全文获取类型
收费全文 | 3469篇 |
免费 | 147篇 |
国内免费 | 32篇 |
专业分类
化学 | 2393篇 |
晶体学 | 35篇 |
力学 | 157篇 |
综合类 | 1篇 |
数学 | 446篇 |
物理学 | 616篇 |
出版年
2023年 | 21篇 |
2022年 | 107篇 |
2021年 | 120篇 |
2020年 | 81篇 |
2019年 | 91篇 |
2018年 | 78篇 |
2017年 | 71篇 |
2016年 | 121篇 |
2015年 | 99篇 |
2014年 | 116篇 |
2013年 | 251篇 |
2012年 | 199篇 |
2011年 | 220篇 |
2010年 | 118篇 |
2009年 | 102篇 |
2008年 | 123篇 |
2007年 | 145篇 |
2006年 | 131篇 |
2005年 | 124篇 |
2004年 | 110篇 |
2003年 | 92篇 |
2002年 | 89篇 |
2001年 | 57篇 |
2000年 | 72篇 |
1999年 | 34篇 |
1998年 | 45篇 |
1997年 | 30篇 |
1996年 | 44篇 |
1995年 | 32篇 |
1994年 | 34篇 |
1993年 | 34篇 |
1992年 | 28篇 |
1991年 | 31篇 |
1990年 | 34篇 |
1989年 | 29篇 |
1988年 | 22篇 |
1987年 | 27篇 |
1986年 | 16篇 |
1985年 | 40篇 |
1984年 | 30篇 |
1983年 | 34篇 |
1982年 | 30篇 |
1981年 | 29篇 |
1980年 | 31篇 |
1979年 | 18篇 |
1978年 | 24篇 |
1977年 | 24篇 |
1975年 | 27篇 |
1974年 | 24篇 |
1973年 | 17篇 |
排序方式: 共有3648条查询结果,搜索用时 31 毫秒
71.
Ibrahim Y Alsharaeh E Dias K Meot-Ner Mautner M El-Shall MS 《Journal of the American Chemical Society》2004,126(40):12766-12767
We studied the stepwise hydration and solvent-mediated deprotonation of the benzene*+ cation (Bz*+) and found several unusual features. The solvent binding energies DeltaH on-1,n for the reactions Bz*+(H2O)n-1 + H2O --> Bz*+(H2O)n are nearly constant at 9 +/- 1 kcal mol-1 for n = 1 to 8. We observed a remarkable sudden decrease in the entropy of association accompanying the formation of Bz*+(H2O)7 and Bz*+(H2O)8, indicating strong orientational restraint in the hydration shells of these clusters consistent with the formation of cagelike structures. We observed the size-dependent deprotonation of Bz*+ in a cooperative multibody process, where n H2O molecules (n >/= 4) can remove a proton from Bz*+ to form protonated water clusters. We measured, for the first time, the temperature dependence of such a process and found a negative temperature coefficient of a magnitude unprecedented in any chemical reaction, of the form k = AT-67+/- 4, or in an Arrhenius form having an activation energy of -34 +/- 1 kcal mol-1. The temperature effect may be explained by Bz*+ and four H2O molecules needing to be assembled from gas-phase components to form the reactive species. Such large temperature effects may be therefore general in solvent cluster-mediated reactions. 相似文献
72.
Ibrahim Isildak Murat Yolcu Omer Isildak Nadir Demirel Giray Topal Halil Hosgoren 《Mikrochimica acta》2004,144(1-3):177-181
Two diaza-crown ether compounds were synthesized and evaluated as Ag+-selective carriers in polyvinylchloride (PVC) membrane electrodes of solid-state type. The all-solid-state PVC membrane electrode based on N,N-Dibenzyl-dibenzo-diaza-18-crown-6 exhibited a super-Nernstian response (75±10mV per decade) over the concentration range of 1×10–1 to 7×10–6M of Ag+ ion and a detection limit of 3×10–6M, at a wide range of pH (pH 4–7). The response time of the electrode was fast (less than 10s), and it can be used for three months without any significant deviation in potential. The proposed all-solid-state PVC membrane electrodes revealed high selectivity toward Ag+ ion with respect to alkali, alkaline earth, heavy and transition metal ions. A flow-through cell of all-solid-state PVC membrane Ag+-selective electrode based on N,N-Dibenzyl-dibenzo-diaza-18-crown-6 has also been prepared and applied for flow-injection analysis of Ag+ ion in solution. 相似文献
73.
5-Arylidenes 1a and 1b, on reaction with ethyl cyanoacetate and diethyl malonate in the presence of ammonium acetate under Michael condensation, yield pyridine derivatives 2 and 3, respectively. Cyclopentapyrimidine derivative 4 can also be obtained by the reaction of 1a with malononitrile in the presence of piperidine. The reaction of 5-arylidene lb with monochloroacetic acid in an alkaline medium gives the thiazol derivative 5. Also, spiro-[3′, 5′]cyclohexenyl pyrimidine derivative 6 could be obtained from the reaction of 1d with maleic anhydride. On the other hand, 5-arylidene 1e reacts with maleic anhydride to give 2-thiobarbituric acid derivative 7. The condensation reaction of 2-thiovioluric acid 8 with some hydrazines affords the triazole derivatives 9a-d. Finally, barbituric acid condenses with isatin to give 5-arylidene 1f, which can be cyclized with phosphorous pentoxide to afford 10. 相似文献
74.
Reppert PM Morgan FD Lesmes DP Jouniaux L 《Journal of colloid and interface science》2001,234(1):194-203
An experimental apparatus and data acquisition system was constructed to measure the streaming potential coupling coefficients as a function of frequency. The purpose of the experiments was to measure, for the first time, the real and imaginary portion of streaming potentials. In addition, the measured frequency range was extended beyond any previous measurements. Frequency-dependent streaming potential experiments were conducted on one glass capillary and two porous glass filters. The sample pore diameters ranged from 1 mm to 34 μm. Two frequency-dependent models (Packard and Pride) were compared to the data. Both Pride's and Packard's models have a good fit to the experimental data in the low- and intermediate-frequency regime. In the high-frequency regime, the data fit the theory after being corrected for capacitance effects of the experimental setup. Pride's generalized model appears to have the ability to more accurately estimate pore sizes in the porous medium samples. Packard's model has one unknown model parameter while Pride's model has four unknown model parameters, two of which can be independently determined experimentally. Pride's additional parameters may allow for a determination of permeability. Copyright 2001 Academic Press. 相似文献
75.
The potassium enolate of 4-methoxy-3-buten-2-one reacts with acid chlorides anhydrides and acylimidazoles by C-acylation and cyclization to afford 2-substituted γ-pyrones directly. 相似文献
76.
The methacrylate monomer, 2-[(5-methylisoxazol-3-yl)amino]-2-oxo-ethyl methacrylate (IAOEMA), was synthesized by reacting 2-chloro-N-(5-methylisoxazol)acetamide dissolved in acetonitrile with sodium methacrylate in the presence of triethylbenzylammoniumchloride (TEBAC). The free-radical-initiated copolymerization of IAOEMA, with styrene (ST) and methyl methacrylate (MMA) was carried out in dimethylsulphoxide (DMSO) solution at 65 °C using 2,2′-azobisisobutyronitrile (AIBN) as an initiator with different monomer-to-monomer ratios in the feed. The monomer (IAOEMA) and copolymers were characterized by FTIR, 1H- and 13C-NMR spectral studies. The copolymer composition was evaluated by nitrogen content in polymers led to the determination of reactivity ratios. The reactivity ratios of the monomers were determined by the application of Fineman-Ross and Kelen-Tüdös methods. The analysis of reactivity ratios revealed that ST and MMA are more reactive than IAOEMA, and copolymers formed are statisticalle in nature. The molecular weights (Mw and Mn) and polydispersity index of the polymers were determined using gel permeation chromagtography. Glass transition temperatures of the copolymers were found to increase with an increase in the mole fraction of IAOEMA in the copolymers. The apparent thermal decomposition activation energies (Ed) were calculated by Ozawa method using the SETARAM Labsys TGA thermobalance. 相似文献
77.
Tetsuro Ito Toshiyuki TanakaMunekazu Iinuma Ibrahim IliyaKen-ichi Nakaya Zulfiqar AliYoshikazu Takahashi Ryuichi SawaYoshiaki Shirataki Jin MurataDedy Darnaedi 《Tetrahedron》2003,59(28):5347-5363
Five new resveratrol oligomers; pauciflorols A-C (1-3), isovaticanols B (6) and C (8), and three new oligostilbene glucosides; pauciflorosides A (11), B (13), C (14), were isolated from the stem bark of Vatica pauciflora (Dipterocarpaceae) together with known 17 resveratrol oligomers (4, 5, 7, 9, 10, 12 and 15-25) and bergenin (26). The structures of isolates were established on the basis of detailed spectroscopic analysis. The typical and characteristic spectral properties of some resveratrol oligomers were also discussed. 相似文献
78.
Gehan M. El-Subruiti Kamal H. Halawani Cecil F. Wells Ibrahim M. Sidahmed 《Transition Metal Chemistry》1993,18(3):323-328
Summary The kinetics of the solvolysis of complex ions trans-[Co(Rpy)4Cl2]+, with R = 4-t-Bu, 3-Me and 3-Et, have been investigated in mixtures formed by adding urea to water, which enhances the dielectric constant and decreases solvent structure. Differential effects of the changes in solvent structure on the initial and transition states are found to be important factors controlling changes in the rate constant with solvent composition. The variation of the enthalpy and the entropy of activation with solvent composition are contrasted with their variations found for the solvolysis of [Co(Rpy)4Cl2]+ in mixtures where solvent structure is enhanced by additions of a co-solvent to water. The application of a free energy cycle to the process of the initial state going to the transition state suggests that the Co3+ cation in the transition state is more stable than the Co3+ cation in the initial state in the water + urea mixtures. 相似文献
79.
Aisha I. Ibrahim 《Transition Metal Chemistry》1994,19(6):561-563
Summary By the interaction of anhydrous CoBr2 or CoBr2·2THF with different sodium aryloxides, a new series of complexes of general formula Na2[Co(OAr)4]·nTHF (OAr =o-nitro,o-chloro,o-bromo,m-chloro,p-bromo, 2,4-dichloro, 2,6-dichloro, or 2,4-dimethylphenoxide;n = 1, 3, 4 or 5) were prepared and characterized by physicochemical means. The electronic spectra and magnetic measurements suggest a tetrahedral geometry for cobalt(II). Heating the complexes led to reversible loss of THF with an accompanying colour change. 相似文献
80.
Ethylene tetramerization: a new route to produce 1-octene in exceptionally high selectivities 总被引:11,自引:0,他引:11
Bollmann A Blann K Dixon JT Hess FM Killian E Maumela H McGuinness DS Morgan DH Neveling A Otto S Overett M Slawin AM Wasserscheid P Kuhlmann S 《Journal of the American Chemical Society》2004,126(45):14712-14713
Linear alpha-olefins, such as 1-hexene and 1-octene, are important comonomers in the production of linear low-density polyethylene (LLDPE). The conventional method of producing 1-hexene and 1-octene is by oligomerization of ethylene, which yields a wide spectrum of linear alpha-olefins (LAOs). While there exists several processes for producing 1-hexene via ethylene trimerization, a similar route for the selective production of 1-octene has so far been elusive. We now, for the first time, report an unprecedented ethylene tetramerization reaction that produces 1-octene in selectivities exceeding 70%, using an aluminoxane-activated chromium/((R2)2P)2NR1 catalyst system. 相似文献