全文获取类型
收费全文 | 11938篇 |
免费 | 722篇 |
国内免费 | 700篇 |
专业分类
化学 | 2256篇 |
晶体学 | 24篇 |
力学 | 672篇 |
综合类 | 102篇 |
数学 | 3222篇 |
物理学 | 1566篇 |
综合类 | 5518篇 |
出版年
2024年 | 26篇 |
2023年 | 83篇 |
2022年 | 113篇 |
2021年 | 133篇 |
2020年 | 187篇 |
2019年 | 178篇 |
2018年 | 198篇 |
2017年 | 234篇 |
2016年 | 243篇 |
2015年 | 267篇 |
2014年 | 441篇 |
2013年 | 551篇 |
2012年 | 515篇 |
2011年 | 598篇 |
2010年 | 567篇 |
2009年 | 673篇 |
2008年 | 753篇 |
2007年 | 850篇 |
2006年 | 729篇 |
2005年 | 690篇 |
2004年 | 560篇 |
2003年 | 565篇 |
2002年 | 626篇 |
2001年 | 458篇 |
2000年 | 364篇 |
1999年 | 333篇 |
1998年 | 321篇 |
1997年 | 258篇 |
1996年 | 264篇 |
1995年 | 234篇 |
1994年 | 213篇 |
1993年 | 183篇 |
1992年 | 146篇 |
1991年 | 126篇 |
1990年 | 99篇 |
1989年 | 106篇 |
1988年 | 76篇 |
1987年 | 73篇 |
1986年 | 56篇 |
1985年 | 46篇 |
1984年 | 31篇 |
1983年 | 18篇 |
1982年 | 35篇 |
1981年 | 41篇 |
1980年 | 23篇 |
1979年 | 25篇 |
1978年 | 19篇 |
1977年 | 5篇 |
1976年 | 9篇 |
1973年 | 6篇 |
排序方式: 共有10000条查询结果,搜索用时 781 毫秒
171.
Halina Y. Neujahr 《Applied biochemistry and biotechnology》1982,7(1-2):107-111
The enzyme phenol 2-hydroxylase was immobilized on Sepharose and used in conjunction with an O2 electrode for quantitating phenol. Similarly, catechol 1,2-oxygenase was used for quantitating catechol. A third probe was
prepared by immobilization ofTrichosporon cutaneum cells rather than purified phenol 2-hydroxylase for phenol quantitation. The whole cell system gave results comparable to
the immobilized enzyme system. 相似文献
172.
G. J. Dear D. N. Mallett D. M. Higton A. D. Roberts S. A. Bird H. Young R. S. Plumb I. M. Ismail 《Chromatographia》2002,55(3-4):177-184
Summary In this paper we investigate the potential of alkyl-bonded silica monolithic columns for the isolation and identification
of drug-related components in biological fluids. Up to 6 columns have been connected in series to produce a chromatographic
system with up to 40,000 plates. This high-resolution chromatography system has been coupled to both MS and NMR to enable
efficient detection and characterisation of drug-related components in biological fluids. The use of six coupled columns has
been shown to give enhanced resolution over a high quality silica particulate column packed with 3 μm material which exhibits
the same back pressure. The effect of volume and mass load on the performance of monolithic columns for semi-preparative chromatography
of biological fluids has also been investigated. In these studies it was possible to inject up to 100 mL of neat urine with
no loss of chromatographic performance. Furthermore, upon re-testing, the columns showed similar chromatographic performance.
Again several columns were serially connected, producing enhanced resolution in the semi-preparative mode. 相似文献
173.
K. Jinno 《Journal of separation science》1982,5(7):364-367
The chromatographic performance of the deuterated solvents, CD3OD and D2O, has been investigated in reversed-phase micro high performance liquid chromatography. The chromatographic performance of CD3OD is only slightly superior to that of CH3OH. However, the performance of D2 is significantly superior to that of H2O, separation of aromatics being improved by about 30%. D2 is a particularly powerful solvent for the separation iof deuterated and non-deuterated compounds. 相似文献
174.
The structure and stability of classical and bridged C2H
3
+
is reinvestigated. The SCF and CEPA-PNO computations performed with flexibles andp basis sets including twod-sets on carbon confirm our previous results. We find the protonated acetylene structure to be more stable than the vinyl
cation by 3.5–4 kcal/mol. The energy barrier for the interconversion of these two structures is at most a few tenths of a
kcal/mol. The equilibrium SCF geometries of Weberet al. [15] are affected insignificantly by further optimization at the CEPA-PNO level.
Several structures for the interaction of C2H
3
+
with HF have been investigated at the SCF level. With our largest basis set which includes a complete set of polarization
functions we find a remarkable levelling of the stabilities of most of the structures. In these cases the stabilization energy
ΔE ranges from −10 to −13 kcal/mol. 相似文献
175.
Organoboranes, readily available via the hydroboration of unsaturated organic compounds, exhibit a remarkable versatility
in their reactions. The boron atom in these organoboranes can be readily converted into a wide variety of organic groups under
very mild conditions, providing simple versatile syntheses of organic compounds. Exploration of these substitution reactions
reveal that, with rare exceptions, the organoboranes transfer the alkyl group to other elements of synthetic interest with
complete retention of stereochemistry. Recently we have discovered a method of synthesizing essentially optically pure organoborane
intermediates. These optically active alkyl groups attached to boron can also be transferred with complete retention of optical
activity. Consequently, it is now possible to achieve by a rational synthesis the preparation of almost any optically active
compound with a chiral center, either R- or S-, in essentially 100% enantiomeric excess. 相似文献
176.
M. V. Alfimov S. P. Gromov O. B. Stanislavskii E. N. Ushakov O. A. Fedorova 《Russian Chemical Bulletin》1993,42(8):1385-1389
Styryl dyes containing a crown ether group and a heteroaromatic moiety with a sulfoalkylN-substituent (1a,b) undergo photocyclodimerization in acetonitrile in the presence of Mg(ClO4)2 to give only the typeA isomer of cyclobutane derivative (2a,b). The photochemical regio- and stereoselectivity of the cycloaddition is explained by self-organization of thetrans-isomers of the styryl dyes upon complexation with the Mg2+ cations into dimers with a fixed mutual arrangement of multiple bonds.For part 7, see ref. 1.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1449–1452, August, 1993. 相似文献
177.
Various diblocks, triblocks and a graft copolymer of butadiene with 4-vinylpyridine short blocks have been prepared. They were complexed with ZnCl2 to give ionomer-like materials. For all copolymers, the Tg of the elastomeric block (?84°C to ?91°C) was unchanged by complexation. For all diblocks and triblocks with short blocks (DP n ~ 3) the storage modulus was only slightly increased by comparison with uncomplexed materials. For the graft copolymer even with short blocks the material is less sensitive to temperature after complexation. For triblocks, when the DP n of the vinylpyridine blocks was high enough (15 units), complexes were associated in multiplets of large size and the elastomeric properties were retained up to 200°C. 相似文献
178.
2-Amino-and 2-hydrazino-5-(3 or 4-pyridyl)-1, 3, 4-oxadiazoles [IIi-k] have been prepared by racting 2-chloro derivatives with the corresponding amines or hydrazines, the 2-hydrazino (IIi-k) compounds that obtained were heated with carbon disulphide and alcoholic potassium hydroxide where 5-(3 or 4-pyridyl)-1,3,4-oxadiazolo (2,3-C)-1,2,4-triazole 5-thione (IIIa-c) were obtained, the given structures were biologically screened. 相似文献
179.
SAPO—11分子筛用i—Pr2NH导向合成及其酸性研究 总被引:3,自引:0,他引:3
以AlPO4、H3PO4、SiO2等为原料采用单一模板剂iPr2NH合成了SAPO11分子筛,利用Avrami方程等对合成过程进行了定量描述。还利用红外(IR)、程序升温脱附(TPD)、线性丁烯骨架异构反应催化活性测试等手段表征了SAPO11的酸性。结果表明,合成过程随温度有明显变化,晶化阶段的活化能远高于核化阶段的值。可用Avrami方程的参数来表征合成过程的难易程度。分子筛中存在B酸和L酸位,主要在中等强度范围,从而对线性丁烯骨架异构反应有较好的催化活性。提高分子筛中硅含量可明显增大酸位浓度,酸强度也有轻度增强。 相似文献
180.
A model has been developed to describe the chemistry which occurs in CF4 plasmas and the etching of Si both in the plasma and downstream. One very important feature of this model is that for discharge residence times which vary by more than an order of magnitude, the amount of CF4 consumed is low and relatively constant. This is because the gas-phase combination reactions between F and both CF3 and CF2 lead to the rapid reforming of CF4. The model predicts that CF2 is a major species in the gas phase and that the [F] detected as a sample point downstream is a very sensitive function of [CF2]/[F] in the discharge. Even though the calculations show that [F] in the discharge varies only slightly over the wide range of experimental conditions considered, large variations in [F] at the sample point occur because the [CF2]/[F] ratio in the discharge changes. The concentrations of C2F6 and SiF4 are predicted to within a factor of 2 over a very wide range of experimental conditions. This confirms the importance of gas-phase free radical reactions in the etching of Si. 相似文献