全文获取类型
收费全文 | 5343篇 |
免费 | 261篇 |
国内免费 | 23篇 |
专业分类
化学 | 4032篇 |
晶体学 | 51篇 |
力学 | 132篇 |
综合类 | 1篇 |
数学 | 769篇 |
物理学 | 642篇 |
出版年
2023年 | 57篇 |
2022年 | 47篇 |
2021年 | 102篇 |
2020年 | 140篇 |
2019年 | 114篇 |
2018年 | 70篇 |
2017年 | 71篇 |
2016年 | 195篇 |
2015年 | 170篇 |
2014年 | 195篇 |
2013年 | 295篇 |
2012年 | 335篇 |
2011年 | 394篇 |
2010年 | 229篇 |
2009年 | 203篇 |
2008年 | 318篇 |
2007年 | 293篇 |
2006年 | 284篇 |
2005年 | 266篇 |
2004年 | 222篇 |
2003年 | 178篇 |
2002年 | 189篇 |
2001年 | 106篇 |
2000年 | 95篇 |
1999年 | 80篇 |
1998年 | 68篇 |
1997年 | 56篇 |
1996年 | 42篇 |
1995年 | 55篇 |
1994年 | 47篇 |
1993年 | 43篇 |
1992年 | 43篇 |
1991年 | 57篇 |
1990年 | 48篇 |
1989年 | 32篇 |
1988年 | 15篇 |
1987年 | 21篇 |
1985年 | 25篇 |
1984年 | 25篇 |
1983年 | 29篇 |
1982年 | 22篇 |
1981年 | 31篇 |
1980年 | 40篇 |
1979年 | 21篇 |
1978年 | 25篇 |
1977年 | 34篇 |
1976年 | 23篇 |
1975年 | 26篇 |
1974年 | 24篇 |
1973年 | 19篇 |
排序方式: 共有5627条查询结果,搜索用时 15 毫秒
41.
The electron capture negative ion (ECNI) mass spectra of two complex mixtures of polychlorinated decanes (PCDe) and polychlorinated
dodecanes (PCDo) are presented. The number of isomers in these mixtures is still high but is drastically reduced in comparison
to technical products of chlorinated paraffins (CP), due to their fixed chain length. As a result, the mass spectra are simplified
and less complex. Different modes of negative ion formation were observed in the spectra of the PCDe and PCDo. [M+Cl]– adduct ions were the most abundant ions in the spectra of lower chlorinated molecules. Higher chlorinated isomers formed
prominently [M-Cl]– and [M-HCl]– fragments besides [M+Cl]–. Possible consequences for the determination of chlorinated paraffins by ECNI-MS that result from the variation in ion formation
are addressed.
Received: 18 August 1997 / Revised: 26 January 1998 / Accepted: 31 January 1998 相似文献
42.
The primary amino group of 3-(2-aminoethyl)-3-(4-chlorophenyl)-2,3-dihydro-1H-isoindol-1-one ( 1 ) was acylated with acetyl chloride, benzoyl chloride and phenyl acetyl chloride to form the amides 2a -c, respectively. These were cyclized in phosphorus oxychloride to give the 1-substituted-4a-(4-chlorophenyl)-4,4a-dihydropyrimido [6,1-a]isoindol-9(3H)-ones 3a-c . Heating of 1 in formic acid lead to the formation of 4a-(4-chlorophenyl)-4,4a-dihydropyrimido[6,1-a]isoindol-9(3H) -one (3d) . Heating of 1 in the presence of phosgene lead to the formation of 4a-(4-chlorophenyl)-2,3,4,4a-tetrahydropyrimido[6,1-a]isoindole-1, 9-dione (4). 相似文献
43.
Henri-Edouard Audier Marcel Fetizon Yannik Henry Thierry Prange 《Journal of mass spectrometry : JMS》1976,11(10):1047-1055
The fragmentation mechanisms of oxazole have been studied in detail on using various experimental techniques (refocusing of metastable ions, deuteration, AP measurements) and by theoretical calculations. 相似文献
44.
The temperature dependence of the 35Cl nuclear quadrupole resonance spectra of tetrachloro-o-benzoquinone (TOB) is reported. An analysis of the change in line multiplicities suggests that TOB undergoes three phase changes in going from 77 to 330 K. The transition temperatures have been determined. 相似文献
45.
Chiral carbenium ions can be attacked by arene nucleophiles with high facial diastereoselectivity (dr >/= 94/6). Benzylic cations, such as 2, were generated under acidic conditions and reacted with arenes in intra- and intermolecular Friedel-Crafts alkylation reaction. The depicted reaction 1 --> 3 represents one example for the unprecedented, highly diastereoselective intermolecular Friedel-Crafts alkylation reactions which were observed in this study. 相似文献
46.
Mohamed Boumerzoug Marcel Boudreau Peter Mascher 《Plasma Chemistry and Plasma Processing》1997,17(2):181-192
Real-time optical emission spectroscopy (OES) was used to monitor the deposition of TiN both from mixtures of tetrakis(dimethylamino)titanium
(TDMATi)-N2 and TiCl4-H2-N2 in an electron cyclotron resonance chemical vapor deposition system. The accurate control of the ratio of the emission intensities
of ionized nitrogen at 391.4 nm and molecular nitrogen at 357.7 nm (N
2
+
/N2) led to low temperature deposition of stoichiometric TiN (Ti/N ≈ 1) and very low resistivity in both cases. It was found
that high ion density plasmas are crucial for a considerable reduction of the deposition temperature while maintaining good
film quality. OES shows that the abundance of certain excited plasma species is not only dependent on the gas mixture and
the deposition parameters, such as total pressure and microwave power, but also is strongly affected by the magnetic field
configuration. The deposition rate and the film resistivity can be related to the emission intensity ratio, I(N
2
+
)/I(N2). Finally, the two processes are compared in terms of the quality of as-deposited and heat-treated films. The comparison
shows that the films obtained with TDMATi exhibit lower resistivity and are thermally more stable than with TiCl4. 相似文献
47.
José M. Bartoloméa Jesús AlcázarJ.Ignacio Andrés Marcel De BruynJavier Fernández Encarna MatesanzKristof Van Emelen 《Tetrahedron letters》2003,44(47):8545-8548
The synthesis of a series of novel analogues of the 3-substituted-2,3-dihydro-1,4-dioxino[2,3-b]pyridine core, modified in the non-aromatic ring, is described. Due to the presence of a versatile hydroxymethyl group in their structure, these novel scaffolds are attractive intermediates for the preparation of potential new therapeutic agents. 相似文献
48.
Kratzsch C Tenberken O Peters FT Weber AA Kraemer T Maurer HH 《Journal of mass spectrometry : JMS》2004,39(8):856-872
A liquid chromatographic/mass spectrometric assay with atmospheric pressure chemical ionization (LC/APCI-MS) is presented for fast and reliable screening and identification and also for precise and sensitive quantification in plasma of the 23 benzodiazepines alprazolam, bromazepam, brotizolam, camazepam, chlordiazepoxide, clobazam, clonazepam, diazepam, flunitrazepam, flurazepam, desalkylflurazepam, lorazepam, lormetazepam, medazepam, metaclazepam, midazolam, nitrazepam, nordazepam, oxazepam, prazepam, temazepam and tetrazepam, triazolam, their antagonist flumazenil and the benzodiazepine BZ1 (omega 1) receptor agonists zaleplone, zolpidem and zopiclone. It allows confirmation of the diagnosis of an overdose situation and monitoring of psychiatric patients' compliance. The analytes were isolated from plasma using liquid-liquid extraction and were separated on a Merck LiChroCART column with Superspher 60 RP Select B as the stationary phase. Gradient elution was performed using aqueous ammonium formate and acetonitrile. After screening and identification in the scan mode using the authors' LC/MS library, the analytes were quantified in the selected-ion monitoring mode. The quantification assay was fully validated. It was found to be selective proved to be linear from sub-therapeutic to over therapeutic concentrations for all analytes, except bromazepam. The corresponding reference levels the assay's accuracy and precision data for all studied substances are listed. The accuracy and precision data were within the required limits with the exception of those for bromazepam. The analytes were stable in frozen plasma for at least 1 month. The validated assay was successfully applied to several authentic plasma samples from patients treated or intoxicated with various benzodiazepines or with zaleplone, zolpidem or zopiclone. It has proven to be appropriate for the isolation, separation, screening, identification and quantification of the drugs mentioned above in plasma for clinical toxicology, e.g. in cases of poisoning, and forensic toxicology, e.g. in cases of driving under the influence of drugs. 相似文献
49.
Elke Barsties Stefan Schaible Marc-Heinrich Prosenc Ursula Rief Werner Rll Oliver Weyand Birgit Dorer Hans-Herbert Brintzinger 《Journal of organometallic chemistry》1996,520(1-2):63-68
Bis(2-N,N-dimethylamino-indenyl) zirconium dichloride, (2-(CH3)2N-C9H6)2ZrCl2, and dimethylsilyl-bridged bis(2-N,N-dimethylamino-indenyl) zirconium dichloride, (CH3)2Si(2-(CH3)2N-C9H5)2ZrCl2, were prepared by reaction of the corresponding ligand lithium salts with ZrCl4 in toluene. Diffractometric structure determinations reveal C2-symmetric complex geometries for both complexes. An increased electron density at the Zr center of the dimethylamino-substituted complexes is indicated by reduction potentials which are 0.3–0.4 V more negative than those of their unsubstituted analogs. When activated with methyl aluminoxane in toluene solution, (CH3)2Si(2-(CH3)2N-C9H5)2ZrCl2 catalyzes the polymerization of propene to polymers with a microstructure comparable with that of polymers produced with other Me2Si-bridged bis(indenyl)ZrCl2 complexes, but with a substantially increased fraction of i-propyl end groups derived from alkyl exchange between Zr-polymer and Al---Me species. 相似文献
50.
The intramolecular cyclization reactions of tri-1-hex-5-enyl Group III derivatives and of 1-hex-5-enyllithium have been investigated and it is proposed that the reactions may be depicted as internal addition across the terminal double bonds of the alkenyl species. The cyclization reaction proceeds more readily for the 1-hex-5-enyl derivatives than for any other chain length and is dependent on temperature, concentration and solvent. 1H NMR data and cryoscopic molecular weight data are presented for several diisobutyialkenyl- and diisobutylalkyl-aluminum derivatives. These data have been interpreted in terms of a direct intramolecular interaction between the metal center and the π-electron system of the olefinic site. The intramolecular cyclization reactions for the 1-hept-6-enyl, 1-oct-7-enyl- and 1-undec-10-enylaluminum derivatives also were investigated and it was found that cyclization occurred only for the 1-hept-6-enyl derivative. 相似文献