全文获取类型
收费全文 | 2619篇 |
免费 | 130篇 |
国内免费 | 23篇 |
专业分类
化学 | 1692篇 |
晶体学 | 26篇 |
力学 | 58篇 |
综合类 | 16篇 |
数学 | 272篇 |
物理学 | 429篇 |
无线电 | 279篇 |
出版年
2023年 | 20篇 |
2022年 | 17篇 |
2021年 | 40篇 |
2020年 | 53篇 |
2019年 | 60篇 |
2018年 | 49篇 |
2017年 | 34篇 |
2016年 | 63篇 |
2015年 | 55篇 |
2014年 | 68篇 |
2013年 | 152篇 |
2012年 | 168篇 |
2011年 | 175篇 |
2010年 | 90篇 |
2009年 | 112篇 |
2008年 | 188篇 |
2007年 | 161篇 |
2006年 | 156篇 |
2005年 | 176篇 |
2004年 | 131篇 |
2003年 | 105篇 |
2002年 | 110篇 |
2001年 | 32篇 |
2000年 | 37篇 |
1999年 | 26篇 |
1998年 | 30篇 |
1997年 | 25篇 |
1996年 | 31篇 |
1995年 | 22篇 |
1994年 | 25篇 |
1993年 | 18篇 |
1992年 | 14篇 |
1991年 | 13篇 |
1990年 | 28篇 |
1989年 | 16篇 |
1988年 | 18篇 |
1987年 | 18篇 |
1986年 | 10篇 |
1985年 | 32篇 |
1984年 | 21篇 |
1983年 | 20篇 |
1982年 | 21篇 |
1981年 | 19篇 |
1980年 | 22篇 |
1979年 | 13篇 |
1978年 | 8篇 |
1977年 | 14篇 |
1976年 | 11篇 |
1975年 | 9篇 |
1974年 | 11篇 |
排序方式: 共有2772条查询结果,搜索用时 0 毫秒
21.
22.
23.
24.
25.
26.
Several scenarios were evaluated to explain the large "dendrimer effect" observed in the bromination of cyclohexene with H(2)O(2) and NaBr catalyzed by the addition of Frechét-type dendrimers terminating in -O(CH(2))(3)SePh groups. Although phenylseleninic acid was an efficient catalyst for the oxidation of NaBr with H(2)O(2), first-order rate constants for the selenoxide elimination were too small to produce PhSeO(2)H at a rate sufficient to explain the rates of catalysis and no dendrimer effect was observed in the rates of selenoxide elimination. An induction period was observed using 1-SePh as a catalyst for the oxidation of Br(-) with H(2)O(2). The addition of preformed selenoxide 1-Se(=O)Ph gave immediate catalysis with no induction period. However, rates of oxidation of the selenides with H(2)O(2) under homogeneous or biphasic conditions or with t-BuOOH under homogeneous conditions were too slow to account for the rates of catalysis, and no dendrimer effect was observed in the rates of oxidation. The primary oxidant for converting selenides to selenoxides was "Br(+)" produced initially by the uncatalyzed background reaction of H(2)O(2) with NaBr and then produced catalytically following formation of selenoxide groups. Autocatalysis is observed, and the rate of oxidation increases with the number of SePh groups. Autocatalysis is the source of the large dendrimer effect observed with the SePh series of catalysts. 相似文献
27.
A series of new complexes, Mo(2)O(2)S(2)[S(2)P(OR)(2)](2) (where R = Et, n-Pr, i-Pr) and Mo(2)O(2)S(2)[S(2)POGO](2) (where G = -CH(2)CMe(2)CH(2)-, -CMe(2)CMe(2)-) have been prepared by the dropwise addition of an ethanolic solution of the ammonium or sodium salt of the appropriate O,O-dialkyl or -alkylene dithiophosphoric acid, or the acid itself, to a hot aqueous solution of molybdenum(V) pentachloride. The complexes were also formed by heating solutions of Mo(2)O(3)[S(2)P(OR)(2)](4) or Mo(2)O(3)[S(2)POGO](4) species in glacial acetic acid. The Mo(2)O(2)S(2)[S(2)P(OR)(2)](2) and Mo(2)O(2)S(2)[S(2)POGO](2) compounds were characterized by elemental analyses, (1)H, (13)C, and (31)P NMR, and infrared and Raman spectroscopy, as were the 1:2 adducts formed on reaction with pyridine. The crystal structures of Mo(2)O(2)S(2)[S(2)P(OEt(2))](2), Mo(2)O(2)S(2)[S(2)P(OEt)(2)](2).2NC(5)H(5), and Mo(2)O(3)[S(2)P(OPh)(2)](4) were determined. Mo(2)O(2)S(2)[S(2)P(OEt)(2)](2) (1) crystallizes in space group C2/c, No. 15, with cell parameters a = 15.644(3) ?, b = 8.339(2) ?, c = 18.269(4) ?, beta = 103.70(2) degrees, V = 2315.4(8) ?(3), Z = 4, R = 0.0439, and R(w) = 0.0353. Mo(2)O(2)S(2)[S(2)P(OEt)(2)](2).2NC(5)H(5) (6) crystallizes in space group P&onemacr;, No. 2, with the cell parameters a = 12.663(4) ?,b = 14.291(5) ?, c = 9.349(3) ?, alpha = 100.04(3) degrees, beta = 100.67(3) degrees, gamma = 73.03(3) degrees V = 1557(1) ?(3), Z = 2, R = 0.0593, and R(w) = 0.0535. Mo(2)O(3)[S(2)P(OPh)(2)](4) (8) crystallizes in space group P2(1)/n, No. 14, with cell parameters a = 15.206(2)?, b = 10.655(3)?, c = 19.406(3)?, beta = 111.67(1) degrees, V = 2921(1)?(3), Z = 2, R = 0.0518, R(w) = 0.0425. The immediate environment about the molybdenum atoms in 1 is essentially square pyramidal if the Mo-Mo interaction is ignored. The vacant positions in the square pyramids are occupied by two pyridine molecules in 6, resulting in an octahedral environment with very long Mo-N bonds. The terminal oxygen atoms in both 1 and 6 are in the syn conformation. In 8, which also has a distorted octahedral environment about molybdenum, two of the dithiophosphate groups are bidentate as in 1 and 6, but the two others have one normal Mo-S bond and one unusually long Mo-S bond. 相似文献
28.
29.
Badham NF Mendelson WL Allen A Diederich AM Eggleston DS Filan JJ Freyer AJ Killmer LB Kowalski CJ Liu L Novack VJ Vogt FG Webb KS Yang J 《The Journal of organic chemistry》2002,67(15):5440-5443
A convenient two-step homologation of both aliphatic and aromatic ketones to the corresponding carboxylic acid has been developed. First ketones were converted to epoxynitriles with the Darzens reaction. Second, a Lewis acid mediated rearrangement of these epoxynitriles with lithium bromide was achieved to give homologated secondary alkanoic acids (as well as aryl-alkanoic) in good yields. The mechanism and the scope of the rearrangement reaction were investigated. This strategy constitutes a two-step homologation of ketones to secondary carboxylic acids. 相似文献
30.
作为一种新型结构材料,非晶态合金的韧性需要进一步提高.提高非晶态合金韧性的方法有引入枝晶相、调整其成分改变其泊松比影响其剪切带衍生、裂纹扩展等.本文通过表面机械加工的方法来调控非晶态合金的微观结构及韧性.我们采用真空电弧熔炼、亚稳态薄板离心浇铸系统制备了Zr52.5Cu17.9Ni14.6Al10Ti5(原子百分比)(Vit105)非晶合金板,并用表面机械研磨处理方法 (surface mechanical attrition treatment, SMAT),在Vit105板上形成纳米尺度局域类晶体序结构.基于差示扫描量热分析、纳米压痕实验,我们发现SMAT处理后的Vit105合金板表面附近弛豫焓更低,微观结构更加均匀、稳定.通过显微维氏硬度计测试,发现SMAT处理后样品的表面附近硬度增大,硬度值分布也更均匀.通过三点弯断裂实验,可得到SMAT处理后合金板缺口韧度值从70.7±4.7 MPa·m1/2提高到112.8±3.7 MPa·m1/2<... 相似文献