全文获取类型
收费全文 | 5146篇 |
免费 | 196篇 |
国内免费 | 35篇 |
专业分类
化学 | 3339篇 |
晶体学 | 17篇 |
力学 | 148篇 |
数学 | 882篇 |
物理学 | 991篇 |
出版年
2023年 | 43篇 |
2022年 | 60篇 |
2021年 | 97篇 |
2020年 | 115篇 |
2019年 | 126篇 |
2018年 | 91篇 |
2017年 | 96篇 |
2016年 | 182篇 |
2015年 | 107篇 |
2014年 | 153篇 |
2013年 | 266篇 |
2012年 | 331篇 |
2011年 | 409篇 |
2010年 | 243篇 |
2009年 | 175篇 |
2008年 | 301篇 |
2007年 | 370篇 |
2006年 | 304篇 |
2005年 | 235篇 |
2004年 | 213篇 |
2003年 | 173篇 |
2002年 | 142篇 |
2001年 | 61篇 |
2000年 | 62篇 |
1999年 | 71篇 |
1998年 | 50篇 |
1997年 | 61篇 |
1996年 | 56篇 |
1995年 | 40篇 |
1994年 | 32篇 |
1993年 | 38篇 |
1992年 | 46篇 |
1991年 | 23篇 |
1990年 | 19篇 |
1989年 | 30篇 |
1988年 | 26篇 |
1987年 | 17篇 |
1986年 | 20篇 |
1985年 | 34篇 |
1984年 | 28篇 |
1983年 | 15篇 |
1982年 | 24篇 |
1981年 | 36篇 |
1980年 | 32篇 |
1979年 | 21篇 |
1978年 | 33篇 |
1977年 | 22篇 |
1976年 | 23篇 |
1975年 | 14篇 |
1974年 | 19篇 |
排序方式: 共有5377条查询结果,搜索用时 15 毫秒
101.
Kaval N Ermolat'ev D Appukkuttan P Dehaen W Kappe CO Van der Eycken E 《Journal of combinatorial chemistry》2005,7(3):490-502
The "click chemistry" approach has been explored on the 2-(1H)-pyrazinone scaffold for the generation of pharmacologically interesting heterocyclic moieties. Huisgen 1,3-dipolar cycloaddition has been evaluated as the key step for the construction of the 1,2,3-triazole ring at the C-3 position of 2-(1H)-pyrazinones. Two different pathways have been successfully evaluated: (1) via C-C or C-O linkage of the acetylenic part to the C-3 position of the 2-(1H)-pyrazinone scaffold or (2) via azide introduction in the C-3 position. The subsequent application of "click chemistry" resulted in the formation of hitherto unknown skeletons. Microwave irradiation has successfully been applied in different steps of the sequence. 相似文献
102.
Ruifeng Liu Paula R. Moody Alex S. Vanburen Jeffrey A. Clark Joel A. Krauser Dennis R. Tate 《Vibrational Spectroscopy》1996,10(2):325-329
Results of ab initio and density functional theory calculations on the structure and vibrational frequencies of hypophosphite anion indicate earlier experimental assignments of the fundamental vibrational modes are correct while the recent reassignments of several modes proposed by Bickley et al. are inconsistent with the calculated results. 相似文献
103.
Lee LF Adronov A Schaller RD Fréchet JM Saykally RJ 《Journal of the American Chemical Society》2003,125(2):536-540
Near-field scanning optical microscopy (NSOM) has been used to investigate the photophysical characteristics of first- to fourth-generation (G1 to G4) light-harvesting dendrimer thin films containing coumarin-343 and coumarin-2 as the core and peripheral chromophores, respectively. Thin film photoluminescence (PL) spectra exhibit a significant red shift in the lower generations (G1, G2, and G3) as compared to their respective solution PL spectra, implying the formation of excimers. Spatially resolved PL NSOM images exhibit pronounced nanoscopic domains in G1, which become more homogeneous in higher generations due to site-isolation of the core chromophore. G4 exhibits complete site-isolation for these light-harvesting dendrimer films. 相似文献
104.
Wang T Frederick KK Igumenova TI Wand AJ Zuiderweg ER 《Journal of the American Chemical Society》2005,127(3):828-829
The fast dynamics of protein backbones are often investigated by nuclear magnetic relaxation experiments that report on the degree of spatial restriction of the amide bond vector. By comparing calmodulin in the peptide-bound and peptide-free states with these classical methods, we observe little difference in the dynamics of the polypeptide main chain (average order parameter decrease of 0.01 unit upon binding). However, when using NMR methods that monitor the mobility of the CO-Calpha bond vector, we reveal a significant reduction of dynamics of the protein main chain (average order parameter decrease of 0.048 units). Previous investigations have suggested that the side-chain dynamics is reduced by an average of 0.07 order parameter units upon ligand binding (Lee, A. L.; Kinnear, S. A.; Wand, A. J. Nat. Struct. Biol. 2000, 7, 72-77). The current findings suggest that the change of the CO-Calpha bond vector dynamics is intermediate between the changes in NH and side-chain dynamics and report a previously undetected loss of main-chain entropy. Weak site-to-site correlations between the different motional indicators are also observed. 相似文献
105.
Erik Larsson 《Fresenius' Journal of Analytical Chemistry》1930,79(5-6):170-175
Zusammenfassung Auf Grund der Dissoziatio nskonstanten der Thioglykolsäure,- und-Thiomilchsäure,-Mercaptoisobuttersäure,-Thiomalamidsäure und Thioäpfelsäure wurde gezeigt, dass von diesen Säuren nur die-Mercaptoisobuttersäure und Thioäpfelsäure gut mit Phenolphthalein alkalimetrisch titriert werden können, aber auch nur dann, wenn man viel Indikator benutzt. Bei den anderen Säuren hat man Indikatoren mit saurerem Umschlag zu wählen. Für die ersten drei Säuren dürften Neutralrot und Phenolrot geeignete Indikatoren sein. Dies wird auch bei der Thioglykolsäure experimentell erwiesen. Für die alkalimetrische Titration von-Thiomalamidsäure soll man Bromthymolblau als Indikator verwenden. 相似文献
106.
The aim of this work was the preparation of enantiomerically pure bis(pinene-bipyridine) ligands containing the ferrocenyl moiety. Several such ligands (1-3) were synthesized and completely characterized. These molecules can be diastereoselectively deprotonated at the acidic methylene group of the pinene moiety using a strong and sterically hindered base such as LDA. Subsequent reaction of the formed anion with alkyl halides yield the family of C(2)-symmetric enantiopure compounds (1a-c). Copper(I), silver(I), or zinc(II) complexes with several ligands (C1-C8) were prepared and structurally characterized in the solid state and in solution. Self-assembled helical species are formed in several cases. It became evident that the chiral groups present in the ligand do not completely determined the helical configuration of the assemblages. Diastereoselectivity is thus not complete with this type of ligands, contrary to other, similar ligands studied before. 相似文献
107.
An Assay for the Quantitation of Photofrin in Tissues and Fluids 总被引:1,自引:0,他引:1
David A. Bellnier William R. Greco John C. Parsons Allan R. Oseroff Alex Kuebler Thomas J. Dougherty 《Photochemistry and photobiology》1997,66(2):237-244
A method for determining the concentration of Photofrin in tissues and biological fluids was developed. The procedure is based on the dissolution of biological material with Solvable a commercially available tissue so-lubilizer, followed by porphyrin-specific fluorescence detection and measurement. It was found necessary to use a quadratic standard curve for the estimation of unknown Photofrin concentrations. While this method is limited to compounds that are stable in strong base, it has the advantages of being sensitive, rapid and low cost . 相似文献
108.
Alex B. Scholten Jan W. de Haan Hans-Gerd Janssen Leo J. M. van de Ven Carel A. Cramers 《Journal of separation science》1997,20(1):17-23
Retention gape deactivated with Silicone OV-1701-OH show good chromatographic performance and remarkable stability against water induced stationary phase degradrdation. In an attempt to better understand the findamentals off the deactivation process using silanol terminated polysiloxanes, a fumed silica was deactivated with Silicon OV-1701-OH. In contrast to fused silic capillaries, fumed silica (Aerosil A-200) can be studied by 29Si cross-polarization magic-angle-spinning (CPMAS) NMR, thus serving as a model substrate for fused silica. Retention data from inverse gas chromatography at infinite dilurion and 29Si CP MAS NMR data of five Aerosil phases, differing in residual silanol surface concentration, are correlated with the aim of validating this approach for stationary phase characterization. A comparatively detailed model of the deactivating polymer layer that explains the observed absorption activities is deduced. Surface silanols are shown to play a key role in the polymer layer, the structure of which is of primary importance for the absorption behavior after deactivation. Contrary to common belief, the absolute silanol surface concentration after deativation is only of secondary importance for the overall absorption activity. High silanol surface concentrations enhance degradation of the polysiloxane chains into small cyclic fragments as well as subsequent absorption and immobolization to the silica substrate surface. The mobility of linear polysiloxane chains in the kHz regime (as determined bby NMR cross-polarization dynamics) appears to determine the extent which the residual silanols are accessible for analytes. It is therefore anticipated that there is an optimum silanol surface concentration of fused silica surfaces to be deactivated with silanol terminated polysiloxanes; it should be lazrge enough to adsord polymer fragments, but not large to avoid excessive residual silanol activity. 相似文献
109.
Deering AL Van Lue SM Kandel SA 《Langmuir : the ACS journal of surfaces and colloids》2005,21(23):10260-10263
Scanning tunneling microscopy was used to characterize self-assembled monolayers (SAMs) of octanethiol on Au(111), created using vapor deposition at elevated temperatures and ambient pressure. Monolayers contained large, close-packed ( radical3 x radical3)R30 degrees domains with sizes considerably larger than those typically formed from conventional solution-phase preparation and with crystallographically straight domain boundaries. New striped surface phases were also observed, including a 13 x radical3 phase with a density that was 69% of the close-packed density; these striped phases appeared topographically higher in STM images than close-packed monolayers. 相似文献
110.
Voinov MA Polienko JF Schanding T Bobko AA Khramtsov VV Gatilov YV Rybalova TV Smirnov AI Grigor'ev IA 《The Journal of organic chemistry》2005,70(24):9702-9711
[reaction: see text] An approach to the synthesis of new imidazoline nitroxides bearing an N',N'-disubstituted amidine group is reported. The approach is based on the alkylation of diamagnetic 4-R-amino-1,2,2,5,5-pentamethyl-3-imidazolines with bromoacetic acid ethyl ester; the products of alkylation are further oxidized to the corresponding nitroxides. The approach allows a variety of functional groups to be introduced into the nitroxide molecule structure. Alkylation with bromoacetic acid ethyl ester was found to proceed with high regioselectivity and afford the products of exo-alkylation. The regiochemical assignment is made on the basis of 13C NMR spectra and confirmed by X-ray diffraction study. All of the nitroxides synthesized here were shown to have pH-dependent EPR spectra with pKa ranging from 3.5 to 6.2. For nitroxides 13 bearing the carboxylic group remote to the nitroxide moiety, the changes in isotropic magnetic parameters of EPR spectra due to reversible deprotonation of the carboxylic group were found to be small. For these nitroxides, we demonstrate an alternative approach for pKa determination that is based on measuring the peak-to-peak line width of the EPR spectrum in the presence of the paramagnetic broadening agent potassium ferricyanide. The partition coefficients of nitroxides in octanol/H2O and octanol/phosphate buffer solution mixtures were measured to reveal a range of their lipophilicities. 相似文献