全文获取类型
收费全文 | 90225篇 |
免费 | 16927篇 |
国内免费 | 9230篇 |
专业分类
化学 | 61654篇 |
晶体学 | 916篇 |
力学 | 5761篇 |
综合类 | 529篇 |
数学 | 10199篇 |
物理学 | 37323篇 |
出版年
2024年 | 344篇 |
2023年 | 2048篇 |
2022年 | 3302篇 |
2021年 | 3456篇 |
2020年 | 3938篇 |
2019年 | 3523篇 |
2018年 | 3223篇 |
2017年 | 2876篇 |
2016年 | 4598篇 |
2015年 | 4369篇 |
2014年 | 5340篇 |
2013年 | 6796篇 |
2012年 | 8236篇 |
2011年 | 8429篇 |
2010年 | 5559篇 |
2009年 | 5397篇 |
2008年 | 5800篇 |
2007年 | 5084篇 |
2006年 | 4778篇 |
2005年 | 3827篇 |
2004年 | 2950篇 |
2003年 | 2310篇 |
2002年 | 2118篇 |
2001年 | 1824篇 |
2000年 | 1611篇 |
1999年 | 1851篇 |
1998年 | 1601篇 |
1997年 | 1578篇 |
1996年 | 1563篇 |
1995年 | 1325篇 |
1994年 | 1152篇 |
1993年 | 996篇 |
1992年 | 860篇 |
1991年 | 783篇 |
1990年 | 644篇 |
1989年 | 503篇 |
1988年 | 370篇 |
1987年 | 310篇 |
1986年 | 327篇 |
1985年 | 262篇 |
1984年 | 154篇 |
1983年 | 117篇 |
1982年 | 101篇 |
1981年 | 57篇 |
1980年 | 42篇 |
1979年 | 15篇 |
1976年 | 1篇 |
1974年 | 1篇 |
1957年 | 31篇 |
1922年 | 1篇 |
排序方式: 共有10000条查询结果,搜索用时 0 毫秒
921.
A novel chemiluminescence (CL) flow system for the determination of quinine is described. It is based on the direct chemiluminescence reaction of quinine and cobalt(III) in sulfuric acid medium. The unstable Co(III) was on-line electrogenerated by constant-current electrolysis. The chemiluminescence intensity was linear with a quinine concentration in the range of 0.1-100 mug ml(-1). The determination limit was 3.3x10(-8) g ml(-1). The whole process could be completed in 1 min. The proposed method is suitable for automatic and continuous analysis, and has been applied successfully to the analysis of quinine in pharmaceutical preparation. 相似文献
922.
Potentiodynamic deposition of Prussian blue from a solution containing single component of ferricyanide and its mechanism investigation 总被引:1,自引:0,他引:1
Dai?Zhang Kang?Wang Dacheng?Sun Xinghua?XiaEmail author Hongyuan?Chen 《Journal of Solid State Electrochemistry》2003,7(9):561-566
Potentiodynamic techniques were used for the direct electrodeposition of Prussian blue nano-clusters from an acidic solution of ferricyanide. Electrochemical, EQCM, IR, AFM, and UV/vis measurements were carried out to characterize deposited nano-sized Prussian blue and to explore the formation mechanism. Results showed that ferricyanide could partially dissociate to free ferric and cyanide ions. The driving force of this dissociation is the formation of PB and the evolution of HCN. The optimal potential window for the potentiodynamic formation of PB from an acidic solution (pH 1.6) is between –0.5 V and 0.4 V. In addition, the influence of surface adsorption of CN- ions on the formation of PB was discussed.Dedicated to Professor W. Vielstich on the occasion of his 80th birthday. 相似文献
923.
Zhang H Paulsen ES Walker KA Krakowiak KE Dearden DV 《Journal of the American Chemical Society》2003,125(31):9284-9285
Cucurbit[6]uril forms a doubly charged complex with 1,4-butanediammonium cation that is observed using electrospray ionization Fourier transform mass spectrometry. Such 1:1 complexes are not observed for the smaller cucurbit[5]uril, which forms a 2:1 ammonium:cucurbituril complex instead. The 1:1 complex with cucurbit[6]uril is difficult to fragment via collisional activation; when it does fragment, both breakup of the cucurbituril cage and loss of the amine are observed. Further, the complex reacts with tert-butylamine via slow adduction. In contrast, nonrotaxane analogues (such as doubly charged 2:1 complexes of either protonated 1,4-butanediamine or protonated ethylenediamine with cucurbit[6]uril) fragment via easy loss of the intact amine upon collisional activation and react with tert-butylamine via rapid displacement of the original amine. On the basis of stoichiometry, fragmentation behavior, and reactivity, we conclude that the doubly charged complex of cucurbit[6]uril with 1,4-butanediammonium is a gas-phase pseudorotaxane. 相似文献
924.
Wender PA Hegde SG Hubbard RD Zhang L 《Journal of the American Chemical Society》2002,124(18):4956-4957
(-)-Laulimalide (1), a structurally novel macrolide isolated in trace amounts from marine sponges, promotes abnormal tubulin polymerization and apoptosis in vitro, with a similar mode of action to that of Taxol(R), but with potentially less susceptibility to multidrug resistance. Herein, a flexible and convergent asymmetric synthesis of (-)-laulimalide is described. This synthesis featured a highly diastereoselective Sakurai reaction of 2 with 3 and a regioselective macrolactonization of an unprotected vicinal diol. Laulimalide was synthesized in 25 steps (longest linear; 36 overall) in 3.5% overall yield, providing a uniquely short and efficient route to 1 and its analogues. 相似文献
925.
Squalene synthase (SQase) catalyzes two consecutive reactions in sterol biosynthesis. The first is the condensation of two molecules of farnesyl diphosphate (FPP) to form a cyclopropylcarbinyl intermediate, presqualene diphosphate (PSPP). The subsequent conversion of PSPP to squalene (SQ) involves an extensive rearrangement of the carbon skeleton and a NADPH-dependent reduction. Incubation of a truncated soluble form of recombinant yeast SQase with FPP in buffer lacking NADPH gave (1R,2R,3R)-PSPP. As the incubation continued, SQase catalyzed the subsequent conversion of PSPP to a mixture of triterpenes. Two of the major products, (Z)-dehydrosqualene (DSQ) and (R)-12-hydroxysqualene (HSQ), have the same 1'-1 linkage between the farnesyl units from FPP that is found in squalene. The other major product, (10S,13S)-10-hydroxybotryococcene (HBO), has a 1'-3 linkage between the farnesyl units. Small quantities of (S)-HSQ and (10R,13S)-HBO were also formed. Three additional triterpenes, the allylic isomers of HSQ and HBO, and an unidentified alcohol were produced in minor amounts. A methyl ether corresponding to HSQ was detected when methanol was present in the incubation buffer. These compounds are the expected "solvolysis" products from PSPP. They provide strong support for mechanisms that propose cyclopropylcarbinyl cations as intermediates in the SQase-catalyzed rearrangement of PSPP to SQ and unambiguously demonstrate that the catalytic machinery of SQase is capable of synthesizing a variety of irregular isoprenoids. 相似文献
926.
本文研究了氢硼酸根(B_(12)H_(12)~(2-)、B_(10)H_(10)~(1-)、B_(11)H_(14)~-)和π-芳烃-π-环戊二烯基铁阳离子的反应,合成了36个氢硼酸π-芳烃-π-环戊二烯基铁化合物。通过元素分析和红外光谱测定确定了化合物的组成。部份化合物还作了~1H NMR鉴定。对化合物的性质,包括它们的热行为,进行了较详细的研究。DTA仪测得的结果表明,(1)当阳离子相同时,化合物的热稳定性的顺序为:[ArFeC_5H_5]_2B_(12)H_(12)>[ArFeC_5H_5]_2B_(10)H_(10)>[ArFeC_5H_5]B_(11)H_(14);(2)当氢硼酸根相同时,其热稳定性受芳环上取代基的影响。 相似文献
927.
乳状液法制备憎液溶胶Ⅰ.BaCO_3均匀粒子的制备 总被引:1,自引:0,他引:1
均匀胶体粒子的形成,除与反应条件(反应物浓度、陈化时间和温度、介质种类等)有关外,反应体系的环境也影响最终产物的形态,《至结晶结构.气溶胶法和微乳液法正是利用微环境中的‘水池效应”;分别制备出球形亚微米和纳米级的均匀粒子[‘-‘]、这些方法与水解法和相转化法等方法比较,反应物浓度要大几个数量级,而反应时间却短很多,因而受到研究人员的关注.乳状液也能提供亚微米、微米及以上级的微环境,因此,可以应用O/W乳状液乳液中的聚合反应制备亲液的分散体系.然而,极少有关利用w/O乳状液制备僧液溶胶的报导问;最近… 相似文献
928.
Cp2TiCl2及(MeCp)2TiCl2在Et3N或NaNH2存在下与苄醇类化合物反应,高产率地合成了6个未见文献报道的二茂钛(Ⅳ)苄氧基衍生物,甲基二茂钛(Ⅳ)苄氧基化合物,经元素分析,HNMR和IR光谱确定了化合物的结构,并对其部分性质进行了讨论。 相似文献
929.
Reactions in the CsCl? TiCl3? Ti system afford CsTiCl3 (CsNiCl3 type, a = 7.3086(7) Å, c = 6.0670(8) Å) and the new phase CsTi2Cl7, the structure of which was determined by single crystal X-ray diffraction means (P2/c, Z = 2, a = 7.0076(4) Å, b = 6.2256(4) Å, c = 12.000(2) Å, β = 92.175(6)°, R/Rw = 0.026/0.035 for 1403 reflections, 2Θ ≤ 60°, MoKα). The structure can be generated by condensation of TiCl6 groups first through cis edges to form TiCl2Cl4/2 ribbons and then by interconnection of these with one chlorine per titanium to give layers, viz., [Ti(Cl)Cl4/2Cl1/2]?. The remaining, singly bonded chlorine projects into the interlayer region and has a Ti? Cl distance 0.208 Å less than the average for the five, 2.466 Å, reflecting significant pi bonding of the chlorine to titanium. Possible interaction of the d orbitals on adjacent titanium(III) atoms is also considered. 相似文献
930.