)?H insertions. However, diazosulfonamides only undergo aromatic 1,5-C(sp²)?H insertion.     

A general and convenient synthesis of 4-(tosylmethyl)semicarbazones and their use in amidoalkylation of hydrogen,heteroatom, and carbon nucleophiles

A general synthesis of previously unknown semicarbazone-based α-amidoalkylating reagents, 4-(tosylmethyl)semicarbazones, has been developed. The synthesis involved three-component condensation of semicarbazones of aliphatic or aromatic aldehydes with the same or other aldehydes and p-toluenesulfinic acid. The scope and limitations of this reaction were investigated. The compounds obtained were demonstrated to be an efficient α-(4-semicarbazono)alkylating agents. They were reacted with H- (sodium borohydride), O- (sodium methylate), S- (sodium phenylthiolate), N- (pyrrolidine, sodium succinimide), P- (trialkyl phosphites), and C-nucleophiles (sodium diethyl malonate) to give the corresponding products of the tosyl group substitution, 4-substituted semicarbazones, including analogues of nitrofurazone. Among the prepared compounds tested in vitro for antibacterial and antifungal activity, three nitrofuryl-containing semicarbazones exhibited high biological activities with minimum inhibitory concentration (MIC) values of 8–32 μg/mL.     

Toward new camptothecins. Part 6: Synthesis of crucial ketones and their use in Friedländer reaction

In the context of the preparation of camptothecin and luotonin A analogs, the synthesis of some key keto-precursors and their use in Friedländer condensation are described. This paper also focuses on the stability of these keto intermediates and emphasizes the major differences between indolizinones and pyrroloquinazolinones series. Noteworthy is also the report of some original structures isolated as by-products of some experiments.     

Synthesis of novel chiral bidentate hydroxyalkyl-N-heterocyclic carbene ligands and their application in palladium-catalyzed Mizoroki–Heck couplings and asymmetric addition of diethylzinc to benzaldehyde

A small library of new chiral bidentate hydroxyalkyl-imidazolium salts 1 is conveniently synthesized on multi-gram scale from inexpensive and commercially available chiral pool amino acids. The corresponding carbenes, generated by deprotonation of imidazolium salts 1, in combination with palladium(II) chloride were tested in the Mizoroki–Heck coupling reaction. The most significant results in terms of yields and reactivities were achieved with low catalyst loading. The catalytic activities of these imidazolium salts were also investigated in the asymmetric addition of diethylzinc to benzaldehyde. The use of MgO nanoparticles as an additive in conjunction with these ligands played a crucial role in increasing the efficiency of these reactions.     

N-Heterocyclic carbene-palladacyclic complexes: synthesis,characterization and their applications in the C-N coupling and α-arylation of ketones using aryl chlorides

N-Heterocyclic carbene-palladacyclic complexes 3 were successfully achieved in a one-pot procedure under mild conditions. The structure of 3a was unambiguously confirmed by X-ray single crystal diffraction and it was an active catalyst in the Buchwald-Hartwig amination and α-arylation of ketones even at very low catalyst loadings (0.01?mol%).     

Iodine-mediated oxidative Pictet-Spengler reaction using terminal alkyne as the 2-oxoaldehyde surrogate for the synthesis of 1-aroyl-β-carbolines and fused-nitrogen heterocycles

An efficient iodine-mediated oxidative Pictet-Spengler reaction in dimethyl sulphoxide (DMSO) using terminal alkynes as the 2-oxoaldehyde surrogate for the synthesis of aryl (9H-pyrido[3,4-b]indol-1-yl)methanones is described. The scope of the protocol includes the total synthesis of Fascaplysin, Eudistomins Y₁ and Y₂. The methodology is extended for preparing pyrrolo[1,2-a]-quinoxaline and indolo[1,5-a]quinoxaline derivatives. The utility of 1-aroyl-β-carbolines was demonstrated by performing palladium-catalyzed β-carboline directed ortho-C(sp2)-H functionalization of the phenyl ring with thiomethyl (SMe) group using DMSO as source and for accessing 4-aryl-canthin-6-ones.     

Facile synthesis of bicyclic 1-arylpyrazol-5-ones

In this Letter, we described a facile method for constructing fused bicyclic 1-arylpyrazol-5-one ring system. We employed various methylene-containing carboxylic acids as the substrates and proved that the pyrazolone ring closure requires activated methylene group in intermediate II. Accordingly, a series of structurally diversified, fused bicyclic 1-arylpyrazol-5-ones was prepared in moderate to high yields using the requisite substrates.