全文获取类型
收费全文 | 41095篇 |
免费 | 4002篇 |
国内免费 | 3983篇 |
专业分类
化学 | 27016篇 |
晶体学 | 415篇 |
力学 | 2694篇 |
综合类 | 346篇 |
数学 | 5579篇 |
物理学 | 13030篇 |
出版年
2023年 | 295篇 |
2022年 | 533篇 |
2021年 | 774篇 |
2020年 | 948篇 |
2019年 | 1078篇 |
2018年 | 1013篇 |
2017年 | 1001篇 |
2016年 | 1416篇 |
2015年 | 1248篇 |
2014年 | 1646篇 |
2013年 | 2192篇 |
2012年 | 2433篇 |
2011年 | 2704篇 |
2010年 | 2257篇 |
2009年 | 2230篇 |
2008年 | 2458篇 |
2007年 | 2290篇 |
2006年 | 2068篇 |
2005年 | 1638篇 |
2004年 | 1381篇 |
2003年 | 1298篇 |
2002年 | 1375篇 |
2001年 | 1172篇 |
2000年 | 916篇 |
1999年 | 734篇 |
1998年 | 590篇 |
1997年 | 512篇 |
1996年 | 531篇 |
1995年 | 468篇 |
1994年 | 377篇 |
1993年 | 406篇 |
1992年 | 384篇 |
1991年 | 378篇 |
1990年 | 371篇 |
1989年 | 348篇 |
1987年 | 298篇 |
1985年 | 312篇 |
1984年 | 304篇 |
1983年 | 292篇 |
1979年 | 303篇 |
1978年 | 334篇 |
1977年 | 326篇 |
1976年 | 404篇 |
1975年 | 359篇 |
1974年 | 392篇 |
1973年 | 396篇 |
1972年 | 373篇 |
1971年 | 335篇 |
1970年 | 316篇 |
1969年 | 298篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
941.
The potentiometric titration of N-acetylamino acids and their sodium salts in nitromethane-acetic anhydride (2:1) with a nitromethane solution of perchloric acid has been investigated. A procedure has been developed for the quantitative determination of N-acetylamino acids in the presence of acetic acid in aqueous solutions. A differentiation determination of N-acetylamino acids and their salts in the presence of sodium acetate has been carried out. 相似文献
942.
Kicha A. A. Kalinovskii A. I. Levina É. V. Rashkes Ya. B. Stonik V. A. Elyakov G. B. 《Chemistry of Natural Compounds》1985,21(3):332-337
From the glycoside fraction of the starfishPatiria pectinifera, after its desulfation, an artefactural glycoside has been obtained: 29(-L-arabinofuranosyloxy)-5-stigmastane-3,6,8,15,16-pentaol (I). The structure of (I) was shown by1H and13C NMR spectra and mass spectra and by acetylation and high-temperature hydrogenation.Pacific Ocean Institute of Bioorganic Chemistry, Far Eastern Scientific Center, Academy of Sciences of the USSR, Vladivostok. Institute of Plant Substances, Academy of Sciences of the Uzbek SSR, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 356–361, May–June, 1985. 相似文献
943.
K. B. Yatsimirskii M. I. Kabachnik T. Ya. Medved' N. P. Nesterova É. I. Sinyavskaya L. V. Tsymbal F. I. Bel'skii 《Russian Chemical Bulletin》1988,37(1):44-49
1. | Stability constants for alkali metal complexes of composition [ML]+ and a copper complex [CuLCl]+, which are formed via treatment of alkali metal 2,4-dinitrophenolate or copper chloride with a series of carbamoyl phosphine oxide derivatives, have been determined in anhydrous solutions. |
2. | The most stable complexes are formed by ligands containing an aryl substituent attached to the phosphorus atom. |
944.
Conclusions A model has been suggested to explain the observed relationship between the measured heats of dissolution of uranyl nitrate in aqueous nitrate solutions and the concentration of the salting-out agent. The model describes the change in the structure of water in the solution with change in its concentration. On the one hand, a destruction of the water structure by ions occurs, which is weakened with increase in the distance from the ion, and leads to such irregularity in the distribution of water molecules in the solution that the mean number of molecules of water in unit volume is increased with increase in the distance from the ions. In experiments on the heat of dissolution this increase leads to increased hydration of the uranyl cation and reduction in the endothermicity of the dissolution with increase in the concentration of the solution. On the other hand, an interaction occurs between the ions of the salting-out agent and the water molecules in the solution, leading to the opposite result: There is an increase in the mean number of water molecules of the solution in unit volume in the direction of these ions. In experiments on the heat of dissolution this is revealed in the dehydration of the uranyl cation, and correspondingly in an increase in the endothermicity of the dissolution with increase in the concentration of the solution. The proposed model is in harmony with data on vapor pressure above the solutions (the relationship between the activity coefficient of the water and the concentration of the solution).Translated from Zhurnal Strukturnoi Khimii. Vol. 3, No. 2, pp. 143–150, March–April. 1962 相似文献
945.
富氧条件下乙炔选择催化还原NOx 总被引:1,自引:0,他引:1
Acetylene as a reducing agent of metal exchanged HY catalysts, for selective catalytic reduction of NO in the reaction system of 0.16% NO, 0 (C2H2-SCR) was investigated over a series 08% C2H2, and 9.95% O2 (volume percent) in He. 75% of NO conversion to N2 with hydrocarbon efficiency about 1.5 was achieved over a Ce-HY catalyst around 300 ℃. The NO removal level was comparable with that of selective catalytic reduction of NOx by C3H6 reported in literatures, although only one third of the reducing agent in carbon moles was used in the C2H2-SCR of NO. The protons in zeolite were crucial to the C2H2-SCR of NO, and the performance of HY in the reaction was significantly promoted by cerium incorporation into the zeolite. NO2 was proposed to be the intermediate of NO reduction to N2, and the oxidation of NO to NO2 was rate-determining step of the C2H2-SCR of NO over Ce-HY. The suggestion was well supported by the results of the NO oxidation with O2, and the C2H2 consumption under the conditions in the presence or absence of NO. 相似文献
946.
Migration behavior and enantioseparation of racemic hydrobenzoin and structurally related compounds, including benzoin and benzoin methyl ether, in CZE with a dual CD system consisting of heptakis-(2,3-dihydroxy-6-O-sulfo)-beta-CD (SI-S-beta-CD) and beta-CD as chiral selectors in the presence and absence of borate complexation at pH 9.0 were investigated. The results indicate that enantioseparation of hydrobenzoin is mainly governed by CD complexation of hydrobenzoin-borate complexes with SI-S-beta-CD when SI-S-beta-CD concentration is relatively high. Whereas CD complexation of hydrobenzoin-borate complexes with beta-CD plays a significant role in enantioseparation when SI-S-beta-CD concentration is comparatively low. The (S,S)-enantiomer of the hydrobenzoin-borate complex was found to interact more strongly than the corresponding (R,R)-enantiomer with both SI-S-beta-CD and beta-CD. These two types of CD show the same chiral recognition pattern, but they exhibit opposite effects on the mobility of the enantiomers of hydrobenzoin-borate complexes. Enantiomer migration reversal of hydrobenzoin occurred in the presence of borate complexation when varying the concentration of beta-CD, while keeping SI-S-beta-CD at a relatively low concentration. Binding constants of the enantiomers of benzoin-related compounds to beta-CD and those of hydrobenzoin-borate complexes to SI-beta-CD were evaluated; the mobility contributions of all complex species to the effective mobility of the enantiomers of hydrobenzoin as a function of beta-CD concentration in a borate buffer were analyzed. In addition, comparative studies on the enantioseparation of benzoin-related compounds with SI-S-beta-CD and with randomly sulfate-substituted beta-CD were made. 相似文献
947.
Pt/Au双金属纳米粒子的制备及表征 总被引:6,自引:1,他引:6
Poly (N-vinyl-2-pyrrolidone)-protected Pt/Au bimetallic nanoparticles were obtained by reducing the mixture of HAuCl4 and H2PtCl6 with sodium borohydride. UV-vis spectra, transmission electronic microscopy and X-my diffraction reveal that the prepared bimetallic nanoparticles are of alloy structure. 相似文献
948.
Systematic synthesis and characterization of single-crystal lanthanide orthophosphate nanowires 总被引:8,自引:0,他引:8
Fang YP Xu AW Song RQ Zhang HX You LP Yu JC Liu HQ 《Journal of the American Chemical Society》2003,125(51):16025-16034
A simple hydrothermal method has been developed for the systematic synthesis of lanthanide orthophosphate crystals with different crystalline phases and morphologies. It has been shown that pure LnPO(4) compounds change structure with decreasing Ln ionic radius: i.e., the orthophosphates from Ho to Lu as well as Y exist only in the tetragonal zircon (xenotime) structure, while the orthophosphates from La to Dy exist in the hexagonal structure under hydrothermal treatment. The obtained hexagonal structured lanthanide orthophosphate LnPO(4) (Ln = La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, and Dy) products have a wirelike morphology. In contrast, tetragonal LnPO(4) (Ln = Ho, Er, Tm, Yb, Lu, Y) samples prepared under the same experimental conditions consist of nanoparticles. The obtained hexagonal LnPO(4) (Ln = La --> Tb) can convert to the monoclinic monazite structured products, and their morphologies remained the same after calcination at 900 degrees C in air (Hexagonal DyPO(4) is an exceptional case, it transformed to tetragonal DyPO(4) by calcination), while the tetragonal structure for (Ho--> Lu, Y)PO(4) remains unchanged by calcination. The resulting LnPO(4) (Ln = La --> Dy) products consist almost entirely of nanowires/nanorods with diameters of 5-120 nm and lengths ranging from several hundreds of nanometers to several micrometers. Europium doped LaPO(4) nanowires were also prepared, and their photoluminescent properties were reported. The optical absorption spectrum of CePO(4) nanowires was measured and showed some differences from that of bulk CePO(4) materials. The possible growth mechanism of lanthanide phosphate nanowires was explored in detail. X-ray diffraction, field-emission scanning electron microscopy, transmission electron microscopy, electron diffraction, infrared absorption spectra, X-ray photoelectron spectroscopy, optical absorption spectra, and photoluminescence spectra have been employed to characterize these materials. 相似文献
949.
本文利用单羧基二茂铁Fc-COOH和1,1′-二羧基二茂铁HOOC-Fc-COOH作为配体分别合成了双核铈配合物Ce2(FcCOO)6 (1)和二维层状配位聚合物Ce2(OOC-Fc-COO)3(2),测定了两种配合物的晶体结构。配合物1中的金属铈离子为九配位结构,分别与周围的羧基二茂铁上的氧原子和作为辅助配体的水分子配位,茂铁间的π-π相互作用将配合物1的二聚体单元连结在一起形成二维的网状结构。配合物2中的金属铈离子亦为九配位结构,分别与周围的羧基二茂铁上的氧原子,作为辅助配体的水分子和甲醇配位形成类似于配合物1的二聚体单元,1,1′-二羧基二茂铁HOOC-Fc-COOH作为桥基配体将二聚体单元连结在一起,形成二维网状的配位聚合物。 相似文献
950.
Application of multivariate curve resolution with alternating least squares (ALS) methods to second-order data from capillary electrophoresis diode array detector (CE-DAD) is shown. Second-order data are easily obtained by setting individual data matrix of CE run one in top of the other. Initial qualitative solutions obtained by evolving factor analysis can be further optimized by simultaneous analysis of multiple electrophoresis run data with ALS regression. Quantification is achieved by the comparison of the analyte peak areas with that of pure standards. During the ALS regression procedure, the following constraints were applied: (i) both concentrations and unit pure spectra of the resolved components must be positive; (ii) elution profiles have an unimodal shape; (iii) correspondence exists between common species in the different data matrices; (iv) the pure spectrum of each species is the same in all runs where it is present. The above methods were applied for the determination of dinitrotoluene (DNT) isomeric compounds in overlapping peaks from CE. 相似文献