全文获取类型
收费全文 | 6895篇 |
免费 | 1022篇 |
国内免费 | 575篇 |
专业分类
化学 | 4848篇 |
晶体学 | 32篇 |
力学 | 371篇 |
综合类 | 23篇 |
数学 | 800篇 |
物理学 | 2418篇 |
出版年
2024年 | 22篇 |
2023年 | 154篇 |
2022年 | 219篇 |
2021年 | 276篇 |
2020年 | 286篇 |
2019年 | 247篇 |
2018年 | 223篇 |
2017年 | 182篇 |
2016年 | 294篇 |
2015年 | 288篇 |
2014年 | 381篇 |
2013年 | 466篇 |
2012年 | 607篇 |
2011年 | 622篇 |
2010年 | 417篇 |
2009年 | 354篇 |
2008年 | 431篇 |
2007年 | 378篇 |
2006年 | 353篇 |
2005年 | 272篇 |
2004年 | 203篇 |
2003年 | 161篇 |
2002年 | 134篇 |
2001年 | 136篇 |
2000年 | 126篇 |
1999年 | 137篇 |
1998年 | 110篇 |
1997年 | 97篇 |
1996年 | 126篇 |
1995年 | 106篇 |
1994年 | 73篇 |
1993年 | 66篇 |
1992年 | 71篇 |
1991年 | 61篇 |
1990年 | 75篇 |
1989年 | 56篇 |
1988年 | 34篇 |
1987年 | 29篇 |
1986年 | 24篇 |
1985年 | 19篇 |
1984年 | 17篇 |
1983年 | 16篇 |
1982年 | 15篇 |
1981年 | 10篇 |
1979年 | 20篇 |
1978年 | 15篇 |
1977年 | 14篇 |
1976年 | 10篇 |
1975年 | 13篇 |
1973年 | 13篇 |
排序方式: 共有8492条查询结果,搜索用时 15 毫秒
161.
The time-resolved orientational anisotropies of the OD hydroxyl stretch of dilute HOD in H(2)O confined on a nanometer length scale in sodium bis(2-ethylhexyl) sulfosuccinate (AOT) reverse micelles are studied using ultrafast infrared polarization and spectrally resolved pump-probe spectroscopy, and the results are compared to the same experiments on bulk water. The orientational anisotropy data for three water nanopool sizes (4.0, 2.4, and 1.7 nm) can be fitted well with biexponential decays. The biexponential decays are analyzed using a wobbling-in-a-cone model that involves fast orientational diffusion within a cone followed by slower, full orientational relaxation. The data provide the cone angles, the diffusion constants for motion within the cones, and the final diffusion constants as a function of the nanopool size. The two processes can be interpreted as a local angular fluctuation of the OD and a global hydrogen bond network rearrangement process. The trend in the relative amplitudes of the long and short exponential decays suggest an increasing rigidity as the nanopool size decreases. The trend in the long decay constants indicates a longer hydrogen bond network rearrangement time with decreasing reverse micelle size. The anisotropy measurements for the reverse micelles studied extrapolate to approximately 0.33 rather than the ideal value of 0.4, suggesting the presence of an initial inertial component in the anisotropy decay that is too fast to resolve. The very fast decay component is consistent with initial inertial orientational motion that is seen in published molecular-dynamics simulations of water in AOT reverse micelles. The angle over which the inertial orientational motion occurs is determined. The results are in semiquantitative agreement with the molecular-dynamics simulations. 相似文献
162.
Weawkamol Leelapornpisit Minh‐Tan Ton‐That Florence Perrin‐Sarazin Kenneth C. Cole Johanne Denault Benoit Simard 《Journal of Polymer Science.Polymer Physics》2005,43(18):2445-2453
The effect of different concentrations of single‐walled carbon nanotubes (SWNTs) on the nonisothermal crystallization kinetics, morphology, and mechanical properties of polypropylene (PP) matrix composites obtained by melt compounding was investigated by means of X‐ray diffraction, differential scanning calorimetry, optical and scanning electron microscopy, and dynamic mechanical thermal analysis. Microscopy showed well‐dispersed nanotube ropes together with small and large aggregates. The modulus was found to increase by about 75% at a level of 0.5 wt % nanotubes. The SWNTs displayed a clear nucleating effect on the PP crystallization, favoring the α crystalline form rather than the β form. The crystallization kinetics analysis showed a significant increase in activation energy on incorporating nanotubes. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 2445–2453, 2005 相似文献
163.
Two new cyclopeptides, named arenariphilin A ( 1 ) and arenariphilin B ( 2 ), were isolated from the whole plants of Arenaria oreophila. Their structures were determined as cyclo‐(Thr‐Gly) ( 1 ) and cyclo‐(Ser1‐Gly ‐Ser2‐Ile ‐Phe1‐Phe2) ( 2 ) on the basis of spectral data, especially by 2D‐NMR. 相似文献
164.
Tan B Dozier A Lehmler HJ Knutson BL Rankin SE 《Langmuir : the ACS journal of surfaces and colloids》2004,20(17):6981-6984
Mesoporous silica materials with pore structures such as 2D hexagonal close packed, bicontinuous cubic, lamellar, sponge, wormhole-like, and rectangular have been made by using surfactant templating sol-gel processes. However, there are still some "intermediate" phases, in particular mesh phases, that are formed by surfactants but which have not been made into analogous silica pore structures. Here, we describe the one-step synthesis of mesoporous silica with a mesh phase pore structure. The cationic fluorinated surfactant 1,1,2,2-tetrahydroperfluorodecylpyridinium chloride (HFDePC) is used as the template. Like many fluorinated surfactants, HFDePC forms intermediate phases in water (including a mesh phase) over a wider range of compositions than do hydrocarbon surfactants. The materials produced by this technique are novel elongated particles in which the layers of the mesh phase are oriented orthogonal to the main axis of the particles. 相似文献
165.
The intermolecular coupling of unactivated alkenes to a range of heterocycles using a Rh(I) catalyst was investigated. A variety of functional groups were incorporated into the alkene, including esters, nitriles, acetals, and phthalimide. Furthermore, the heterocycle tolerated substitution with both electron-rich and electron-deficient groups. The intermolecular coupling became possible after it was discovered that weak acids dramatically increase the rate of both the inter- and intramolecular reactions. An extensive optimization of additives was performed, and HCl.PCy(3) (Cy = cyclohexyl) and HCl.P-t-Bu(2)Et were in general found to be the best additives for the reaction. 相似文献
166.
Systematic studies were performed on SnCl2-mediated carbonyl allylation reaction between aldehydes and allyl halides in fully aqueous media. Totally three valuable reaction systems were discovered, which were SnCl2/CuCl2, SnCl2/TiCl3, and SnCl2/PdCl2. They all provided good to excellent yields in the allylation of aliphatic and aromatic aldehydes under very mild and convenient conditions. SnCl2, by itself, was also found to be effective for the allylation reaction when allyl bromide was employed. However, the SnCl2-only reaction could only tolerate very small amount of water as the solvent. The SnCl2/CuCl2, SnCl2/TiCl3, and SnCl2/PdCl2-mediated reactions exhibited good regioselectivity favoring the γ-adduct when cinnamyl halides were employed as the allylation reagent. The same reactions with cinnamyl halides also showed good diastereoselectivity favoring the anti-product. Mechanistic studies using proton NMR techniques suggested that the additive (i.e., CuCl2, TiCl3, PdCl2) could accelerate the formation of allyltin intermediate, but this step was shown not to be the most important for the allylation. Thus we proposed that the Lewis acid catalysis effect exerted by the additive was the main reason for the observed reactivity enhancement. 相似文献
167.
Analysis of rabbit tear proteins by high-pressure liquid chromatography/electrospray ionization mass spectrometry 总被引:4,自引:0,他引:4
Zhou L Beuerman RW Barathi A Tan D 《Rapid communications in mass spectrometry : RCM》2003,17(5):401-412
The aim of this study was to develop a fast and reliable analytical procedure for the display of the protein components of tears that can be used to differentiate the status of the ocular surface. Using this new procedure, we analyzed the tear protein components following a corneal wound in the rabbit. Calibrated 10-microL glass, fire-polished capillary micropipettes were used to collect tears from New Zealand White rabbits prior to and daily for 9 days following a unilateral 6-mm diameter centrally placed anterior keratectomy. Tear proteins were eluted by a reversed-phase high-performance liquid chromatography (RP-HPLC) column and the tear protein profile was monitored by electrospray ionization (ESI) mass spectrometry positive total ion current (TIC) chromatography. Tear proteins were reliably separated into 17 peaks, each of which contained one or a number of protein components. The molecular weight of each protein component was determined by on-line ESI. Major tear protein components, lactoferrin, lysozyme (minimally detectable in rabbit tears), albumin, lipocalin, lipophilin and beta2-microglobulin, were tentatively identified by this method. Based on the mass spectrometric data, beta2-microglobulin was found to be glycosylated with N-acetylhexosamine. ESI-positive TIC chromatograms and mass spectra revealed comparative differences in the tear protein spectra after corneal wounding. One day after wounding, rabbit lysozyme with a molecular weight of 14,717 Da was found to be 8-fold higher in the tears of wounded eyes when compared with tears from unwounded eyes. It dropped back to normal 3 days after wounding. The expression of an unidentified tear protein with the molecular weight of 16,060 Da was also elevated after corneal wounding and returned to normal level by day 5. In this study, LC/ESI-MS was developed as a fast, reproducible and simple method for the identification and analysis of many of the protein components of the tears. Importantly, this technique also allows quantification of each component resolved in the chromatogram. This method is very suitable for mapping peptides and proteins (<80 kDa) in tears. 相似文献
168.
Guo‐Fu Chen Chang‐Heng Tan Zhu‐Lian Li Shan‐Hao Jiang Da‐Yuan Zhu 《Helvetica chimica acta》2003,86(3):787-792
Pseudolarolides O ( 1 ) and P ( 2 ), two novel triterpenoids with a cycloartane‐type framework, were isolated from the seeds of Pseudolarix kaempferi Gord. (Pinaceae). Their structures were elucidated as (16R,23S,25R)‐16,23‐epoxy‐3,4 : 9,10‐disecocycloartan‐1(10),9(11)‐diene‐3(4),26(23)‐diolide ( 1 ), and (9S,16R,23S,25R)‐1,9 : 16,23‐diepoxy‐8,9 : 9,10‐disecocycloartan‐1(29),5(6),10(19)‐triene‐3(4),26(23)‐diolide ( 2 ), respectively, on the basis of spectroscopic techniques and X‐ray‐diffraction studies. 相似文献
169.
Chu YP Gong Y Tan XL Zhang L Zhao S An JY Yu JY 《Journal of colloid and interface science》2004,276(1):182-187
Alkylnaphthalene sulfonates with high purity were selected as model components to research synergism for lowering interfacial tension (IFT) in surfactant/alkali/acidic oil systems. The dynamic IFTs between alkylnaphthalene sulfonates with different alkyl chain length and n-decane, oleic acid model oil, or Shengli crude oil were measured. The results showed that the alkylnaphthalene sulfonates with different alkyl chain lengths had different synergism with different acidic components and their ionized acids under the same conditions. The synergism for lowering dynamic IFT in alkylnaphthalene sulfonate/alkali/acidic oil systems was controlled by alkylnaphthalene sulfonate concentration, alkyl chain length, alkali concentration, alkali type, and oleic acid concentration: optimal physicochemical conditions were necessary to the best synergism. This indicates that the synergism among added surfactant acidic components in crude oil and their ionized acids is controlled by the ratio of their interfacial concentrations. 相似文献
170.
R. S. Judson Y. T. Tan E. Mori C. Melius E. P. Jaeger A. M. Treasurywala A. Mathiowetz 《Journal of computational chemistry》1995,16(11):1405-1419
A genetic algorithm (GA) conformation search method is used to dock a series of flexible molecules into one of three proteins. The proteins examined are thermolysin (tmn), carboxypeptidase A (cpa), and dihydrofolate reductase (dfr). In the latter two proteins, the crystal ligand was redocked. For thermolysin, we docked eight ligands into a protein conformation derived from a single crystal structure. The bound conformations of the other ligands in tmn are known. In the cpa and dfr cases, and in seven of the eight tmn ligands, the GA docking method found conformations within 1.6 Å root mean square (rms) of the relaxed crystal conformation. © 1995 John Wiley & Sons, Inc. 相似文献