全文获取类型
收费全文 | 2185篇 |
免费 | 111篇 |
国内免费 | 431篇 |
专业分类
化学 | 2586篇 |
晶体学 | 24篇 |
力学 | 8篇 |
综合类 | 16篇 |
物理学 | 93篇 |
出版年
2024年 | 2篇 |
2023年 | 14篇 |
2022年 | 49篇 |
2021年 | 43篇 |
2020年 | 59篇 |
2019年 | 47篇 |
2018年 | 68篇 |
2017年 | 76篇 |
2016年 | 86篇 |
2015年 | 75篇 |
2014年 | 115篇 |
2013年 | 258篇 |
2012年 | 112篇 |
2011年 | 112篇 |
2010年 | 114篇 |
2009年 | 119篇 |
2008年 | 133篇 |
2007年 | 129篇 |
2006年 | 133篇 |
2005年 | 145篇 |
2004年 | 123篇 |
2003年 | 113篇 |
2002年 | 71篇 |
2001年 | 68篇 |
2000年 | 57篇 |
1999年 | 72篇 |
1998年 | 48篇 |
1997年 | 49篇 |
1996年 | 46篇 |
1995年 | 41篇 |
1994年 | 28篇 |
1993年 | 28篇 |
1992年 | 24篇 |
1991年 | 16篇 |
1990年 | 6篇 |
1989年 | 9篇 |
1988年 | 8篇 |
1987年 | 4篇 |
1986年 | 3篇 |
1985年 | 5篇 |
1984年 | 5篇 |
1983年 | 1篇 |
1982年 | 4篇 |
1981年 | 1篇 |
1980年 | 6篇 |
1978年 | 1篇 |
1970年 | 1篇 |
排序方式: 共有2727条查询结果,搜索用时 15 毫秒
51.
Molecular routes to metal oxides has become an area of intensescientific interest due to the technological relevance of thesematerials. Molecular routes are proving important as a result ofthe possibility to control the physical and chemical propertiesof the final materials.We have chosen to study non-hydrolytic methods, namely esterelimination reactions between two prototypical molecularprecursors metal alkoxides, M(OR)n, and metal carboxylates, M(O2CR)n, to synthesize metal oxides:
This method allows for the synthesis of pure metal oxides bycomplete elimination of the organic supporting ligands withconcomitant formation of M-O-M bridges.Furthermore, incomplete esterelimination can lead to isolation of molecular clusters asintermediates which can also be used as building blocks for theformation of metal oxides with controlled microstructure.Here we report a series of reactions between Sn and Si alkoxidesand carboxylates designed to gain further insight into thefactors governing ester elimination reactions. By choosingcompounds with varying coordination environments and stericaccessibility we have devised a set of criteria which shouldallow for successful ester elimination between metal alkoxide andcarboxylate compounds. Furthermore we have also shown theability of ester elimination derived molecular clusters withspecific microstructure to be used in the synthesis of bulkmaterials retaining the structural attributes of the precursor cluster. 相似文献
52.
In the enantioselective esterification of racemic naproxen with 4(2-hydroxyethyl) morpholine by Lipase MY in organic solvents,
a productivity improvement of the desired (S)-naproxen ester from 0.42 to 0.72 mM at the reaction time of 130 h was observed,
when the surfactantbis (2-ethylhexyl) sodium sulfosuccinate (AOT) was added in the reaction mixture. The presence of a small amount of exogenously
added water dramatically activated the enzyme in AOT/cyclohexane-reversed micelles. Desorption of the surfactant molecule
from the enzyme mass and solubilization of the enzyme into reversed micelles were used to elucidate an existing maximum of
the initial rate of (S)-naproxen synthesis with the water content. Moreover, the effects of alcohol and surfactant concentration
on the enzyme activity are reported. 相似文献
53.
M. Fujiwara T. Okano T. -H. Nakashima A. A. Nakamura G. Sugihara 《Colloid and polymer science》1997,275(5):474-479
For a sodium salt of α-sulfonatomyristic acid methyl ester (14SFNa), one of the α-SFMe series surfactants, critical micellization
concentration (CMC), solubility and degree of counterion binding (β) were determined by means of electrocon-ductivity measurements
at different temperatures (at every 5 °C) ranging from 15 to 50 °C. The phase diagram of 14SFNa in pure water was constructed
from the CMC- and solubility-temperature data, in which the Krafft temperature (critical solution temperature) was found around
0 °C. The changes in the Gibbs energy, ΔG
0
m, enthalpy, ΔH
0
m, and entropy, ΔS
0
m, upon micelle formation as a function of temperature were evaluated taking βvalues into calculation.
Received: 28 August 1996 Accepted: 5 November 1996 相似文献
54.
Jordan De Jesus Silva Niccolò Bartalucci Benson Jelier Samantha Grosslight Tobias Gensch Claas Schünemann Bernd Müller Paul C. J. Kamer Christophe Copéret Matthew S. Sigman Antonio Togni 《Helvetica chimica acta》2021,104(12):e2100200
A synthetic method for the palladium-catalyzed cyanation of aryl boronic acids using bench stable and non-toxic N-cyanosuccinimide has been developed. High-throughput experimentation facilitated the screen of 90 different ligands and the resultant statistical data analysis identified that ligand σ-donation, π-acidity and sterics are key drivers that govern yield. Categorization into three ligand groups – monophosphines, bisphosphines and miscellaneous – was performed before the analysis. For the monophosphines, the yield of the reaction increases for strong σ-donating, weak π-accepting ligands, with flexible pendant substituents. For the bisphosphines, the yield predominantly correlates with ligand lability. The applicability of the designed reaction to a wider substrate scope was investigated, showing good functional group tolerance in particular with boronic acids bearing electron-withdrawing substituents. This work outlines the development of a novel reaction, coupled with a fast and efficient workflow to gain understanding of the optimal ligand properties for the design of improved palladium cross-coupling catalysts. 相似文献
55.
Mara K. Kuenen James A. Mullin Rachel A. Letteri 《Journal of polymer science. Part A, Polymer chemistry》2021,59(19):2212-2221
With a vast, synthetically accessible compositional space and highly tunable hydrolysis rates, poly(β-amino ester)s (PBAEs) are an attractive degradable polymer platform. Leveraging PBAEs in a wide range of applications hinges on the ability to program degradation, which, thus far, has been frustrated by multiple confounding phenomena contributing to the degradation of these charged polyesters. Basic conditions accelerate hydrolysis, yet reduce solubility, limiting water access to amines and esters. Further, the high buffering capacity of PBAEs can render buffers ineffective at controlling solution pH. To unify understanding of PBAE degradation and solution properties, this study examines PBAE hydrolysis as a function of pH and buffer concentration as well as polymer hydrophobicity. At low buffer concentrations, the PBAE amines and the acid produced during hydrolysis control solution pH. Meanwhile, at high buffer concentrations that afford relatively constant pH, hydrolysis rate increases with pH, despite the reduced PBAE solubility. Increasing the hydrophobic content of PBAEs eventually hinders the capacity of the polymer to accept protons from solution, limiting the pH increase and slowing hydrolysis. These studies showcase the role of buffering on the pH-dependent degradation and solution properties of PBAEs, providing guidance for programming degradation in applications ranging from drug delivery to thermosets. 相似文献
56.
Oliver Andler Prof. Dr. Uli Kazmaier 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(3):949-953
Application of ester dienolates as nucleophiles in Matteson homologations allows for the stereoselective synthesis of highly substituted α,β-unsaturated δ-hydroxy carboxyl acids, structural motifs widespread found in polyketide natural products. The protocol is rather flexible and permits the introduction of substituents and functionalities also at those positions which are not accessible by the commonly used aldol reaction. Therefore, this ester dienolate Matteson approach is an interesting alternative to the “classical” polyketide syntheses. 相似文献
57.
58.
我国大戟二萜酯及其生理活性研究新进展 总被引:11,自引:1,他引:11
介绍了我国近10年来从大戟属植物中发现的二萜酯类新化合物及它们的刺激性,抗癌活性和杀菌作用等生理活性的研究,其中包括5种新发现碳骨架的20个高氧化型二萜多酯类化合物。 相似文献
59.
聚(酪氨酸酯对苯二甲酰胺)碳酸酯药物控制释放材料的研究 总被引:2,自引:0,他引:2
报道了一类生物可降解聚(酪氨酸酯对苯二甲酰胺)碳酸酯的合成和结构表征,研究了聚合物的性质和体外降解性能,并以5 氟脲嘧啶和牛血清白蛋为模型,对它们作为药物控制释放材料的性能进行了初步评价. 相似文献
60.
聚苯乙烯—吡啶树脂的合成及催化水解反应 总被引:4,自引:0,他引:4
在氢氧化钠作用下,氯甲基化聚苯乙烯与吡啶反应制成聚苯乙烯-吡啶树脂,测定了其化学组成和红外光谱,并考察了在酯水解反应中的催化活性。 相似文献