全文获取类型
收费全文 | 29049篇 |
免费 | 4095篇 |
国内免费 | 2689篇 |
专业分类
化学 | 20008篇 |
晶体学 | 275篇 |
力学 | 1904篇 |
综合类 | 273篇 |
数学 | 3280篇 |
物理学 | 10093篇 |
出版年
2024年 | 71篇 |
2023年 | 569篇 |
2022年 | 540篇 |
2021年 | 849篇 |
2020年 | 1099篇 |
2019年 | 1057篇 |
2018年 | 874篇 |
2017年 | 779篇 |
2016年 | 1225篇 |
2015年 | 1171篇 |
2014年 | 1479篇 |
2013年 | 1983篇 |
2012年 | 2560篇 |
2011年 | 2658篇 |
2010年 | 1646篇 |
2009年 | 1632篇 |
2008年 | 1736篇 |
2007年 | 1659篇 |
2006年 | 1489篇 |
2005年 | 1228篇 |
2004年 | 940篇 |
2003年 | 789篇 |
2002年 | 751篇 |
2001年 | 561篇 |
2000年 | 558篇 |
1999年 | 651篇 |
1998年 | 578篇 |
1997年 | 574篇 |
1996年 | 659篇 |
1995年 | 506篇 |
1994年 | 464篇 |
1993年 | 384篇 |
1992年 | 362篇 |
1991年 | 316篇 |
1990年 | 247篇 |
1989年 | 201篇 |
1988年 | 157篇 |
1987年 | 135篇 |
1986年 | 125篇 |
1985年 | 118篇 |
1984年 | 87篇 |
1983年 | 60篇 |
1982年 | 41篇 |
1981年 | 36篇 |
1980年 | 17篇 |
1978年 | 19篇 |
1977年 | 23篇 |
1976年 | 20篇 |
1975年 | 28篇 |
1974年 | 27篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
941.
298.1 K时脂肪酸钠盐对定组成水溶液中非水组分活度系数的影响 总被引:1,自引:0,他引:1
本文报告了298.1 K下甲酸钠(C_1), 乙酸钠(C_2)、丙酸钠(C_3)、丁酸钠(C_4)、戊酸钠(C_5)、已酸钠(C_6)和庚酸钠(C_7)七个盐对水溶液中乙醇、丙酮和乙腈三个溶质的活度系数的影响。实验方法是, 固定水溶液中乙醇、丙酮和乙腈的浓度(摩尔分数约为0.05), 用气相色谱法检测不同盐浓度下平衡气相中溶质分压的变化, 从而得出溶质的盐效应活度系数γ。本文给出了一个可以连续取样的气液平衡装置的设计。由实验结果可见, 不同碳链大小的脂肪酸根离子的盐效应作用差别很大。C_1、C_2的盐效应主要由于静电作用; 对C_3、C_4盐, 除静电作用外,它们的疏水基与溶质疏水基的相互作用对盐效应有显著影响; C_5、C_6和C_7的盐效应则反映了疏水离子的特色, 疏水水化、疏水相互作用、疏水离子形成的聚集体与不同官能团的特定相互作用等几项因素, 导致儿个溶质盐效应的差异。 相似文献
942.
Shu-ning Li Xin-lin Yang Wen-qiang Huang 《高分子科学》2007,(6):555-563
Narrow disperse poly(ethyleneglycol dimethacrylate-co-4-vinylpyridine)(poly(EGDMA-co-4-VPy))microspheres were prepared by distillation-precipitation copolymerization of ethyleneglycol dimethacrylate(EGDMA)and 4-vinylpyridine (4-VPy)with 2,2'-azobisisobutyronitrile(AIBN)as initiator in neat acetonitrile.The polymer microspheres containing pyridyl group were then utilized as stabilizer for gold metallic colloids with the diameter around 7 nm,which were prepared by the in situ reduction of gold chloride trihydrate with sodium borohydride through the coordination of the pyridyl group on the gel layer and surface of the microsphere with the gold metallic nano-particles.The catalytic properties of the pyridyl- functionalized microsphere-stabilized gold metallic colloids and the behavior of the stabilized-catalyst for the recycling were investigated with reduction of 4-nitrophenol to 4-aminophenol as a model reaction. 相似文献
943.
A MORPHOLOGICAL STUDY OF POLY(DIVINYLBENZENE-co-ACRYLIC ACID) IN CROSSLINKING PRECIPITATION POLYMERIZATION 总被引:1,自引:0,他引:1
Feng Bai Xin-lin Yang Wen-qiang Huang 《高分子科学》2006,(2):163-171
Divinylbenzene-80 (DVB-80) and polar monomer acrylic acid (AA) having hydrogen bonding at a total monomer loading of 5 vol% were precipitated-copolymerized in a variety of organic solvents with 2,2'-azobis(isobutyronitrile) (AIBN) as initiator. The experiments were investigated from a two-dimensional matrix, i.e., the actual crosslinking degree of DVB varying from 0 to 80% and the solvent composition varying from 0 to 100% of toluene mixture with acetonitrile, when the mixture of acetonitrile and toluene was used as the reaction solvent. Under various reaction conditions, six distinct morphologies including soluble polymers, swellable microgels, coagulum, irregular microparticles, and nano-/micrometer microspheres were formed and the structures of these polymer architectures were described. A morphological map was utilized to discuss the effects of both crosslinking degree of DVB and composition of solvent on the transitions between morphology domains. The results demonstrated that the microspheres are formed by an internal contraction due to the marginal solvency of the continuous phase and the crosslinking of the polymer network through the covalent bonding from DVB as well as the interchain hydrogen-bonding between the carboxylic acid units. 相似文献
944.
945.
IntroductionThepreparativeapproachofaneffectivebilTldslliccatalystisalwaysasubjectofboortantsignificanceinheterogeneouscatalysis.InourrecentstUdies,wefoundthatthebAnetallitcarbonylclustercoCo3(CO)12favorablygivesthebAnetalliccoCo3clusterontheSiOZsubdueaft… 相似文献
946.
Mass-selected C60 beam produced by laser ablation was accelerated and bombarded the (0001) surface of highly oriented pyrolitic graphite and (111) surface of gold single crystal. The samples were characterized by STM. The STM images showed that, the deposited species collapsed and formed planar structure on the solid surface, but the collapsed species were not dissociated and well oriented on the surface. Both positive and negative C60 ions were observed in the desorption mass spectra, confirming that the species collapsed on the solid surface are still the C60 clusters. 相似文献
947.
Simutaneous analysis of seven commonly used herbicides, 2,4-D methyl ester, 2,4-D methyl ester, 2,4,5-T methyl ester, silvex methyl ester, ramrod, CIPC and DEF, by gas-liquid chromatography with an electron capture detector was attempted. Two packed columns (which are generally used for the analysis of chlorinated pesticides) and two chemically bonded fused silica capillary columns were used for the analysis. When the packed columns were used, ramrod always interfered with the analysis of 2,4-D methyl ester and/or silvex methyl ester. Complete separation with reasonable analysis time can be achieved using one of the chemically bonded fused silica capillary columns. 相似文献
948.
Tsai FT Chiou SJ Tsai MC Tsai ML Huang HW Chiang MH Liaw WF 《Inorganic chemistry》2005,44(16):5872-5881
Dinitrosyl iron complex [(-SC(7)H(4)SN)(2)Fe(NO)(2)](-) (1) was prepared by reaction of [S(5)Fe(NO)(2)](-) and bis(2-benzothiozolyl) disulfide. In synthesis of the analogous dinitrosyl iron compounds (DNICs), the stronger electron-donating thiolates [RS](-) (R = C(6)H(4)-o-NHCOCH(3), C(4)H(3)S, C(6)H(4)NH(2), Ph), compared to [-SC(7)H(4)SN](-) of complex 1, trigger thiolate-ligand substitution to yield [(-SC(6)H(4)-o-NHCOCH(3))(2)Fe(NO)(2)](-) (2), [(-SC(4)H(3)S)(2)Fe(NO)(2)](-) (3), and [(SPh)(2)Fe(NO)(2)](-) (4), respectively. At 298 K, complexes 2 and 3 exhibit a well-resolved five-line EPR signal at g = 2.038 and 2.027, respectively, the characteristic g value of DNICs. The magnetic susceptibility fit indicates that the resonance hybrid of {Fe(+)((*)NO)(2)}(9) and {Fe(-)((+)NO)(2)}(9) in 2 is dynamic by temperature. The IR nu(NO) stretching frequencies (ranging from (1766, 1716) to (1737, 1693) cm(-)(1) (THF)) of complexes 1-4 signal the entire window of possible electronic configurations for such stable and isolable {Fe(NO)(2)}(9) [(RS)(2)Fe(NO)(2)](-). The NO-releasing ability of {Fe(NO)(2)}(9) [(RS)(2)Fe(NO)(2)](-) is finely tuned by the coordinated thiolate ligands. The less electron-donating thiolate ligands coordinated to {Fe(NO)(2)}(9) motif act as better NO-donor DNICs in the presence of NO-trapping agent [Fe(S,S-C(6)H(4))(2)](2)(2-). Interconversion between {Fe(NO)(2)}(9) [(RS)(2)Fe(NO)(2)](-) and {Fe(NO)(2)}(10) [(Ph(3)P)(2)Fe(NO)(2)] was verified in the reaction of (a) [(RS)(2)Fe(NO)(2)](-), 10 equiv of PPh(3) and sodium-biphenyl, and (b) 2 equiv of thiol, [RS](-), and [(Ph(3)P)(2)Fe(NO)(2)], respectively. The biomimetic reaction cycle, transformation between {Fe(NO)(2)}(9) [(RS)(2)Fe(NO)(2)](-) and {Fe(NO)(2)}(9) [(R'S)(2)Fe(NO)(2)](-), reversible interconversion of {Fe(NO)(2)}(9) and {Fe(NO)(2)}(10) DNICs, and degradation/reassembly of [2Fe-2S] clusters may decipher and predict the biological cycle of interconversion of {Fe(NO)(2)}(9) DNICs, {Fe(NO)(2)}(10) DNICs, and the [Fe-S] clusters in proteins. 相似文献
949.
Yi‐Jun Huang Guo‐Rong Qi Yu‐Hua Wang 《Journal of polymer science. Part A, Polymer chemistry》2002,40(8):1142-1150
A double metal‐cyanide catalyst based on Zn3[Co(CN)6]2 was prepared. This catalyst is very effective for the ring‐opening polymerization of propylene oxide. Polyether polyols of moderate molecular weight having low unsaturation (<0.015 meq/g) can be prepared under mild conditions. The molecular weight of polymer is entirely controlled by a reacted monomer‐to‐initiator ratio. The polymers prepared with stepwise addition of monomer exhibit a narrower molecular weight distribution as compared with those prepared with one‐step addition of monomer. Various compounds containing active hydrogen, except basic compounds and low‐carbon carboxylic acid, may be used as initiators. The reaction rate increases with increasing catalyst amount and decreases with rising initiator concentration. Polymerization involves a rapid exchange reaction between the active species and the dormant species. It was also proven that, to a certain extent, the chain termination of this catalytic system is reversible or temporary. 13C NMR analysis showed that the polymer has a random distribution of the configurational sequences and head‐to‐tail regiosequence. It is assumed that the polymerization proceeds via a cationic coordination mechanism. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 1142–1150, 2002 相似文献
950.
The YbFe2O4structure type consists of triangular layers of lanthanide oxygen octahedra stacked with triangular double layers of transition metal oxygen triangular bipyramids. The crystallographic structures determined by neutron diffraction powder profile analysis at 300 and 11 K for new members of this structural family are reported. The compounds are found to be magnetically frustrated, by both lattice geometry and disorder. The magnetic properties of YbCuGaO4, LuCuGaO4, LuZnFeO4, LuCoGaO4, and LuCuFeO4reveal the effects of total spin, spin mixing, and interaction between spins on different sublattices on the magnetic frustration. The magnetism is increasingly frustrated as the spin on the magnetic ions is decreased. 相似文献