全文获取类型
收费全文 | 68812篇 |
免费 | 5998篇 |
国内免费 | 11019篇 |
专业分类
化学 | 46161篇 |
晶体学 | 1878篇 |
力学 | 704篇 |
综合类 | 424篇 |
数学 | 12706篇 |
物理学 | 13608篇 |
无线电 | 10348篇 |
出版年
2024年 | 224篇 |
2023年 | 1346篇 |
2022年 | 1894篇 |
2021年 | 2158篇 |
2020年 | 2158篇 |
2019年 | 2229篇 |
2018年 | 1840篇 |
2017年 | 2206篇 |
2016年 | 2264篇 |
2015年 | 2025篇 |
2014年 | 2801篇 |
2013年 | 5589篇 |
2012年 | 3990篇 |
2011年 | 4618篇 |
2010年 | 3923篇 |
2009年 | 4776篇 |
2008年 | 4742篇 |
2007年 | 4857篇 |
2006年 | 4407篇 |
2005年 | 3656篇 |
2004年 | 3385篇 |
2003年 | 2916篇 |
2002年 | 2410篇 |
2001年 | 1953篇 |
2000年 | 1777篇 |
1999年 | 1545篇 |
1998年 | 1329篇 |
1997年 | 1093篇 |
1996年 | 1076篇 |
1995年 | 1046篇 |
1994年 | 949篇 |
1993年 | 771篇 |
1992年 | 677篇 |
1991年 | 521篇 |
1990年 | 393篇 |
1989年 | 339篇 |
1988年 | 264篇 |
1987年 | 190篇 |
1986年 | 165篇 |
1985年 | 206篇 |
1984年 | 159篇 |
1983年 | 90篇 |
1982年 | 133篇 |
1981年 | 158篇 |
1980年 | 121篇 |
1979年 | 107篇 |
1978年 | 91篇 |
1977年 | 87篇 |
1976年 | 70篇 |
1973年 | 35篇 |
排序方式: 共有10000条查询结果,搜索用时 0 毫秒
971.
水解胶原蛋白热氧化及CaSO4形成机理探讨;水解胶原蛋白; L-抗坏血酸; H2O2; 热氧化; CaSO4 相似文献
972.
973.
Yizhen Tang Jingyu Sun Xiujuan Jia Hao Sun Xiumei Pan Rongshun Wang 《Journal of computational chemistry》2010,31(7):1520-1527
The reaction of N2H4 with OH has been investigated by quantum chemical methods. The results show that hydrogen abstraction mechanism is more feasible than substitution mechanism thermodynamically. The calculated rate constants agree with the available experimental data. The calculated results show that the variational effect is small at lower temperature region, while it becomes significant at higher temperature region. On the other hand, the small‐curvature tunneling effect may play an important role in the temperature range 220?3000 K. Moreover, the calculated rate constants show negative temperature dependence at the temperatures below 500 K, which is in accordance with Vaghjiani's report that slightly negative temperature dependence is found over the temperature range of 258?637 K. The mechanism of the major product (N2H3) with OH has also been investigated theoretically to understand the title reaction thoroughly. © 2009 Wiley Periodicals, Inc. J Comput Chem, 2010 相似文献
974.
Yoshihiro Sugi 《中国化学会会志》2010,57(1):1-13
Steric interaction of reagents with zeolites was studied in isopropylation, sec‐butylation, and tert‐butylation of naphthalene (NP) over several large‐pore zeolites to elucidate the mechanism of selective catalysis. Selectivities for dialkylnaphthalene (DAN) isomers were influenced by the type of zeolite and bulkiness of alkylating agent. Selective formation of β,β‐ and 2,6‐diisopropylnaphthalene (DIPN) occurred only over H‐mordenite (MOR) in the isopropylation of NP using propene; bulky transition states of α,α‐ and α,β‐DIPN are excluded because of steric restriction by the channels, resulting in selective formation of β,β‐ and 2,6‐DIPN. However, low selectivities for β,β‐ and 2,6‐DIPN were observed over the zeolites, SSZ‐24 (AFI), SSZ‐55 (ATS), and SSZ‐42 (IFR) with 12‐membered‐ring (12‐MR) pore entrances of one‐dimensional channels, CIT‐5 (CFI), UTD‐1 (DON), and SSZ‐53 (SFH) with 14‐membered‐ring (14‐MR) pore entrances of one‐dimensional channels, and Y‐zeolite (FAU), zeolite β (BEA), and CIT‐1 (CON) with 12‐MR pore entrances of three‐dimensional channels, because their channels are too large for the exclusion of bulky isomers. Catalysis over these zeolites occurs under kinetic and/or thermodynamic control, resulting in predominant formation of α,α‐ and α,β‐DIPN at lower temperatures and an increase of the stable isomer β,β‐DIPN at higher temperatures. The selectivities for β,β‐ and 2,6‐DAN were enhanced with the increase in bulkiness of alkylating agents: 1‐butene for sec‐butylation and 2‐methylpropene for tert‐butylation. In particular, β,β‐di‐tert‐butylnaphthalene (DTBN) was selectively formed in the tert‐butylation. The selectivities for β,β‐ and 2,6‐DAN were enhanced even in large channels: the transition states of the least bulky isomers only fit the channels because other bulky isomers are excluded by steric restriction of the channels. However, tert‐butylation over FAU, BEA, and CON had selectivities for 2,6‐DTBN of around 50–60%, although selectivities for β,β‐DTBN were almost 100% selectivity; these zeolites can hardly recognize the differences between 2,6‐ and 2,7‐DTBN. The results indicate that the fitting of the least bulky isomers to zeolite channels, leading to the exclusion of other bulky isomers, is essential for highly shape‐selective catalysis. 相似文献
975.
Yanfang Shen Tianying Xiong Hao Du Huazi Jin Jianku Shang Ke Yang 《Journal of Sol-Gel Science and Technology》2009,50(1):98-102
P, N, and Mo ternary co-doped nano TiO2 photocatalysts ((P, N, Mo)-TiO2) were prepared by a single step sol–gel method, which show much enhanced photocatalytic activities over Mo-TiO2, (P, N)-TiO2, un-doped TiO2 and Degussa P25 under visible light irradiation. The degradation rate of 0.72Mo–P-TiO2 is as high as 65.3%, which is about 6.7 times of that of Degussa P25. Possible reasons for the improvement of photocatalytic
activities were analyzed. 相似文献
976.
Christopher M. Burba Roger Frech Agneta Seidel Lennart Häggström Anton Nytén John O. Thomas 《Journal of Solid State Electrochemistry》2009,13(8):1267-1272
The first discharge of the Li+ ion anode material LiSn2(PO4)3 was investigated with Mössbauer spectroscopy and electrochemical techniques. Mössbauer spectroscopy provided insight into the structure of the tin atoms of the fully discharged anode materials. Spectra consist of overlapping peaks, which are assigned to noncrystalline β-Sn and Li–Sn alloy domains. An analysis of the relative intensities of the Mössbauer spectra shows the relative abundance of β-Sn increases at the expense of the Li–Sn alloy as the discharge rate increases. Cell polarization occurs at higher discharge rates, leading to inefficient electrode utilization and poor cycling performance. Sluggish Li+ ion diffusion through the amorphous Li3PO4 network that is formed early in the discharge process might be responsible for the poor electrochemical performance and the accumulation of unalloyed tin. 相似文献
977.
Stefano Freguia Masaki Masuda Seiya Tsujimura Kenji Kano 《Bioelectrochemistry (Amsterdam, Netherlands)》2009,76(1-2):14
Lactococcus lactis is a gram-positive, normally homolactic fermenter that is known to produce several kinds of membrane associated quinones, which are able to mediate electron transfer to extracellular electron acceptors such as Fe3+, Cu2+ and hexacyanoferrate. Here we show that this bacterium is also capable of performing extracellular electron transfer to anodes by utilizing at least two soluble redox mediators, as suggested by the two-step catalytic current developed. One of these two mediators was herein suggested to be 2-amino-3-dicarboxy-1,4-naphthoquinone (ACNQ), via evaluation of standard redox potential, ability of the bacterium to exploit the quinone when exogenously provided, as well as by high performance liquid chromatography coupled with UV spectrum analysis. During electricity generation, L. lactis slightly deviated from its normal homolactic metabolism by excreting acetate and pyruvate in stoichiometric amounts with respect to the electrical current. In this metabolism, the anode takes on the role of electron sink for acetogenic fermentation. The finding that L. lactis self-catalyses anodic electron transfer by excretion of redox mediators is remarkable as the mechanisms of extracellular electron transfer by pure cultures of gram-positive bacteria had previously never been elucidated. 相似文献
978.
Poly(styrene-co-glycidyl methacrylate) latex microspheres with uniform size and high-density epoxy groups on the surface were prepared by soap-free emulsion polymerization with batch wise operation mode in the presence of 2.2′- azobis(2-methylpropionamidine) dihydrochloride as an initiator.The kinetics of soap-free emulsion polymerization and the effects of polymerization factors were examined.In addition,the optimum polymerization conditions of poly(styrene-co- glycidyl methacrylate) latex microspheres ... 相似文献
979.
山楂果和桑枝提取物中总黄酮含量的Fe(phen)2+3探针共振瑞利散射法测定 总被引:2,自引:0,他引:2
在pH值约为8.0的BR缓冲介质中,桑色素、槲皮素和芦丁等黄酮类物质能与Fe(phen)2+3反应形成离子缔合物,此时将引起共振瑞利散射(RRS)显著增强,最大RRS波长均位于310 nm. 在一定范围内散射强度(ΔI)与黄酮类物质的浓度成正比,据此可以建立用Fe(phen)2+3测定某些黄酮类物质的新RRS法. 对桑色素、槲皮素和芦丁的检出限(3σ/K)分别为1.25×10-7 mol/L(37.74 μg/L),1.80×10-7 mol/L(54.42 μg/L),2.72×10-7 mol/L(167.30 μg/L). 研究了反应的适宜条件和影响因素,考察了共存物质的影响. 结果表明,方法有较好的选择性.分别以芦丁和桑色素为对照品测定了中药材山楂果和桑枝中的总黄酮含量,对反应机理进行了初步探讨. 相似文献
980.
Synthesis of magnetic nickel spinel ferrite nanospheres by a reverse emulsion-assisted hydrothermal process 总被引:1,自引:0,他引:1
Nickel ferrite nanospheres were successfully synthesized by a reverse emulsion-assisted hydrothermal method. The reverse emulsion was composed of water, cetyltrimethyl ammonium bromide, polyoxyethylene(10)nonyl phenyl ether, iso-amyl alcohol and hexane. During the hydrothermal process, β-FeO(OH) and Ni0.75Fe0.25(CO3)0.125(OH)2·0.38H2O (INCHH) nanorods formed first and then transformed into nickel spinel ferrite nanospheres. The phase transformation mechanism is proposed based on the results of X-ray powder diffraction, transmission electron microscopy and energy-dispersive X-ray spectroscopy, etc. Nickel ferrite may form at the end of the INCHH nanorods or from the solution accompanied by the dissolution of β-FeO(OH) and INCHH nanorods. The X-ray photoelectron spectroscopy analysis shows that a few Fe3+ ions have been reduced to Fe2+ ions during the formation of nickel ferrite. The maximum magnetization of the nickel ferrite nanospheres obtained after hydrothermal reaction for 30 h is 55.01 emu/g, which is close to that of bulk NiFe2O4. 相似文献