全文获取类型
收费全文 | 27188篇 |
免费 | 4179篇 |
国内免费 | 2068篇 |
专业分类
化学 | 5252篇 |
晶体学 | 57篇 |
力学 | 3180篇 |
综合类 | 629篇 |
数学 | 14581篇 |
物理学 | 9736篇 |
出版年
2024年 | 39篇 |
2023年 | 275篇 |
2022年 | 505篇 |
2021年 | 618篇 |
2020年 | 667篇 |
2019年 | 638篇 |
2018年 | 613篇 |
2017年 | 931篇 |
2016年 | 1026篇 |
2015年 | 817篇 |
2014年 | 1452篇 |
2013年 | 1987篇 |
2012年 | 1490篇 |
2011年 | 1732篇 |
2010年 | 1561篇 |
2009年 | 1814篇 |
2008年 | 1959篇 |
2007年 | 1997篇 |
2006年 | 1597篇 |
2005年 | 1405篇 |
2004年 | 1351篇 |
2003年 | 1163篇 |
2002年 | 1080篇 |
2001年 | 854篇 |
2000年 | 740篇 |
1999年 | 707篇 |
1998年 | 627篇 |
1997年 | 533篇 |
1996年 | 505篇 |
1995年 | 477篇 |
1994年 | 350篇 |
1993年 | 294篇 |
1992年 | 226篇 |
1991年 | 229篇 |
1990年 | 164篇 |
1989年 | 115篇 |
1988年 | 134篇 |
1987年 | 94篇 |
1986年 | 90篇 |
1985年 | 104篇 |
1984年 | 79篇 |
1983年 | 45篇 |
1982年 | 77篇 |
1981年 | 62篇 |
1980年 | 47篇 |
1979年 | 55篇 |
1978年 | 32篇 |
1977年 | 22篇 |
1976年 | 16篇 |
1973年 | 8篇 |
排序方式: 共有10000条查询结果,搜索用时 359 毫秒
971.
《Phosphorus, sulfur, and silicon and the related elements》2013,188(10):2097-2105
The reactions of N -dichlorophosphoryl- P -trichlorophosphazene, Cl 3 P=N--P(O)Cl 2 with the sodium salts of cyclopentanol, cyclohexanol, 4-methylcyclohexanol, 3-methylcyclohexanol, 3-methylcyclopentanol are discussed. Pentacycloalkoxy-substituted phosphazenes were obtained from cyclopentanol, 4-methylcyclohexanol, 3-methylcyclohexanol, 3-methylcyclopentanol. Tetrasubstituted derivative also was obtained from cyclohexanol at the same conditions. The structure of products was defined by IR, 1 H, 13 C, 31 P NMR, and mass spectroscopy. 相似文献
972.
Majid M. Heravi Fereshteh Hydarzadeh Yahya Farhangi Mitra Ghassemzadeh 《Phosphorus, sulfur, and silicon and the related elements》2013,188(8):1473-1475
Primary and secondary trimethylsilyl ethers are effeciently converted to the corresponding carbonyl compounds using HZSM-5 zeolite-supported CrO 3 under microwave irradiation in solventless system. 相似文献
973.
Svetlana F. Malysheva Natal’ya A. Belogorlova Nina K. Gusarova Alexander V. Artem’ev Alexander I. Albanov Boris A. Trofimov 《Phosphorus, sulfur, and silicon and the related elements》2013,188(8):1688-1693
Abstract Red phosphorus reacts with allylbenzene in the superbase system KOH-DMSO (130°C, 3 h, Ar) to give a mixture of bis(1-methyl-2-phenylethyl)phosphane (1), bis(1-methyl-2-phenylethyl)phosphane oxide (2), and 1-methyl-2-phenylethylphosphinic acid (3). Secondary phosphane oxide 2 and phosphinic acid 3 have been isolated from this mixture in 35% and 32% yield, respectively. Microwave activation of the reaction (200 W, 30 min) affords secondary phosphane 1 as the main product in 48% yield. GRAPHICAL ABSTRACT 相似文献
974.
The surface contact disinfecting technique is a newly developed method for water sterilization. In this paper, the grafted quaternary ammonium salts (QAS) antibacterial fibers were prepared and designed to apply for the surface contact disinfecting process in water treatment. The antibacterial fibers were directly prepared by grafting methacryloxylethyl benzyl dimethyl ammonium chloride (DMAE-BC) onto cellulose fiber using thiocarbonate-H2O2 redox system. All kinds of factors in the grafting reactions, such as reaction time, reaction temperature, monomer concentration, initiator concentration, which influence the percentage of grafting, were studied and optimized. The modified cellulose fibers were characterized by Fourier transform infrared spectroscopy (FTIR) and scanning electron microscope(SEM). The effects of the percentage of grafting of the grafted cellulose fibers on bactericidal activity were also studied. The spread plate method was used to characterize the bactericidal activity. The disinfection process was further investigated by directly observing the morphology of the bacterial cells adsorbed on the antibacterial fibers with SEM and measuring extracelluar total protein concentration in suspension. The poly(DMAE-BC)-grafted cellulose ?ber was found to exhibit particularly high activity against E.coli. 相似文献
975.
The present study deals with the modification of sterculia gum to develop the novel colon specific delivery system for use in colon cancer. The sterculia and acrylic acid based hydrogels were synthesized and characterized with FTIR, SEMs, TGA and swelling behavior. Swelling studies of the hydrogels were carried out as a function of reaction parameters such as monomer concentration, initiator concentration, amount of sterculia gum and crosslinker concentration and nature of swelling mediums. Swelling kinetics of the hydrogels and in vitro release dynamics of anticancer model drug methotrexate from the hydrogels were studied to evaluate the swelling mechanism and drug release mechanism from the drug-loaded hydrogels. The values of diffusion exponent for the release of drug were 0.883, 0.910 and 0.787 in distilled water, pH 2.2 buffer and pH 7.4 buffer, respectively. The release of drug from the polymer matrix occurred through a non -Fickian type diffusion mechanism. 相似文献
976.
In this paper, the diffusion mechanism of as‐spun PAN fiber was investigated in dimethyl sulfoxide‐water by determining the dynamic compositions of the fibers and the diffusion coefficients of solvent and nonsolvent during coagulation. The diffusion process could be divided into two stages. Results showed that the first stage of the diffusion process was the most important during the whole process, which was fundamental to further study on the formation mechanism. Also, compared with wet spinning, the dry‐jet wet spinning method had the advantage of mild coagulating at a high jet‐stretch. At high concentrations, the diffusion coefficients increased and the ratio of solvent diffusion coefficient to nonsolvent diffusion coefficient decreased; an increasing temperature resulted in the increase of both diffusion coefficients with a decrease in their ratios. To some extent, for the PAN‐DMSO‐water system, the more the ratios Ds*/Dn* tended to 1, the more the cross‐section shapes of as‐spun PAN fiber tended to be circular. 相似文献
977.
《高分子科学杂志,A辑:纯化学与应用化学》2013,50(12):1435-1450
ABSTRACT The kinetics of the free radical bulk polymerization of methyl methacrylate (MMA) was studied by DSC, using the benzoyl peroxide (BPO)/amine initiation system. N,N dimethyl-4-aminophenethyl alcohol (DMPOH), which is a newly synthesized and used amine in the preparation of acrylic dental resins and bone cements was examined, and the results compared to the most commonly used in these applications amine, the N,N dimethyl-p-toluidine (DMT). For both amines, the effect of the molar ratio of BPO/amine and of the reaction temperature, on the polymerization kinetics was investigated. The prepared polymers were characterized by determination of the average molecular weights (M¯ n and M¯ w ) and molecular weights distribution (M¯ w /M¯ n ) using Gel Permeation Chromatography. DMPOH was found to lead in slightly higher polymerization rates, lower gel times and lower molecular weights than DMT. The values of these parameters for both amines were influenced by the molar ratio of BPO to amine, when the product of the concentrations of these was kept constant. The highest polymerization rate occurred in the lowest gel time, resulting in polymers with the lowest molecular weight, and was observed when a molar ratio of about 1.5 BPO/amine was used. However, the final monomer conversion was found to be independent of the molar ratio and amine used. The activation energy of polymerization was found to be 51.8 kJ/mol K for BPO/DMPOH and 47.1 kJ/mol K for BPO/DMT. 相似文献
978.
The ability of β-cyclodextrin (β-CD), γ-CD, hydroxypropyl-β-CD (HP-β-CD), trimethyl-β-CD (TM-β-CD), sulfurbutylether-β-CD (SBE-β-CD) and carboxymethyl-β-cyclodextrin (CM-β-CD) to break the aggregate of the meso-tetrakis(4-N-trimethylaminobenzyl)porphyrin (TAPP) and to form 2:1 inclusion complexes has been studied by absorption and fluorescence spectroscopy. The formation constants are calculated, respectively, by fluorimetry, from which the inclusion capacity of different CDs is compared and the inclusion mechanism of charged-β-CD (SBE-β-CD and CM-β-CD) is quite different from that of the parent β-CD. At lower pH, the complexation between TM-β-CD and H2TAPP2+ (the form of the diprotonated TAPP) hampers the continuous protonation of the pyrrole nitrogen of TAPP and the hydrophobic cavity may prefer to bind an apolar neutral porphyrin molecule. 1HNMR data support the inclusion conformation of the porphyrin–cyclodextrin supramolecular system, indicating the interaction of the meso-phenyl groups of TAPP with the cavity of CDs. For this host–guest inclusion model, cyclodextrin being regarded as the protein component, which acts as a carrier enveloping the active site of heme prosthetic group within its hydrophobic environment, provides a protective sheath for the porphyrin, creating artificial analogues of heme-containing proteins. However, for TAPP, encapsulated within this saccharide-coated barrier, its photophysical and photochemical properties changed strongly. 相似文献
979.
This report describes development of an in silico, expert rule-based method for the classification of chemicals into irritants or non-irritants to eye, as defined by the Draize test. This method was developed to screen data-poor cosmetic ingredient chemicals for eye irritancy potential, which is based upon exclusion rules of five physicochemical properties – molecular weight (MW), hydrophobicity (log P), number of hydrogen bond donors (HBD), number of hydrogen bond acceptors (HBA) and polarizability (Pol). These rules were developed using the ADMET Predictor software and a dataset of 917 eye irritant chemicals. The dataset was divided into 826 (90%) chemicals used for training set and 91 (10%) chemicals used for external validation set (every 10th chemical sorted by molecular weight). The sensitivity of these rules for the training and validation sets was 72.3% and 71.4%, respectively. These rules were also validated for their specificity using an external validation set of 2011 non-irritant chemicals to the eye. The specificity for this validation set was revealed as 77.3%. This method facilitates rapid screening and prioritization of data poor chemicals that are unlikely to be tested for eye irritancy in the Draize test. 相似文献
980.
Several N-alkyl/aryl-Se-alkyl/(aryl)selenocarbamates were prepared from various isocyanates and diselenides by reductive cleavage of Se-Se bond with the Zn/AlCl3 system in dry acetonitrile at 80℃. 相似文献