全文获取类型
收费全文 | 70716篇 |
免费 | 5988篇 |
国内免费 | 14580篇 |
专业分类
化学 | 70142篇 |
晶体学 | 2107篇 |
力学 | 676篇 |
综合类 | 629篇 |
数学 | 3326篇 |
物理学 | 14404篇 |
出版年
2024年 | 139篇 |
2023年 | 1097篇 |
2022年 | 1939篇 |
2021年 | 2410篇 |
2020年 | 2453篇 |
2019年 | 2309篇 |
2018年 | 1901篇 |
2017年 | 2425篇 |
2016年 | 2641篇 |
2015年 | 2343篇 |
2014年 | 2998篇 |
2013年 | 6492篇 |
2012年 | 4705篇 |
2011年 | 4602篇 |
2010年 | 3978篇 |
2009年 | 4774篇 |
2008年 | 4655篇 |
2007年 | 4903篇 |
2006年 | 4617篇 |
2005年 | 4117篇 |
2004年 | 3869篇 |
2003年 | 3198篇 |
2002年 | 2674篇 |
2001年 | 2119篇 |
2000年 | 2000篇 |
1999年 | 1629篇 |
1998年 | 1369篇 |
1997年 | 1261篇 |
1996年 | 1112篇 |
1995年 | 1077篇 |
1994年 | 962篇 |
1993年 | 781篇 |
1992年 | 747篇 |
1991年 | 555篇 |
1990年 | 403篇 |
1989年 | 380篇 |
1988年 | 298篇 |
1987年 | 201篇 |
1986年 | 154篇 |
1985年 | 158篇 |
1984年 | 139篇 |
1983年 | 63篇 |
1982年 | 104篇 |
1981年 | 116篇 |
1980年 | 84篇 |
1979年 | 85篇 |
1978年 | 65篇 |
1977年 | 54篇 |
1976年 | 33篇 |
1973年 | 35篇 |
排序方式: 共有10000条查询结果,搜索用时 31 毫秒
991.
992.
Xavier Fradera Michael De Rosa Modesto Orozco F. Javier Luque 《Theoretical chemistry accounts》2004,111(2-6):223-230
The tautomeric preferences of the conjugated acids of 2-aminopyrrole derivatives have been examined both in the gas phase and in aqueous solution by using a combination of quantum mechanical, self-consistent reaction field and Monte Carlo–free-energy perturbation methods. The results show that the nature of substituents, the solvent and the presence of cosolute are relevant factors in modulating the relative stability between the tautomeric conjugate acids protonated at the heterocyclic ring and at the exocyclic amino nitrogen. Thus, attachment of electron-withdrawing groups to the ring, solvation in polar solvents, and the presence of negatively charged cosolutes tend to favor protonation at the exocyclic amino nitrogen. Nevertheless, none of these factors alone suffice to change the tautomeric preference for the ring-protonated forms. The results point out that the concerted occurrence of the three factors is necessary to shift the tautomeric preference towards the conjugated species protonated at the exocyclic nitrogen.Contribution to the Jacopo Tomasi Honorary Issue 相似文献
993.
TiSiW12O40/TiO2催化合成苹果酯 总被引:33,自引:0,他引:33
以固载杂多酸盐TiSiW12O40/TiO2为多相催化剂,通过乙酰乙酸乙酯和乙二醇反应合成了苹果酯,探讨TiSiW12O40/TiO2对缩酮反应的催化活性,较系统地研究了原料量比,催化剂肜量,反应时间诸因素对产品收率的影响,实验表明:TiSiW12O40/TiO2是合成苹果酯的良好催化剂,在n(乙酰乙酸乙酯):n(乙二醇)=1:1.5,催化剂用量为反应物料总质量的1.0%,环己烷为带水剂,反应时间50min的优化条件下,苹果酯的收率可达84.1%。 相似文献
994.
1-(2,6-二氯-4-硝基苯)-3-(4-硝基苯)-三氮烯与铜的显色反应研究及其应用 总被引:9,自引:0,他引:9
研究了新试剂1-(2,6-二氯-4-硝基苯)-3-(4-硝基苯)-三氮烯(DCNPNPT)与铜(Ⅱ)显色反应。在表面活性剂Tween-80存在下,pH 9.0~10.0范围内,铜(Ⅱ)与DCNPNPT形成1:4黄色配合物,其最大吸收波长为460nm,用双峰双波长法测定,表观摩尔吸光系数为1.I×10~5L·mol~(-1)·cm~(-1)。铜(Ⅱ)含量在0~240μg·L~(-1)范围内符合比耳定律。拟定方法用于铜矿和环境水标样中铜的测定,结果满意。 相似文献
995.
Synthesis, structure and magnetic properties of the S=1/2, one-dimensional antiferromagnet, Y5Re2O12
Lisheng Chi 《Journal of solid state chemistry》2003,172(2):451-457
Single crystals of Y5Re2O12 have been grown, and the crystal structure has been determined by X-ray diffraction. This compound crystallizes in space group C2/m with cell dimensions of a=12.4081(10) Å b=5.6604(5)Å, c=7.4951(6) Å, β=107.837(3)°, Z=2. The final refinement led to R1=0.0238, WR2=0.0459 for 1053 observed reflections with F>4σ(F0). Edge-sharing ReO6 octahedra form infinite linear [ReO2O4/2]n chains along the b direction with alternating short and long Re-Re distances. Three crystallographically independent yttrium atoms surround O2 to form OY4 tetrahedra, which share edges and corners in the ab plane to form a two-dimensional Y5O4 network which separates the [ReO2O4/2]n magnetic chains. This compound is therefore isostructural with the series Ln5Re2O12Ln=Gd-Lu, which have been known since 1969. The average Re oxidation state is +4.5 in the chains and a reasonable, if qualitative MO scheme results in one unpaired electron per Re dimer. Consistent with this, magnetic susceptibility data can be fitted to the one-dimensional antiferromagnetic Heisenberg model with S=1/2 and parameters Jintra/k=−89(1)K, g=2.15(4) and χ(TIP)=5(1)×10−4 emu/mol. There is no sign of long-range magnetic order down to 2 K. These results are contrasted with those for the isostructural Y5Mo2O12. 相似文献
996.
Labeling experiments using several deuterated lipids were pursued to study the biosynthesis of macrocyclic isoprenoidal lipids of thermophilic methanogenic archaea, Methanothermobacter thermautotrophicus. The isopropylidene terminal of geranylgeranyl group of monomeric precursor appeared to be important for the CC bond formation at the hydrophobic end in the macrocyclic lipids. A mechanism involving a radical trigger at the allylic methyl group is proposed for this CC bond formation. 相似文献
997.
The reductions of several substituted acetophenones using supercritical 2-propanol were carried out to estimate the Hammett's reaction constant (ρ=0.33). Also, the reduction of acetophenone using supercritical deuteriated 2-propanol was carried out to determine the rate-determining step. The kinetic isotope effects were observed in the reduction using 2-deuterio-2-propanol (kH/kD=1.6) and O-deuterio-2-propanol (kH/kD=2.0). These findings suggest that the reaction proceeds via a cyclic transition state between acetophenone and 2-propanol similar to that of the Meerwein-Ponndorf-Verley reduction. 相似文献
998.
A new separation system of capillary electrophoresis for the simultaneous determination of metals by using ethylenediamine tetraacetic acid (EDTA) as complexing agent and employing vancomycin as complex selector was described. The Z-shape cell capillary electrophoresis was used to enhance the sensitivity for the determination of the complexes of Cu(Ⅱ), Ni(Ⅱ), Co(Ⅱ) and Fe(Ⅲ) with EDTA. The partial filling method (co-current mode) was used in order to increase the selectivity of the electrophoretic method, meanwhile vancomycin was not present at the detector path during the detection of metal-EDTA complexes. The vancomycin concentration, phosphate concentration and pH of the buffer strongly influenced mobility, resolution and selectivity of the studied analytes. Under the optimal condition, the relative standard deviations (n=5) of the migration time and the peak area were less than 3.14% and 7.35%, respectively. Application of the Z-shape cell capillary electrophoresis method with UV detection and vancomycin loading led to the reliable determination of these metal ions in tap water and the recoveries were 97%-101%. The detection limits based on a signal to noise ratio of 3 : 1 were found in the range of 2-10 μg·L^-1. 相似文献
999.
1000.
相转移催化合成对甲氧基肉桂酸-2-乙基己酯的研究 总被引:5,自引:1,他引:5
对甲氧基肉桂酸 2 乙基己酯是一种有效的UVB防晒剂[1 ,2 ] ,一般采用Claisen Schmidt缩合反应制得[3] ,但由于催化剂KOH处于水相 ,对反应物不能充分起到催化作用导致产率较低[4] 。我们利用乙二醇 (PEG)为相转移催化剂合成立体专一的反式对甲氧基肉桂酸 2 乙基己酯 ,产率提高到 72 .5 %。合成路线如下 :1 实验部分1 .1 仪器与试剂BIO RAPFT45 0红外光谱仪 ,用液膜法测试 ;Brurer AM 30 0超导核磁共振仪 (溶剂DC Cl3) ;MAT/44S ,GC MS型色质联用谱仪 ;试剂均为分析纯 ,上海化学试剂… 相似文献