全文获取类型
收费全文 | 88篇 |
免费 | 11篇 |
国内免费 | 44篇 |
专业分类
化学 | 128篇 |
晶体学 | 4篇 |
力学 | 2篇 |
数学 | 1篇 |
物理学 | 8篇 |
出版年
2024年 | 1篇 |
2023年 | 1篇 |
2022年 | 3篇 |
2021年 | 4篇 |
2019年 | 5篇 |
2018年 | 2篇 |
2017年 | 1篇 |
2016年 | 2篇 |
2015年 | 9篇 |
2014年 | 4篇 |
2013年 | 14篇 |
2012年 | 4篇 |
2011年 | 6篇 |
2010年 | 1篇 |
2009年 | 4篇 |
2008年 | 6篇 |
2007年 | 5篇 |
2006年 | 6篇 |
2005年 | 9篇 |
2004年 | 15篇 |
2003年 | 11篇 |
2002年 | 6篇 |
2001年 | 3篇 |
2000年 | 4篇 |
1999年 | 5篇 |
1997年 | 2篇 |
1996年 | 1篇 |
1995年 | 1篇 |
1993年 | 1篇 |
1991年 | 4篇 |
1982年 | 1篇 |
1976年 | 2篇 |
排序方式: 共有143条查询结果,搜索用时 15 毫秒
1.
About the Structure and Reactivity of Diammonium Hexafluoromanganate(IV) Electrolytic oxidation of an aqueous suspension of MnF2 containing NH4F, and subsequent crystallization in 40% HF yields yellow crystals of (NH4)2MnF6. It crystallizes in the hexagonal K2MnF6 type structure with the space group P63mc and a = 5.903; c = 9.565 Å; Z = 2. With in situ powder diffraction studies it is shown, that (NH4)2MnF6 is gradually reduced in a NH3 atmosphere between 30 and 230 °C to afford (NH4)3MnF6, (NH4)2MnF5, and finally NH4MnF3. (NH4)3MnF6, thereby, forms a hitherto unknown cubic (a = 9.082 Å) high temperature modification with the cryolite type structure. Under N2 the thermal decomposition of (NH4)2MnF6 proceeds via NH4MnF4 to yield MnF2. 相似文献
2.
邻氯苄基氯与锡反应合成三(邻氯苄基)氯化锡,经x射线方法测定了新化合物 的晶体结构,化合物属三方晶系,空间群为R-3,晶体学参数:α=b=1.3583(4) mn,c=2.1147(8)am,v=3.3790(19)nm~3,Z=6,μ(Mo kα)=16.11cm~-1, r (000):1572,R_1=O.0755;Sn-C键长分别为0.2148(13)和0.220(2)nm,Sn-C1 键为0.2528(15)和0.2477(13)Bill.中心锡原子与亚甲基碳和氯原子构成畸型四 面体.并对其结构进行量子化学从头计算,探讨化合物的稳定性、分子轨道能量、 原子净电荷布居规律以及一些前沿分子轨道的组成特征. 相似文献
3.
工业氨基三甲叉膦酸中副产物的核磁共振分析 总被引:1,自引:0,他引:1
采用多种核磁共振(NMR)技术测定了工业氨基三甲叉膦酸(ATMP)产品中副产物的分子结构,发现该物质为甲氨基二甲叉膦酸(MADMP),它是甲醛歧化反应导致的副产物;给出了可能的反应方程式;测出了MADMP的相对含量,MADMP与ATMP摩尔比约为2。 相似文献
4.
V. Ya. Sosnovskikh M. A. Barabanov B. I. Usachev R. A. Irgashev V. S. Moshkin 《Russian Chemical Bulletin》2005,54(12):2846-2850
Condensation of 4-acetyl-5-hydroxy-3-methyl-1-phenylpyrazole with RFCO2Et (RF = CF2H, CF3) in the presence of LiH affords 4-di(tri)fluoroacetoacetyl-5-hydroxy-3-methyl-1-phenylpyrazoles from which 6-di(tri)fluoromethyl-and
5-di(tri)fluoroacetyl-3-methyl-1-phenylpyrano[2,3-c]pyrazol-4(1H)-ones were synthesized. The reactions of pyrano-pyrazoles with hydrazine hydrate, ethyl mercaptoacetate, or aromatic amines
proceed at the C(6) atom with pyrone ring opening and formation of aminoenones, pyrazoles, or thiophenes with the 5-hydroxy-3-methyl-1-phenyl-4-pyrazolyl
fragment.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2750–2754, December, 2005. 相似文献
5.
A vanadium oxide-modified glassy carbon electrode was simply and conveniently fabricated by casting vanadium tri(isoproxide) oxide (VO(OC3H7)3) and poly(propylene carbonate) (PPC) onto the glassy carbon electrode surface. The electrochemical properties of iodide at the VO(OC3H7)3-PPC film-modified glassy carbon electrode were investigated by cyclic voltammetry, and an anodic peak was observed at approximately +0.71 V (vs. SCE). Based on this, a sensitive and convenient electrochemical method was proposed for the determination of iodide. Flow injection amperometry (FIA) exhibited a good linear relationship with the concentration of iodide in the range of 5 × 10−7 mol L−1 and 1 × 10−3 mol L−1, and the detection limit was 1 × 10−7 mol L−1. Quantitative recovery of iodide in synthetic samples has been obtained and the interferences from different cations and anions have been studied. The method has been successfully applied to the determination of iodide in dry edible seaweed. The concentrations of iodide measured by this method are in good agreement with those obtained by spectrophotometric method. 相似文献
6.
The collagen type I segment long spacing (SLS) crystallite is a well-ordered rod-like molecular aggregate, ∼300 nm in length, which is produced in vitro under mildly acidic conditions (pH 2.5–3.5) in the presence of 1 mM ATP. The formation of the SLS crystallite amplifies the inherent linear structural features of individual collagen heterotrimers, due to the punctate linear distribution and summation of the bulkier amino acid side chains along the length of individual collagen heterotrimers. This can be correlated structurally with the 67 nm D-banded collagen fibril that is found in vivo, and formed in vitro. Although first described many years ago, the range of conditions required for ATP-induced SLS crystallite formation from acid-soluble collagen have not been explored extensively. Consequently, we have addressed biochemical parameters such as the ATP concentration, pH, speed of formation and stability so as to provide a more complete structural understanding of the SLS crystallite. Treatment of collagen type I with 1 mM ATP at neutral and higher pH (6.0–9.0) also induced the formation of D-banded fibrils. Contrary to previous studies, we have shown that the polysulphonated diazo dyes Direct red (Sirius red) and Evans blue, but not Congo red and Methyl blue, can also induce the formation of SLS-like aggregates of collagen, but under markedly different ionic conditions to those employed in the presence of ATP. Specifically, pre-formed D-banded collagen fibrils, prepared in a higher than the usual physiological NaCl concentration (e.g. 500 mM NaCl, 20 mM Tris-HCl pH7.4 or x3 PBS), readily form SLS aggregates when treated with 0.1 mM Direct red and Evans blue, but this did not occur at lower NaCl concentrations. These new data are discussed in relation to the anion (Cl−) and polyanion (phosphate and sulphonate) binding by the collagen heterotrimer and their likely role in collagen fibrillogenesis and SLS formation. 相似文献
7.
Wei Peng Jie Dong Han‐Bin Li Christine Chow Qiao‐Sheng Hu 《Journal of polymer science. Part A, Polymer chemistry》2019,57(14):1606-1611
Room temperature Suzuki cross‐coupling polymerization of aryl dibromides/diiodides with aryldiboronic acids/acid esters with t‐Bu3P‐coordinated 2‐phenylaniline‐based palladacycle complex, [2′‐(amino‐kN)[1,1′‐biphenyl]‐2‐yl‐kC]chloro(tri‐t‐butylphosphine)palladium, as a general precatalyst is described. Such room temperature Suzuki cross‐coupling polymerization is achieved by employing six equivalents or more of the base and affords polymers within an hour, with the yields and the molecular weights in general comparable to or higher than reported results that required higher reaction temperature and/or longer polymerization time. Our study provides a general catalyst system for the room temperature Suzuki cross‐coupling polymerization of aryl dibromides/diiodides with aryldiboronic acids/acid esters and paves the road for the investigation of employing other monodentate ligand‐coordinated palladacycle complexes including other electron‐rich monophosphine‐coordinated ones for room temperature cross‐coupling polymerizations. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 1606–1611 相似文献
8.
A mild and highly efficient stereoselective reaction of 3,4,6‐tri‐O‐acetyl‐d‐glucal with a variety of nucleophiles, viz. alcohols, phenols, thiols, thiophenols, and allyl trimethyl silane (TMS), in the presence of 5 mol% of lanthanum(III) nitrate hexahydrate under solvent‐free conditions yielded the corresponding 2,3‐unsaturated glycopyranosides (pseudoglycals) in excellent yields. 相似文献
9.
The tin hydride–mediated cyclization of a number of sulfides and sulfones under mild and neutral conditions has been investigated. The sulfides were in turn derived from 3(2H) benzothiofuranone and 2‐bromobenzyl bromides by phase‐transfer‐catalyzed reaction, and the corresponding sulfones were prepared by treatment of the corresponding sulfides with m‐CPBA at room temperature. The sulfides and sulfones were then reacted with n Bu3SnH‐AIBN to afford regioselectively benzofuran‐annulated six‐membered sulfur heterocycles. 相似文献
10.
Abstract A series of novel Mahkoside A derivatives was synthesized, and their in vitro cytotoxic activities were evaluated against the human cancer cell line Ec‐9706. A Preliminary structure–activity relationship study showed compounds 7 and 8 have obvious cytotoxic activities (IC50: 30.0 and 12.5 µg · mL?1, respectively). 相似文献