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181.
182.
Johansson A Håkansson M Jagner S 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(18):5311-5318
Stereochemically labile copper and zinc complexes with the N,N'-dimethylethylenediamine ligand (dmeda) have been shown to be promising precursors for the total spontaneous resolution of chiral covalent networks. (N,N')-[Cu(NO3)2(dmeda)]infinity crystallises as a conglomerate and yields either enantiopure (R,R)-1 or enantiopure (S,S)-1. A mixed-valence copper(I/II) complex, [{Cu(II)Br2(dmeda)}3(Cu(I)Br)2]infinity (2), which crystallises as a pair of interpenetrating chiral (10,3)-a nets, is formed from CuBr, CuBr2 and dmeda. One net contains ligands with solely (R,R) configuration and exhibits helices with (P) configuration while the other has solely (S,S)-dmeda ligands and gives rise to a net in which the helices have (M) configuration. The whole crystalline arrangement is racemic, because the interpenetrating chiral nets are of opposite handedness. With zinc chloride (R,S)-[ZnCl(dmeda)2]2[ZnCl4] (3) is obtained, which is a network structure, although not chiral. Total spontaneous resolution of stereochemically labile metal complexes formed from achiral or racemic building blocks is suggested as a viable route for the preparation of covalent chiral networks. Once the absolute structure of the compound has been determined by X-ray crystallography, a quantitative determination of the enantiomeric excess of the bulk product can be undertaken by means of solid-state CD spectroscopy. 相似文献
183.
Changes in the stability of the cadmium(ii) ethylenediamine complexes in mixed water—DMSO solvents were studied by pH-metry and calorimetry. Complex cations [Cd(en)]2+, [Cd(en)2]2+, and [Cd(en)3]2+ are formed in aqueous solutions, and the [Cd(en)4]2+ complex with a partially dentate ligand is stable in DMSO. An increase in the DMSO content in a solvent increases the stability of the complexes. The maximum increase in logK is observed for coordinatively saturated compounds. The thermodynamics of complexation is discussed from the viewpoint of solvation approach. Principal differences in the influence of aqueous-alcohol and aqueous-aprotic solvents on the stability of the metal amino complexes were revealed. Protolytic solvents exert a destabilizing effect on the multiligand complexes, because the coordination sphere is involved in H bonding. 相似文献
184.
超微孔材料具有1~2 nm的孔径,在分离、催化应用中有望展现出择形催化的能力。 寻找经济、简便的合成超微孔材料的表面活性剂体系是一项有意义的工作。 本研究以短链季铵盐(十烷基三甲基溴化铵,记为C10TAB)和不同链长脂肪酸酸盐混合胶束为模板剂,硅酸钠为硅源,成功制备出高度有序超微孔SiO2。 通过小角X射线衍射、N2吸附-脱附、傅里叶变换红外光谱、扫描电子显微镜(SEM)和透射电子显微镜(TEM)等技术手段对产品的结构和性能进行了表征。 结果表明,合成体系中脂肪酸盐碳链长、加入量、晶化温度等对产物孔道有序性有很大影响。 当选择正辛酸钠(SO)为助表面活性剂,当n(C10TAB):n(Na2SiO3):n(SO):n(H2O)=1:1.5:0.3:800,晶化温度为80 ℃时,可以得到高度有序超微孔SiO2。 煅烧后样品比表面积为1300 m2/g,孔体积0.49 cm3/g,孔径分布在1.90 nm。 相似文献
185.
The effect of B2O3 addition on the crystallization of amorphous TiO2-ZrO2 mixed oxide was investigated by X-ray diffraction (XRD), thermogravimetric and differential thermal analysis (TG/DTA). TiO2-ZrO2 mixed oxide was prepared by co-precipitation method with aqueous ammonia as the precipitation reagent. Boric acid was used as a source of boria, and boria contents varied from 2 to 20 wt%. The results indicate that the addition of small amount of boria (<8 wt%) hinders the crystallization of amorphous TiO2-ZrO2 into a crystalline ZrTiO4 compound, while a larger amount of boria (?8 wt%) promotes the crystallization process. FT-IR spectroscopy and 11B MAS NMR results show that tetrahedral borate species predominate at low boria loading, and trigonal borate species increase with increasing boria loading. Thus it is concluded that highly dispersed tetrahedral BO4 units delay, while a build-up of trigonal BO3 promote, the crystallization of amorphous TiO2-ZrO2 to form ZrTiO4 crystals. 相似文献
186.
Small-angle neutron scattering from micelles of alkylpolyoxyethylene sulfate: Effect of chain length
Small-angle neutron scattering (SANS) data have been obtained for (i) a series of solutions of C
m
H2m+1(OCH2–CH2)2SO4Na, for m=18, 16, and 14; (ii) an approximately 0.07M solution of C14H29(OCH2–CH2)2SO4Na to which different amounts of NaCl were added; and (iii) a series of solutions of variable concentration of C12H25(OCH2–CH2)SO4Na. The increase of the number of carbon atoms of the hydrocarbon chain produces a noticeable increase of the aggregation number of the micelles, while the salt tolerance decreases with increasing m. All the data can be described in terms of a monodispersed, charged, hard-spheres model interacting via a screened Coulombic potential, except the run at highest salt concentration, for which an ellipsoid model gives better results. 相似文献
187.
Densities and apparent molar volumes of aqueous 2-chloroethanol were determined at temperatures from 15.0 to 34.4°C using digital densimetry. The results of the volumetric measurements have been used to calculate the following thermodynamic quantites at 25°C: V
2
o = 55.05 ± 0.02 cm3-mol–1, (V
2
o/T)p = 0.01486 ± 0.00318 cm3-K–1-mol–1, and (2
V
2
o/T
2)p = 0.02972 ± 0.00318 cm3-K–2-mol–1. Partial molar volumes of transfer from water to 1 mol-dm–3 2-chloroethanol have also been determined for L-glycine, L-alanine, L-serine, L-glutamic acid, and L-aspartic acid at 35.0°C. The transfer results have been explained in terms of the nature of the interactions of the groups in the solute and solvent. Hydration numbers of L-glycine and L-alanine have also been calculated in aqueous 2-chloroethanol. 相似文献
188.
以水滑石及类水滑石为前体的Mg/Al、Co/Al及Co/Mg/Al混合氧化物的合成、表征和异丙醇催化性能 总被引:11,自引:0,他引:11
以共沉淀法合成的水滑石(HT)和类水滑石(HTLc)为前体制备了镁铝、钴铝、钴镁铝混合氧化物,采用了BET、XRD、TG-DTA、TPR、FTIR和微量量热吸附及异丙醇催化反应进行了研究。结果表明:以HT和HTLc为前体制备的混合氧化物,其比表面积较大、并随着钴含量的增加而降低。在HT中引入Co2+离子后,由于Co2+离子的氧化还原属性,削弱了水滑石层对阴离子的键合能力,从而使其热分解温度及热稳定性降低,导至焙烧后生成的混合氧化物的比表面积比不含钴的2Mg/Al混合氧化物的低。在TPR过程中,镁铝混合氧化物不被还原,而含钴的混合氧化物的还原是经由Co3+ → Co2+ → Co0的过程。混合氧化物表面含有酸性位和碱性位,并随着钴含量的变化而得到调变。含钴氧化物样品的表面以L酸为主和含有很少量的B酸。异丙醇催化反应生成丙酮的选择性最高,表明样品表面的氧化还原位是主要的,随着钴的加入及含量的增大,异丙醇催化反应的转化率也是增大的。 相似文献
189.
用电纺法制备了TiO2/P(VdF-HFP)(聚偏氟乙烯-六氟丙烯共聚物)杂化纤维微孔膜, 用SEM观察了杂化纤维微孔膜的形貌, 并测算了这类由超细纤维相互搭接而形成的微孔膜的孔隙率. 这种微孔膜吸附LiPF6/EC-DMC-EMC(碳酸乙烯酯-二甲基碳酸酯-碳酸甲乙酯)电解质溶液后得到凝胶聚合物电解质膜. 用电化学方法测试了聚合物电解质膜的离子电导率、锂离子迁移数等参数, 并研究了TiO2纳米晶的掺入对聚合物电解质电化学性能的影响. 结果表明, TiO2的掺入降低了P(VdF-HFP)聚合物基体的结晶度, 改善了凝胶聚合物电解质的低温电化学性能. 相似文献
190.