全文获取类型
收费全文 | 702篇 |
免费 | 60篇 |
国内免费 | 99篇 |
专业分类
化学 | 574篇 |
晶体学 | 12篇 |
力学 | 64篇 |
综合类 | 3篇 |
数学 | 59篇 |
物理学 | 149篇 |
出版年
2024年 | 3篇 |
2023年 | 13篇 |
2022年 | 19篇 |
2021年 | 28篇 |
2020年 | 26篇 |
2019年 | 23篇 |
2018年 | 24篇 |
2017年 | 18篇 |
2016年 | 33篇 |
2015年 | 31篇 |
2014年 | 30篇 |
2013年 | 35篇 |
2012年 | 51篇 |
2011年 | 53篇 |
2010年 | 36篇 |
2009年 | 37篇 |
2008年 | 44篇 |
2007年 | 46篇 |
2006年 | 43篇 |
2005年 | 38篇 |
2004年 | 31篇 |
2003年 | 32篇 |
2002年 | 21篇 |
2001年 | 16篇 |
2000年 | 22篇 |
1999年 | 17篇 |
1998年 | 12篇 |
1997年 | 11篇 |
1996年 | 19篇 |
1995年 | 12篇 |
1994年 | 12篇 |
1993年 | 1篇 |
1992年 | 5篇 |
1991年 | 1篇 |
1990年 | 8篇 |
1989年 | 7篇 |
1983年 | 1篇 |
1982年 | 1篇 |
1971年 | 1篇 |
排序方式: 共有861条查询结果,搜索用时 31 毫秒
1.
1-Propyl-3-methylimidazolium chloride ([C3MIm]Cl) ionic liquid and sulfamic acid (NH2SO3H), as a synergetic catalytic medium, were used for the transesterification of acetoacetate with alcohols of different structures. It shows the good ability for the chemoselective transesterificatin of β-ketoesters and maintains its catalytic activity in the reuse. 相似文献
2.
A method was proposed for the simultaneous determination of trace cadmium and mercury by vapor generation non-dispersive atomic fluorescence spectrometry using an intermittent flow system. The effects of the parameters on the performance were studied systematically. The parameters such as acid concentration of the reaction medium, flow rate of the carrier gas and shield gas, the observation height and the atomizer temperature, etc. which affected the sensitivity, were optimized. Ascorbic acid, cobalt ion and thiourea were used as enhancement reagents or masking agents to enhance the generation efficiency of the volatile species of Cd and Hg. The mechanisms of their effects on vapor generation were investigated. In the presence of thiourea and ascorbic acid, the influences of some coexisting elements on the determination of cadmium and mercury were investigated. The detection limits (3sigma) were 0.010 microg l(-1) for Cd and 0.019 microg l(-1) for Hg, respectively. The relative standard deviations for Cd and Hg at 1.00 microg l(-1) were 2.6% and 0.97% (n = 11), respectively. The proposed method has been satisfactorily applied to the determination of trace cadmium and mercury in Chinese herbal medicine. 相似文献
3.
Wei Hong Jinxiong Zhou Zhigang Suo 《Journal of the mechanics and physics of solids》2008,56(5):1779-1793
A large quantity of small molecules may migrate into a network of long polymers, causing the network to swell, forming an aggregate known as a polymeric gel. This paper formulates a theory of the coupled mass transport and large deformation. The free energy of the gel results from two molecular processes: stretching the network and mixing the network with the small molecules. Both the small molecules and the long polymers are taken to be incompressible, a constraint that we enforce by using a Lagrange multiplier, which coincides with the osmosis pressure or the swelling stress. The gel can undergo large deformation of two modes. The first mode results from the fast process of local rearrangement of molecules, allowing the gel to change shape but not volume. The second mode results from the slow process of long-range migration of the small molecules, allowing the gel to change both shape and volume. We assume that the local rearrangement is instantaneous, and model the long-range migration by assuming that the small molecules diffuse inside the gel. The theory is illustrated with a layer of a gel constrained in its plane and subject to a weight in the normal direction. We also predict the scaling behavior of a gel under a conical indenter. 相似文献
4.
负载型双金属簇催化剂的多相一氧化碳加氢反应性能索全伶,李晔(内蒙古工业大学化学工程系,呼和浩特010062)殷元骐,金道森(中国科学院兰州化学物理研究所,兰州730000)关键词一氧化碳加氢,多相催化,双金属簇催化剂,钾效应。1.引言异核金属羰基簇作... 相似文献
5.
Zhengping Hao Lidun An Junling Zhou Hongli Wang 《Reaction Kinetics and Catalysis Letters》1996,59(2):295-300
Supported gold catalyst for eliminating hydrogen from CO2 feed gas in the production of urea is found to be superior to other industrial catalysts (e.g. Pt/Al2O3 and PdPt/Al2O3) in catalytic activity and resistance to sulfur poisoning. 相似文献
6.
Yong Ding Baochun Ma Qiang Gao Guixian Li Liang Yan Jishuan Suo 《Journal of molecular catalysis. A, Chemical》2005,230(1-2):121-128
The epoxidation of cyclopentene with hydrogen peroxide catalyzed by 12-heteropolyacids of molybdenum and tungsten (H3PMo12−nWnO40, n = 1–11), 12-tungstophosphoric acid and 12-molybdophosphoric acid combined with cetylpyridinium bromide as a phase transfer reagent was carried out in acetonitrile. Among 13 heteropolyacids investigated, catalyst of H3PMo6W6O40 showed the highest activity, giving a conversion of 60% and a selectivity of 95% in the epoxidation of cyclopentene. The fresh catalysts and the catalysts under reaction condition were characterized by UV–vis, FT-IR and 31P NMR spectroscopy, which has revealed that all of the molybdotungstophosphoric acids were degraded in the presence of hydrogen peroxide to form a considerable amount of phosphorus-containing species. The active species resulted from H3PMo6W6O40 are new kinds of phosphorus-containing species, which is different from {PO4[WO(O2)2]4}3−. 相似文献
7.
8.
SAPO-5,-11和-34分子筛模板剂的脱除及其结构的热致变化 总被引:2,自引:0,他引:2
用水热法合成了SAPO-5,-11和-34硅磷酸铝类分子筛。并对经不同温度焙烧处理的样品进行表征,结果表明:分子筛中模块剂的热分解过程与其结构和孔大小有较大的关系。在SAPO-5和SAPO-34分子筛中,外部联接的T-O-T键的反对称伸缩振动峰(1240cm~(-1)-1038cm~(-1))和其对称伸缩振动(734cm~(-1)-600cm~(-1))及双环的变形振动(600-500cm~(-1))的吸收峰对样品的结晶度比较敏感。但在SAPO-11中,分子筛骨架中T-O-T反对称伸缩振动(1225cm~(-1)和1038cm~(-1))随结晶度的下降而基本保持不变,但内四面体(TO_4)的对称伸缩振动,反对称伸缩振动峰及T-O弯曲振动峰随样品焙烧温度的升高而减弱并分裂。红外吸收带向低频方向移动。SEM-EDAX结果表明:随样品焙烧温度的升高,结晶度下降,分子筛晶形变得不规则,晶面越来越粗糙,但结晶度的下降并非由于其中PO_4四面体的热分解所引起,而是由外部联结的T-O-T键的断裂,双环被破坏及骨架元素间的重排所引起。 相似文献
9.
A wholly-aromatic thermotropic liquid crystalline polymer (WATLCP) composed ofp-hydroxybenzoic acid (HBA), 4,4'-dihydroxy bisphenyl (BP), terephthalic acid (TPA),m-phthalic acid (MPA) was synthesized. It was symbolized by BP-LCP. Using a simi-lar method, a new copolymer BP-PSF was prepared. BP-PSF has a semi-flexible chainpolysulfone and a rigid-rod chain like BP-LCP. By FT-IR, polarizing microscope and DSCtechnique, the structures and properties of BP-LCP and BP-PSF were studied. 相似文献
10.
Jinmao You Xiangming Chen Xianen Zhao Yourui Suo Honglun Wang Yulin Li Jing Sun 《Chromatographia》2006,63(7-8):337-343
A pre-column derivatization method for the sensitive determination of amines using the labeling reagent 1,2-benzo-3,4-dihydrocarbazole-9-isopropyl
chloroformate (BCIC-Cl) followed by high-performance liquid chromatography with fluorescence detection has been developed.
Identification of derivatives is carried out by high performance liquid chromatography/atmospheric pressure chemical ionization
(LC-APCI-MS-MS). The chromophore of 2-(9-carbazole)-ethyl chloroformate (CEOC) reagent is replaced by 1,2-benzo-3,4-dihydrocarbazole-9-isopropyl
functional group, which results in a sensitive fluorescence derivatizing reagent BCIC-Cl. BCIC-Cl can easily and quickly label
amines. Derivatives are stable enough to be efficiently analyzed by high-performance liquid chromatography and show an intense
protonated molecular ion corresponding m/z [MH]+ under APCI in positive-ion mode. The collision-induced dissociation of protonated molecular ion formed a product at m/z 260 corresponding to the cleavage of CH2-OCO bond. Studies on derivatization demonstrate excellent derivative yields over the pH 9.0–10.0. Maximal yields close to
100% are observed with a 3 to 4-fold molar reagent excess. In addition, the detection responses for BCIC derivatives are compared
with those obtained using CEOC and FMOC as derivatization reagents. The ratios of IBCIC/ICEOC and IBCIC/IFMOC are, respectively, 1.23–3.14 and 1.25–3.08 for fluorescent (FL) responses (here, I is relative fluorescence intensity). Separation of the derivatized amines had been optimized on reversed-phase Eclipse XDB-C8 column. Detection limits are calculated from 1.0 pmol injection, at a signal-to-noise ratio of 3, are 10.6–37.8 fmol. The
mean interday accuracy ranges from 94 to 105% for fluorescence detection with the largest mean %CV<7.5. The mean interday
precision for all standards is < 6.0% of the expected concentration. Excellent linear responses are observed with coefficients
of > 0.9997.
Revised: 12 December 2005 and 13 Febrauary 2006 相似文献