全文获取类型
收费全文 | 2394篇 |
免费 | 434篇 |
国内免费 | 66篇 |
专业分类
化学 | 2675篇 |
晶体学 | 11篇 |
力学 | 7篇 |
综合类 | 5篇 |
数学 | 42篇 |
物理学 | 154篇 |
出版年
2023年 | 26篇 |
2022年 | 94篇 |
2021年 | 120篇 |
2020年 | 147篇 |
2019年 | 102篇 |
2018年 | 74篇 |
2017年 | 60篇 |
2016年 | 149篇 |
2015年 | 148篇 |
2014年 | 167篇 |
2013年 | 217篇 |
2012年 | 164篇 |
2011年 | 164篇 |
2010年 | 134篇 |
2009年 | 145篇 |
2008年 | 147篇 |
2007年 | 133篇 |
2006年 | 127篇 |
2005年 | 103篇 |
2004年 | 75篇 |
2003年 | 88篇 |
2002年 | 29篇 |
2001年 | 24篇 |
2000年 | 36篇 |
1999年 | 28篇 |
1998年 | 36篇 |
1997年 | 25篇 |
1996年 | 16篇 |
1995年 | 22篇 |
1994年 | 17篇 |
1993年 | 8篇 |
1992年 | 8篇 |
1991年 | 6篇 |
1990年 | 1篇 |
1989年 | 8篇 |
1988年 | 10篇 |
1987年 | 7篇 |
1986年 | 5篇 |
1985年 | 10篇 |
1984年 | 5篇 |
1983年 | 1篇 |
1982年 | 1篇 |
1981年 | 2篇 |
1980年 | 1篇 |
1976年 | 1篇 |
1974年 | 1篇 |
1972年 | 1篇 |
1970年 | 1篇 |
排序方式: 共有2894条查询结果,搜索用时 31 毫秒
21.
Breviones A∼E (1∼5), allelopathic agents isolated from Penicillium brevicompactum Dierckx, are structurally unique pentacyclic or hexacyclic diterpenoid derivatives. The first synthesis of brevione B (2) was achieved by employing the double SN2′-type tandem reaction as a key step. 相似文献
22.
Benedetti M Tamasi G Cini R Natile G 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(24):6122-6132
The use of a sterically hindered diamine ligand (Me(4)DACH) has allowed for the first time, the isolation and characterization, both in the solid state (X-ray crystallography) and in solution (circular dichroism), of pure DeltaHT rotamers of [Pt(Me(4)dach)(5'-GMP)(2)] (compounds 1 and 2 for R,R and S,S configurations of the Me(4)DACH ligand, respectively). Comparison of the CD spectra obtained for each rotamer, which differ only in the chirality of the Me(4)DACH ligand (R,R or S,S) or in the chirality of the HT conformation (Delta or Lambda), allowed us to conclude that, in the 200-350 nm range, the contributions to the overall CD spectrum that stem from diamine chirality and diamine-induced chirality of platinum d--d transitions or from sugar chirality are negligible relative to the exciton chiral coupling that occurs for pi-pi* transitions of the cis guanines. Accurate molecular structures of 1.10 D(2)O and 2.14 D(2)O (conventional crystallographic agreement indexes R(1) convergent to 2.07 % and 2.18 %, respectively) revealed that the crystallized rotamers have a DeltaHT conformation that is in agreement with all previously reported X-ray structures of [Pt(diamine)(nucleos(t)ide)(2)] complexes. This conformation allows the 5'-phosphate to be located in proximity to the Me(4)DACH ligand so that (P)O...HC(N) hydrogen-bond interactions exists in both complexes. For both structures, the canting of the guanine planes on the coordination plane is right-handed (R; canting angle (Phi) of 80.9 degrees and 73.2 degrees, respectively); this indicates that the canting direction is driven by the HT conformation chirality (Delta for both compounds) and not by the chirality of the carrier ligand (different for the two compounds). Density functional theory analysis of the conformational space as a function of Phi indicated a good agreement between the computed and experimental structures. The increase in energy for Phi values below 65 degrees and 55 degrees (for 1 and 2, respectively) is mainly due to the short intramolecular contacts between C(8)H and the cis N-Me groups on the same side of the platinum coordination plane. 相似文献
23.
M. Frederick Hawthorne 《Angewandte Chemie (International ed. in English)》1993,32(7):950-984
A therapeutic method that selectively destroys malignant cells in the presence of normal cells is a highly valued goal of oncologists and the possible salvation of cancer patients afflicted with some incurable forms of the disease. Selective cell destruction is, in principle, possible with a binary therapeutic strategy based upon the neutron capture reaction observed with the 10B nucleus and a neutron of low kinetic energy (thermal neutron). This nuclear fission reaction produces both 4He and 7Li+ nuclei along with about 2.4 MeV of kinetic energy and weak γ-radiation. Since the energetic and cytotoxic product ions travel only about one cell diameter in tissue one may specify the cell type to be destroyed by placing innocent 10B nuclei on or within only the doomed cells. This article describes the current status of chemical research aimed at the eventual adoption of this therapeutic method (boron neutron capture therapy or BNCT). The multidisciplinary nature of this research effort involves chemistry, biology, nuclear physics, medicine, and related specialties. Methods devised for bringing 10B nuclei to tumor cells in therapeutic amounts are correlated with the structure of a generalized cell and the various cellular compartments available for boron localization. The synthesis methods employed for the creation of boron-containing biomolecules and drugs are presented along with representative data concerning their efficacy in tumor localization. The outlook for BNCT is especially bright at this time because of rapid developments in the fields of bioorganometallic chemistry, microbiology, immunology, and nuclear science, to name but a few. Very effective boron delivery vehicles have been demonstrated, and through the interaction of chemistry and biology these species are undergoing further improvement and evaluation of their suitability for BNCT. 相似文献
24.
Yu. V. Tomilov I. V. Kostyuchenko G. P. Okonnishnikova I. P. Klimenko E. V. Shulishov 《Russian Chemical Bulletin》2006,55(11):2008-2012
A new way of generating cyclopropyl radicals in the base-catalyzed decomposition of N-cyclopropyl-N-nitrosourea in the presence of organic reducing agents (1-phenylpyrazolidin-3-one and 4-methoxyphenol) was developed. The
cyclopropyl radical generated under these conditions can not only abstract a proton from the substrate to give cyclopropane
but also form C-C or C-Br bonds in reactions with aromatic substrates or polybromomethanes.
Dedicated to Academician O. M. Nefedov on the occasion of his 75th birthday.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 1934–1938, November, 2006. 相似文献
25.
Edith Gößnitzer Ales Krbavcic Winfried Wendelin Marija Krbavcic 《Monatshefte für Chemie / Chemical Monthly》2002,133(9):1177-1185
Summary. Novel N-(3-oxobutyl)-hydroxy- and acetoxypyrido[2,3-d]pyridazinones were synthesized and tested in vivo for their sedative and anticonvulsant activity. The Michael-type reaction of quinolinic acid hydrazide and methyl vinyl ketone afforded a mixture of two isomers, 5-hydroxy-N
7-(3-oxobutyl)-pyrido[2,3-d]pyridazin-8(7H)-one and 8-hydroxy-N
6-(3-oxobutyl)-pyrido[2,3,-d]pyridazin-5-(6H)-one, in a ratio of 2:1 which were separated by crystallization. Subsequent acetylation of both isomers yielded the corresponding
5- and 8-acetoxy compounds. The structures of the compounds were proven and completely assigned on the basis of 1H, 13C, 15N NMR, and 1D NOE difference spectra as well as 2D C,H-correlation experiments. Preliminary pharmacological tests showed low
acute toxicity with a LD
50 > 1000 mg/kg in the mouse and sedative activity for the title compounds. 5-Acetoxy-N
7- (3-oxobutyl)-pyrido[2,3-d]pyridazin-8(7H)-one displayed a borderline anticonvulsant activity in the metrazole test model.
Corresponding author. E-mail: edith.goessnitzer@uni-graz.at
Received March 20, 2002; accepted April 3, 2002 相似文献
26.
Jolanta Obniska Krzysztof Kaminski Agnieszka Dzierzawska-Majewska 《Journal of fluorine chemistry》2006,127(3):417-425
A series of N-phenyl- and N-benzyl-2-azaspiro[4.4]nonane- and [4.5]decane-1,3-diones containing a fluoro or trifluoromethyl substituents at the aryl ring was synthesized and tested for their anticonvulsant activity in the maximal electroshock (MES) and subcutaneous metrazole (sc.Met) tests. Among them, the most active were N-benzyl derivatives with fluoro and trifluoromethyl substituents especially at position-2 of the aryl moiety. The introduction of the phenyl ring at the imide nitrogen atom resulted in less active compounds. The results obtained showed that incorporation of fluoro or trifluoromethyl substituents increased the anticonvulsant activity in comparison to respective chloro, methoxy or methyl analogues. Crystallographically obtained conformation for one active and two inactive derivatives with trifluoromethyl substituents at position-2 or -3 of phenyl ring were initially used for molecular electrostatic potentials (MEP) calculation. The MEP distribution at carbonyl oxygen atoms was different for active and inactive molecules. 相似文献
27.
28.
Summary A small cartridge containing a drying agent is inserted between a solid phase extraction (SPE) column and a gas chromatograph (GC) to enable the introduction of water-free desorption solvent into the GC in on-line liquid chromatography (LC)-type enrichment of trace-level analytes from water samples. Some characteristics of the drying agents, such as their capacity to retain water and their re-usability after heating, have been tested. Possible interactions of the drying agent with the analytes, e.g., irreversible adsorption or catalyzed degradation, have been checked for a wide range of alkanes, alkylbenzenes chlorobenzenes, chlorophenols and phthalate esters. Using the on-line SPE-GC system with flame ionization detection (FID) and spiked samples containing different levels of the test compounds, the repeatability was shown to be satisfactory (6–17%). For 10 mL samples, the detection limits were lower than 0.1 g/L. The on-line SPE-GC-FID system here presented can be used for the repeated analysis of water samples without exchange of the dyring cartridge. The technique is applied to the analysis of tap water. 相似文献
29.
Gavernet Luciana Saraví Cisneros Hebe Saraví Bruno-Blanch Luis E. Estiú Gguillerminal L. 《Theoretical chemistry accounts》2003,110(6):434-440
A theoretical study of the mechanisms associated with the synthesis of anticonvulsant symmetric N,N-substituted sulfamides is presented. Two possible synthetic routes are compared, which mainly differ in the use of pyridine as a nucleophilic agent in the reaction mechanism. Geometry optimization techniques and transition-state detection at the B3LYP/6-31G** level, modeling the solvent by means of an isodensity polarizable continuum approach, allow the most suitable method for the experimental process to be discerned.From the Proceedings of the 28th Congreso de Químicos Teóricos de Expresión Latina (QUITEL 2002) 相似文献
30.
In the work described here, a biosensor was developed for the determination of sulfite in food. Malva vulgaris tissue homogenate containing sulfite oxidase enzyme was used as the biological material. M. vulgaris tissue homogenate was crosslinked with gelatin using glutaraldehyde and fixed on a pretreated Teflon membrane. Sulfite was enzymatically converted to sulfate in the presence of the dissolved oxygen, which was monitored amperometrically. Sulfite determination was carried out by standard curves, which were obtained by the measurement of consumed oxygen level related to sulfite concentration. Several operational parameters had been investigated: the amounts of plant tissue homogenate and gelatin, percentage of glutaraldehyde, optimum pH and temperature. Also, some characterization studies were done. There was linearity in the range between 0.2 and 1.8 mM at 35 °C and pH 7.5. The results of real sample analysis obtained with the biosensor agreed well with the enzymatic reference method using spectrophotometric detection. 相似文献