全文获取类型
收费全文 | 4056篇 |
免费 | 215篇 |
国内免费 | 409篇 |
专业分类
化学 | 1503篇 |
晶体学 | 11篇 |
力学 | 37篇 |
综合类 | 20篇 |
数学 | 2738篇 |
物理学 | 371篇 |
出版年
2024年 | 3篇 |
2023年 | 55篇 |
2022年 | 72篇 |
2021年 | 82篇 |
2020年 | 115篇 |
2019年 | 120篇 |
2018年 | 117篇 |
2017年 | 103篇 |
2016年 | 74篇 |
2015年 | 90篇 |
2014年 | 145篇 |
2013年 | 583篇 |
2012年 | 108篇 |
2011年 | 153篇 |
2010年 | 119篇 |
2009年 | 197篇 |
2008年 | 237篇 |
2007年 | 258篇 |
2006年 | 234篇 |
2005年 | 218篇 |
2004年 | 211篇 |
2003年 | 194篇 |
2002年 | 175篇 |
2001年 | 143篇 |
2000年 | 146篇 |
1999年 | 120篇 |
1998年 | 124篇 |
1997年 | 126篇 |
1996年 | 74篇 |
1995年 | 43篇 |
1994年 | 33篇 |
1993年 | 36篇 |
1992年 | 35篇 |
1991年 | 17篇 |
1990年 | 10篇 |
1989年 | 16篇 |
1988年 | 16篇 |
1987年 | 6篇 |
1986年 | 7篇 |
1985年 | 17篇 |
1984年 | 11篇 |
1983年 | 4篇 |
1982年 | 5篇 |
1981年 | 5篇 |
1980年 | 5篇 |
1978年 | 4篇 |
1977年 | 3篇 |
1976年 | 3篇 |
1974年 | 2篇 |
1973年 | 2篇 |
排序方式: 共有4680条查询结果,搜索用时 31 毫秒
91.
Hans-Detlev?GilsingEmail author Jürgen?Angerer Dietrich?Prescher 《Monatshefte für Chemie / Chemical Monthly》2005,136(5):795-801
Summary. The synthesis of an oxidative major metabolite of bis(2-ethylhexyl) phthalate is described. The target molecule and its ring-deuterated isomer were obtained via acylation of the appropriate -hydroxy benzyl ester or the corresponding carboxylate with phthalic anhydride or phthalic anhydride-d4. All transformation steps proceed with high yields. 相似文献
92.
Immobilized sulfhydryl groups were prepared by partial thiolation of NH2-glass beads. The microenvironment of the immobilized SH groups was varied by different chemical modifications of neighboring
NH2 groups. Introduction of a strong charge in the surroundings of immobilized sulfhydryls results in their dramatic stabilization
against autooxidation. This effect is due to the salting of O2 from the surface microlayer of the thiolated beads. 相似文献
93.
We have been studying the problem of heterogeneity of OH groups in zeolites HY for a long time. The heterogeneity was suggested by the shift of the IR band of OH groups restoring upon ammonia desorption and also by the fact that the band of OH groups forming hydrogen bonds was relatively broad (broader than for homogeneous acidic OH). In the present study we present another important argument for heterogeneity: the splitting of the IR band of free OH and OD groups in a zeolite of Si/Al=8.3 dealuminated by (NH4)2SiF6 treatment. Such a splitting is the best seen in low temperature spectra of OD groups. We found less acidic 3640 cm−1 (AlO)(SiO)2SiO1HAl(OSi)3 and more acidic 3625 cm−1 (SiO)3SiO1HAl(OSi)3 groups. The presence of these two kinds of hydroxyls corresponds to the presence of Si(2Al) and Si(1Al), respectively, detected in 29Si MAS NMR spectra. We also found a small amount of strongly acidic 3599 cm−1 hydroxyls interacting with extraframework Al species. 相似文献
94.
Thermal
degradation of vinylidene chloride/[4-(t-butoxycarbonyloxy)phenyl]methyl
acrylate copolymers
B. A. Howell D. A. Spears P. B. Smith 《Journal of Thermal Analysis and Calorimetry》2006,85(1):115-117
Vinylidene chloride polymers containing comonomer
units capable of consuming evolved hydrogen chloride to expose good radical-scavenging
sites might be expected to display greater thermal stability than similar
polymers containing simple alkyl acrylates as comonomer. Incorporation of
a comonomer containing the phenyl t-butyl
carbonate moiety into a vinylidene chloride polymer has the potential to afford
a polymer with pendant groups which might interact with hydrogen chloride
to expose phenolic groups. Copolymers of vinylidene chloride with [4-(t-butoxycarbonyloxy)phenyl]methyl acrylate have been
prepared, characterized, and subjected to thermal degradation. The degradation
has been characterized by thermal and spectroscopic techniques. The degradation
of vinylidene chloride/[4-(t-butoxycarbonyloxy)phenyl]methyl
acrylate copolymers is much more facile than the same process for similar
copolymers containing either [4-(isobutoxycarbonyloxy)phenyl]methyl acrylate
or methyl acrylate, a simple alkyl acrylate, as comonomer. During copolymer
degradation, [4-(t-butoxycarbonyloxy) phenylmethyl
acrylate units are apparently converted to acrylic acid units by extensive
fragmentation of the sidechain. Thus, the phenyl t-butyl
carbonate moiety does function as a labile acid-sensitive pendant group but
its decomposition in this instance leads to the generation of a phenoxybenzyl
carboxylate capable of further fragmentation. 相似文献
95.
Grohmann K. Mitchell D. J. Himmel M. E. Dale B. E. Schroeder H. A. 《Applied biochemistry and biotechnology》1989,(1):45-61
Xylan backbones in native plant cell walls are extensively acety-lated. Previously, no direct investigations as to their role
in cellulolytic enzyme resistance have been done, though indirect results point to their importance. An in vitro deesterification
of aspen wood and wheat straw has been completed using hydroxylamine solutions. Yields of 90% acetyl ester removal for both
materials have been accomplished, with little disruption of other fractions (i.e., lignin). Apparently, as the xylan becomes
increasingly deacetylated, it becomes 5–7 times more digestible. This renders the cellulose fraction more accessible, and
2–3 times more digestible. This effect levels off near an acetyl removal of 75%, where other resistances become limiting. 相似文献
96.
The two independent elements of the second-order nonlinear optical susceptibility tensor of a range of contact poled, donor–acceptor substitued side-chain polymers are reported. The susceptibilities were measured by second harmonic generation from thin films, typically less than 0.5 μm thick, at a fundamental wavelength of 1064 nm. The largest value was χ = 2.64 pm/V which is three times greater than the χ value of KDP and was measured in a nitrobenzylidene side chain, polyhydroxystyrene polymer with an eleven unit alkyl chain spacer attaching the side group to the backbone. Typical susceptibility values obtained were χ~0.3 pm/V and X(2)33~1 pm/V. The coherence lengths of the materials, which lay in the range 4–12 μm, were measured at 1064 nm by the maker fringe technique using thick, wedge-shaped samples. 相似文献
97.
Bayó N Jiménez JC Rivas L Nicolás E Albericio F 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(5):1096-1103
An optimized solid-phase strategy for the preparation of the cyclic lipononadepsipeptide [N-Mst(L-Ser1), D-Ser4, L-Thr6, L-Asp8, L-Thr9]syringotoxin is reported. The strategy is based on the use of a mild orthogonal protection scheme and the incorporation of the nonproteinogenic amino acid (Z)-Dhb into the peptide chain as the dipeptide Fmoc-Thr(tBu)-(Z)-Dhb-OH. The didehydrodipeptide was synthesized by a water-soluble carbodiimide-induced beta-elimination of a protected dipeptide containing a residue of Thr with its free hydroxy side chain unprotected. 相似文献
98.
A. V. Kurkin V. V. Nesterov A. V. Karchava M. A. Yurovskaya 《Chemistry of Heterocyclic Compounds》2003,39(11):1466-1477
A new approach has been proposed to the synthesis of indole derivatives containing a chiral substituent at the nitrogen atom, comprizing Fischer indolization of phenylhydrazines with a chiral substituent at the -nitrogen atom. The initial hydrazines were obtained by the alkylation (Mitsunobu reaction applying optically active esters of lactic acid) of anilines containing an electron-accepting substituent at the amino group. Subsequent removal of the activating acceptor grouping was realized by nitrosation of the chiral secondary aniline followed by reduction of the corresponding N-nitroso compound. 相似文献
99.
V. B. Murachev A. L. Nesmelov V. S. Byrikhin E. A. Ezhova A. V. Orlinkov L. S. Akhrem M. E. Vol'pin 《Russian Chemical Bulletin》1996,45(5):1115-1119
Polymerization of isobutylene inn-hexane at -78 °C in the presence of the complex of benzoyl chloride with AIBr3 (1 : 2) was investigated. The results were compared to those obtained previously for the polymerization of this monomer induced by the complex of acetyl bromide with AlBr3. Both complexes initiate the polymerization only by acyl cations. The number average molecular weight (M
n
) of the polymer linearly increases as the degree of isobutylene conversion increases. The polymerization restarts after repeated addition of the monomer, andM
n
continues to increase linearly. The efficiency of the initiaton by the benzoyl chloride complex does not exceed 6.2 %; the reaction has the second order with respect to the initiator in the case of PhCOCI · A12Br6; and the chain-propagation rate constant is 13.9 L mol–1 s t. The use of PhCOCI Al2Br6 as the initator of the polymerization of isobutylene allows one to prepare macromolecules with very low contents of the terminal C=C double bonds and with narrow molecular weight distributions. Unlike the MeCOBr·AlBr3 complex, PhCOCl · AlBr3 does not initiate polymerization of isobutylene.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 1175–1179, May, 1996. 相似文献
100.
Ken-ichi Sato Shoji Akai Akira Yoshitomo Yoshimitsu Takai 《Tetrahedron letters》2004,45(44):8199-8201
The merits of an indirect protecting method for hydroxyl groups using allyl groups via allyloxycarbonyl groups in the synthesis of antennary β-d-mannopyranosyl disaccharides from β-d-galactopyranosyl disaccharides were studied. Regioselective allyloxycarbonylation and conversion reactions involving simultaneous double SN2 nucleophilic substitution at C-2′ and C-4′ of benzyl O-[β-d-galactopyranosyl]-(1-4)-3,6-di-O-benzyl-2-deoxy-2-N-phthalimido-β-d-glucopyranoside were examined for comparison with the direct allylation method. The required β-d-mannopyranosyl disaccharide having proper protecting groups was obtained using this indirect method in 52% yield. In contrast, the reported direct allylation method using methyl O-(β-d-galactopyranosyl) disaccharide gave the corresponding β-d-mannopyranosyl disaccharide in only 7.5% yield. 相似文献