首页 | 本学科首页   官方微博 | 高级检索  
文章检索
  按 检索   检索词:      
出版年份:   被引次数:   他引次数: 提示:输入*表示无穷大
  收费全文   37972篇
  免费   9609篇
  国内免费   1417篇
化学   42754篇
晶体学   335篇
力学   548篇
综合类   1篇
数学   2744篇
物理学   2616篇
  2022年   38篇
  2021年   187篇
  2020年   1256篇
  2019年   2609篇
  2018年   1027篇
  2017年   671篇
  2016年   3400篇
  2015年   3559篇
  2014年   3465篇
  2013年   4178篇
  2012年   3008篇
  2011年   2253篇
  2010年   2911篇
  2009年   2862篇
  2008年   2455篇
  2007年   1822篇
  2006年   1523篇
  2005年   1691篇
  2004年   1546篇
  2003年   1401篇
  2002年   2087篇
  2001年   1380篇
  2000年   1308篇
  1999年   392篇
  1998年   91篇
  1997年   96篇
  1996年   87篇
  1995年   63篇
  1994年   73篇
  1993年   72篇
  1992年   68篇
  1991年   42篇
  1990年   46篇
  1989年   47篇
  1988年   42篇
  1987年   41篇
  1986年   39篇
  1985年   48篇
  1984年   66篇
  1983年   56篇
  1982年   71篇
  1981年   72篇
  1980年   74篇
  1979年   82篇
  1978年   78篇
  1977年   83篇
  1976年   76篇
  1975年   74篇
  1974年   75篇
  1973年   54篇
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
971.
972.
We consider two models that are small perturbations of Gaussian or mean field models: the first one is a double well /44 — /22 perturbation of a massless Gaussian lattice field in the weak coupling limit (0, proportional to ). The other consists of a spin 1/2 Ising model with long-range Kac type interactions; the inverse range of the interaction, , is the small parameter. The second model is related to the first one via a sine-Gordon transformation. The lattice d has dimensiond3.In both cases we derive an asymptotic estimate to first order (in or 2) on the location of the critical point. Moreover, we prove bounds on the remainder of an expansion in or around the Gaussian or mean field critical points.The appendix, due to E. Speer, contains an extension of Weinberg's theorem on the divergence of Feynman graphs which is used in the proofs.Supported by NSF Grant # MCS 78-01885Supported by NSF Grant # PHY 78-15920  相似文献   
973.
Background Pillar[n]arene(PA[n])contains a symmetrical structures,where para-bridge connection between the units looks like a column-like or pillar shape and polygonal structure from side and top views,respectively.The attached groups to the PA[n]are pointing towards the opposite directions along the columnar axis.  相似文献   
974.
The preparation of monolithic poly(butyl methacrylate-co-ethylene dimethacrylate) capillary columns using photoinitiated in situ polymerization within 200 microm i.d. capillaries and their application for microHPLC separations of proteins have been studied. The low resistance to flow characteristic of monolithic columns, enabled the use of very high flow rates of up to 100 microL/min representing a flow velocity of 87 mm/s. Very good separations of a model protein mixture consisting of ribonuclease A, cytochrome c, myoglobin, and ovalbumin was achieved in less than 40 s using a very simple single step gradient of the mobile phase. Interestingly, no effect of the pore size on the separations of proteins was observed for these monolithic columns within the size range of 0.66-2.2 microm. The monolithic microHPLC columns are found very robust and no changes in the long term separation performance and back pressure were observed.  相似文献   
975.
The Rose Bengal‐sensitized photooxidations of the dipeptides l ‐tryptophyl‐l ‐phenylalanine (Trp‐Phe), l ‐tryptophyl‐l ‐tyrosine (Trp‐Tyr) and l ‐tryptophyl‐l ‐tryptophan (Trp‐Trp) have been studied in pH 7 water solution using static photolysis and time‐resolved methods. Kinetic results indicate that the tryptophan (Trp) moiety interacts with singlet molecular oxygen (O2(1Δg)) both through chemical reaction and through physical quenching, and that the photooxidations can be compared with those of equimolecular mixtures of the corresponding free amino acids, with minimum, if any, influence of the peptide bond on the chemical reaction. This is not a common behavior in other di‐ and polypeptides of photooxidizable amino acids. The ratio between chemical (kr) and overall (kt) rate constants for the interaction O2(1Δg)‐dipeptide indicates that Trp‐Phe and Trp‐Trp are good candidates to suffer photodynamic action, with krlkt values of 0.72 and 0.60, respectively (0.65 for free Trp). In the case of Trp‐Tyr, a lower krlkt value (0.18) has been found, likely as a result of the high component of physical deactivation of O2(1Δg) by the tyrosine moiety. The analysis of the photooxidation products shows that the main target for O2(1Δg) attack is the Trp group and suggests a much lower accumulation of kynurenine‐type products, as compared with free Trp. This is possibly because of the occurrence of another accepted alternative pathway of oxidation that gives rise to 3a‐oxidized hydrogenated pyrrolo[2,3‐b]indoles.  相似文献   
976.
A new fluorinated polystyrene bearing a p-sulbstiuted perfluoro[1-(2-fluorosulfonylethoxy)]ethyl group was synthesized via one-electron oxidation of polystyrene by perfluoro[2-(2-fluorosulfonylethoxy)]propionyl peroxide at different peroxide to polystyrene molar ratios.The yield of perfluoroalkylation decreases with the increase of the reactant molar ratio.The modified polymer has been characterized by various techniques:the ring pefluoro[1-(2-fluorosulfonylethoxy)]ethylation has been proved by FT-IR and ^19FNMR;the X-ray photoelectron spectra(XPS) show the maximum binding energy of F18,O18,C18(two kinds of carbon atoms,namely C-H and C-F)and S2p,respectively; desulfonylation of the fluorinated polystyrene appearing at 217℃ has been found by its thermogravimetric analysis (TGA).The determinations of contact angle,refractive index and glass transition temperature of the modified polymer have disclosed that when the contact angle increases with the increase of the molar ratio,the refractive index and glass transition temperature decrease.The polydispersity values indicate that the degradation of the polymer chains did not occur during the reaction.  相似文献   
977.
The leaves of some plants, particularly among the Solanacea, contain crystals of calcium oxalate with a peculiar chiral pseudo‐tetrahedral morphology, even though the calcium oxalate crystal structure is centrosymmetric, hence achiral. We studied the morphology of these crystals extracted from the leaves of three Solanacea plants: the potato, the hot pepper, and a species of wild Solanum. The crystal morphology was the same in all three species. Based on the examination of more than 100 crystals from each plant, we showed that the crystal morphology is chiral with invariant chirality. We suggest that morphological chirality is induced by macromolecules during nucleation from a specific, genetically encoded crystal plane, and is further established during subsequent controlled crystal growth. This is one of few examples where it is possible to deduce a molecular mechanism for biologically induced breaking of morphological symmetry in organisms. A very high level of recognition is required by the macromolecules to allow them to distinguish between symmetry‐related crystal planes. It is also surprising that this finely controlled mechanism of crystal formation, including the chiral morphology, has been conserved during evolution.  相似文献   
978.
Xiao‐Hong Fu 《Electroanalysis》2007,19(17):1831-1839
A new electrochemical immunosensor for the detection of carbohydrate antigen‐125 (CA125), a carcinoma antigen, was developed by immobilization CA125 antibody (anti‐CA125) on gold hollow microspheres and porous polythionine (PTH) modified glassy carbon electrodes (GCE). The gold hollow microspheres provided a biocompatible microenvironment for proteins, and greatly amplified the coverage of anti‐CA125 molecules on the electrode surface. The performance and factors influencing the immunosensor were investigated in detail. The detection is based on the current change before and after the antigen‐antibody interaction. Under optimal conditions, the amperometric changes were proportional to CA125 concentration ranging from 4.5 to 36.5 U/mL with a detection limit of 1.3 U/mL (at 3σ). The CA125 immunosensor exhibited good precision, high sensitivity, acceptable stability, accuracy and reproducibility. The as‐prepared immunosensors were used to analyze CA125 in human serum specimens. Analytical results suggest that the developed immunoassay has a promising alternative approach for detecting CA125 in the clinical diagnosis.  相似文献   
979.
Poly [N‐bromo‐benzene‐1,3‐disulfonylamide] [ PBBS ] is a novel and efficient reagent for the conversion of oximes and semicarbazones under solid state to their corresponding carbonyl compounds in high yields.  相似文献   
980.
The three (O‐methyl)‐p‐ethoxyphenyldithiophosphonato triphenylphosphine complexes of copper, silver and gold, [(Ph3P)nM{S2P(OMe)C6H4OEt‐p}] (M = Cu, n = 2; M = Ag, Au, n = 1) investigated structurally by X‐ray diffraction exhibit remarkable structural differences. The copper compound is a four‐coordinate chelate monomer with Cu–S 2.4417(6) and 2.5048(6) Å; P–Cu–S 104.24(2)–114.01(2)°; Cu–S–P 82.49(3)° and 80.85(2)°. The silver compound is a cyclic dimer with bridging dithiophosphonato ligands and three‐coordinate silver atoms [Ag–S 2.5371(5) and 2.6867(5) Å; P–Ag–S 122.88(2)° and 122.17(2)°; Ag–S–P 89.32(2)° and 103.56(2)°]. The gold compound is monomeric with linear dicoordinate gold [Au–S 2.3218(6) Å; P–Au–S 177.72(2)°, Au–S–P 100.97(3)°].  相似文献   
设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号