全文获取类型
收费全文 | 37122篇 |
免费 | 435篇 |
国内免费 | 136篇 |
专业分类
化学 | 18388篇 |
晶体学 | 682篇 |
力学 | 1635篇 |
综合类 | 2篇 |
数学 | 3696篇 |
物理学 | 13290篇 |
出版年
2022年 | 284篇 |
2021年 | 340篇 |
2020年 | 318篇 |
2019年 | 326篇 |
2018年 | 531篇 |
2017年 | 452篇 |
2016年 | 754篇 |
2015年 | 436篇 |
2014年 | 748篇 |
2013年 | 1655篇 |
2012年 | 1516篇 |
2011年 | 1871篇 |
2010年 | 1358篇 |
2009年 | 1361篇 |
2008年 | 1554篇 |
2007年 | 1524篇 |
2006年 | 1421篇 |
2005年 | 1214篇 |
2004年 | 1147篇 |
2003年 | 995篇 |
2002年 | 943篇 |
2001年 | 1352篇 |
2000年 | 974篇 |
1999年 | 807篇 |
1998年 | 610篇 |
1997年 | 591篇 |
1996年 | 512篇 |
1995年 | 474篇 |
1994年 | 446篇 |
1993年 | 391篇 |
1992年 | 466篇 |
1991年 | 477篇 |
1990年 | 465篇 |
1989年 | 430篇 |
1988年 | 446篇 |
1987年 | 433篇 |
1986年 | 379篇 |
1985年 | 451篇 |
1984年 | 486篇 |
1983年 | 349篇 |
1982年 | 394篇 |
1981年 | 380篇 |
1980年 | 326篇 |
1979年 | 408篇 |
1978年 | 386篇 |
1977年 | 404篇 |
1976年 | 392篇 |
1975年 | 348篇 |
1974年 | 328篇 |
1973年 | 343篇 |
排序方式: 共有10000条查询结果,搜索用时 46 毫秒
991.
Lee KJ Mao S Sun C Gao C Blixt O Arrues S Hom LG Kaufmann GF Hoffman TZ Coyle AR Paulson J Felding-Habermann B Janda KD 《Journal of the American Chemical Society》2002,124(42):12439-12446
Overexpression of the cell-surface glycosphingolipid G(M3) is associated with a number of different cancers, including those of the skin, colon, breast, and lung. Antibodies against the G(M3) epitope have potential application as therapeutic agents in the treatment of these cancers. We describe the chemoenzymatic synthesis of two G(M3)-derived reagents and their use in the panning of a phage-displayed human single-chain Fv (scFv) antibody library derived from the blood of cancer patients. Three scFv-phage clones, GM3A6, GM3A8, and GM3A15, were selected for recombinant expression and were characterized using BIAcore and flow cytometry. BIAcore measurements using the purified, soluble scFvs yielded dissociation constants (K(d)) ranging from 4.2 x 10(-7) to 2.1 x 10(-5) M. Flow cytometry was used to evaluate the ability of each scFv to discriminate between normal human cells (human dermal fibroblast, HDFa), melanoma cells (HMV-1, M21, and C-8161), and breast cancer cells (BCM-1, BCM-2, and BMS). GM3A6 displayed cross-reactivity with normal cells, as well as tumor cells, and GM3A15 possessed little or no binding activity toward any of the cell lines tested. However, GM3A8 bound to five of the six tumor cell lines and showed no measurable reactivity against the HDFa cells. Hence, we have demonstrated that a synthetic G(M3) panning reagent can be used to isolate a fully human scFv that is highly specific for native G(M3) on the surface of tumor cells. The result is a significant step toward effective immunotherapies for the treatment of cancer. 相似文献
992.
Z. I. Ermakova A. N. Gritsenko S. V. Zhuravlev 《Chemistry of Heterocyclic Compounds》1974,10(3):324-326
Quaternary salts of imidazo[4,5,1-k,l]phenothiazine were reduced with potassium borohydride to 1,2-dihydro-2-methylimidazo[4,5,1-k,l]phenothiazine, which was converted to 1,2 dihydro-2-methylimidazo[4,5,1-k,l]phenothiazine-1-thione and 1-methylamino-10-formylphenothiazine. The latter was hydrolyzed to 1-methylaminophenothiazine, which was also obtained by reduction of methyl phenothiazine-1-carbamate. The PMR and IR spectra of some of the derivatives are discussed.See [1] for communication XXXV.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 372–374, March, 1974. 相似文献
993.
M. Yu. Burylin Z. A. Temerdashev V. P. Polishchuchenko 《Journal of Analytical Chemistry》2002,57(7):595-600
A procedure was developed for the preconcentration of arsine on palladium-containing adsorbents followed by the determination of arsenic by electrothermal atomic absorption spectrometry. Aqueous suspensions of the adsorbent were placed in a graphite furnace at the determination step. The selection of the adsorbent was substantiated; adsorption properties of palladium-containing adsorbents were studied to validate their modifying properties. The absolute and concentration limits of detection for arsenic were 28 pg and 12 ng/L, respectively (sample volume of 100 mL). 相似文献
994.
S. Stichleutner E. Kuzmann Z. Homonnay Z. Klencsár A. Vértes K. Havancsák W. T. König O. Heiml G. Gritzner 《Journal of Radioanalytical and Nuclear Chemistry》2004,261(1):133-135
57Fe Mössbauer spectroscopy was used to study the effects of heavy ion irradiation on (Bi0.93Pb0.17)Sr1.9Ca2.05(Cu1.02Fe0.01)3Oy superconductors. The Mössbauer spectra of the irradiated superconductor showed significant changes in the subspectra belonging to different Cu microenvironments into which Fe ions were substituted. The relative occurrence of Fe occupying the square pyramidal fivefold oxygen coordinated Cu sites decreased while Fe3 + substituting the square planar fourfold oxygen coordinated Cu sites increased upon bombardment by 246 MeV 86Kr8+ ions. This observation was interpreted on the basis of partial replacement of the apical oxygen atoms in the square pyramids surrounding one of the Cu sites. Such oxygen vacancies create additional square planar coordination sites for Cu. These results also support the covalent character of Cu-O bonds in the superconducting layer as well as the ionic character of bond of apical oxygen to Cu. 相似文献
995.
The interaction of dimethyltin dichloride (Me2SnCl2) with calf thymus DNA was studied at 27 °C, pH 7.6 using various techniques including isothermal titration calorimetry (ITC) and UV-Vis, fluorescence and IR spectrophotometries. The binding isotherm and enthalpy curve for Me2SnCl2-DNA interaction was a biphasic transition process. This was determined by the analysis of the binding data with the Hill equation. The first phase of the enthalpy curve (exothermic process) was consistent with the first set of binding site, the second phase (endothermic process, less exothermicity) was consistent with second set of binding site from the cited interactions. Our results showed that the first set of binding sites is occupied by one mole of ligand bound per near 1 base pair of DNA. The DNA-ethidium bromide (EB) complex, in the presence of Me2SnCl2, caused the quenching of the fluorescence emission. The Scatchard plots illustrated a non-intercalating manner for such quenching. The DNA-EB complex results indicated that the binding of Me2SnCl2 is with the phosphate groups of DNA at low ligand concentrations (<9 mM). This was confirmed with the IR spectrophotometric spectra. However, the binding at higher ligand concentrations (>9 mM) was with the base groups of DNA. Therefore, these results suggest that the Me2SnCl2 binding to DNA at low concentrations occurs through an outside interaction by an exothermic process. However, the partial unfolding of the DNA caused at higher concentrations of Me2SnCl2 is through an endothermic process involving interactions with the base groups. 相似文献
996.
Darr JA Guo ZX Raman V Bououdina M Rehman IU 《Chemical communications (Cambridge, England)》2004,(6):696-697
For the first time, the MOCVD technique has been used to deposit carbonated hydroxyapatite onto Ti6AL4V substrates using volatile monomeric (liquid) complexes [Ca(beta-diketonate)(2)(L)] and P(OEt)(3). 相似文献
997.
A formal total synthesis of cephalotaxine (CET), the parent structure of antileukemia Cephalotaxus alkaloids, was achieved through a novel synthesis of the pentacyclic amino enone 4 by a rapid annulation of readily available beta-(3,4-methylenedioxy)phenethylamine (2), delta-valerolactone, and bromoacetone. 相似文献
998.
Differential thermal analysis and thermogravimetry were used to evaluate the effect of some additives, such as CaSO4, CaCl2 and silica fume amorphous silica from ferrosilicon synthesis on the mechanism and kinetics of reactions occurring in fly
ash-Ca(OH)2 system. The accelerating role of these additives was demonstrated from the data relating to Ca(OH)2 consumption in hydrated pastes, determined by TG measurements.
This revised version was published online in July 2006 with corrections to the Cover Date. 相似文献
999.
Solid-state synthesis of a conducting polythiophene via an unprecedented heterocyclic coupling reaction 总被引:2,自引:0,他引:2
Meng H Perepichka DF Bendikov M Wudl F Pan GZ Yu W Dong W Brown S 《Journal of the American Chemical Society》2003,125(49):15151-15162
Prolonged storage ( approximately 2 years) or gentle heating (50-80 degrees C) of crystalline 2,5-dibromo-3,4-ethylenedioxythiophene (DBEDOT) affords a highly conducting, bromine-doped poly(3,4-ethylenedioxythiophene) (PEDOT), as confirmed by solid-state NMR, FTIR, CV, and vis-NIR spectroscopies. The novel solid-state polymerization (SSP) does not occur for 2,5-dichloro-3,4-ethylenedioxythiophene (DCEDOT), and requires a much higher temperature (>130 degrees C) for 2,5-diiodo-3,4-ethylenedioxythiophene (DIEDOT). X-ray structural analysis of the above dihalothiophenes reveals short Hal.Hal distances between adjacent molecules in DBEDOT and DIEDOT, but not in DCEDOT. The polymerization may also occur in the melt but is significantly slower and leads to poorly conductive material. Detailed studies of the reaction were performed using ESR, DSC, microscopy, and gravimetric analyses. SSP starts on crystal defect sites; it is exothermic by 14 kcal/mol and requires activation energy of approximately 26 kcal/mol (for DBEDOT). The temperature dependence of the conductivity of SSP-PEDOT (sigma(rt) = 20-80 S/cm) reveals a slight thermal activation. It can be further increased by a factor of 2 by doping with iodine. Using this approach, thin films of PEDOT with conductivity as high as 20 S/cm were fabricated on insulating flexible plastic surfaces. 相似文献
1000.
This study presented results on reduction of alumina
supported chromium and platinum–chromium catalysts using temperature
programmed reduction method (TPR). It has been shown that catalysts after
earlier oxidation step but without calcinations one undergo reduction in lower
temperature in comparison to calcined only catalysts. Moreover, addition platinum
to Cr/Al2O3 catalysts also caused
decrease of reduction temperature. It has been observed that over the examined
catalysts oxidation CO to CO2 and reduction CO to CH4
occurs. However, on Pt–Cr catalysts both reactions proceed at lower
temperature compare to Cr catalysts. 相似文献