全文获取类型
收费全文 | 3722篇 |
免费 | 105篇 |
国内免费 | 34篇 |
专业分类
化学 | 2507篇 |
晶体学 | 36篇 |
力学 | 91篇 |
数学 | 716篇 |
物理学 | 511篇 |
出版年
2021年 | 43篇 |
2020年 | 31篇 |
2019年 | 46篇 |
2018年 | 42篇 |
2017年 | 32篇 |
2016年 | 65篇 |
2015年 | 81篇 |
2014年 | 71篇 |
2013年 | 190篇 |
2012年 | 177篇 |
2011年 | 270篇 |
2010年 | 118篇 |
2009年 | 107篇 |
2008年 | 220篇 |
2007年 | 218篇 |
2006年 | 227篇 |
2005年 | 185篇 |
2004年 | 167篇 |
2003年 | 153篇 |
2002年 | 169篇 |
2001年 | 57篇 |
2000年 | 48篇 |
1999年 | 76篇 |
1998年 | 53篇 |
1997年 | 59篇 |
1996年 | 59篇 |
1995年 | 34篇 |
1994年 | 40篇 |
1993年 | 51篇 |
1992年 | 37篇 |
1991年 | 42篇 |
1990年 | 38篇 |
1989年 | 33篇 |
1988年 | 26篇 |
1987年 | 33篇 |
1986年 | 19篇 |
1985年 | 37篇 |
1984年 | 51篇 |
1983年 | 34篇 |
1982年 | 33篇 |
1981年 | 48篇 |
1980年 | 31篇 |
1979年 | 29篇 |
1978年 | 34篇 |
1977年 | 32篇 |
1976年 | 35篇 |
1975年 | 25篇 |
1974年 | 34篇 |
1973年 | 19篇 |
1972年 | 17篇 |
排序方式: 共有3861条查询结果,搜索用时 767 毫秒
21.
Summary The complexestrans-[Ru(NH3)4(H2O)PPh3](PF6)2 and [Ru(NH3)5L](PF6)2, (L=AsPh3 or SbPh3) have been isolated and characterized by microanalysis, cyclic voltammetry and ultraviolet-visible spectroscopy. The specific rate constants for the aquation of [Ru(NH3)5L]2+ totrans-[Ru(NH3)4L(H2O)]2+ are (2.5±0.1)×10–5s–1 and (1.8±0.1)×10–5s–1 for L=AsPh3 and SbPh3, respectively, at 25.0±0.1°C; =0.10 mol dm–3, NaO2CCF3. Under the same conditions, the second-order rate constants for the substitution of water intrans-[Ru(NH3)4(H2O)L]2+ by isonicotinamide (isn) are 1.2±0.1, (6.3±0.3)×10–2 and (3.8±0.2)×10–2
m
–1s–1 for L=PPh3, AsPh3, and SbPh3, respectively, suggesting that the order of decreasingtrans-effect is: PPh3AsPh3>SbPh3. The formation constants for thetrans-[Ru(NH3)4L(isn)]2+ complexes are 75±3, (1.40±0.01)×103 and (1.80±0.02)×103M–1 for L=PPh3, AsPh3, and SbPh3, respectively, suggesting that the order of increasingtrans-influence is: SbPh33PPh3. 相似文献
22.
Nitroacetamidine undergoes a useful cyclocondensation with β-diketones to produce substituted 2-amino-3-nitropyridines. Use of an acylpyruvate generates hitherto unreported 2-amino-3-nitropyridine-4-carboxylates. These may be converted easily to functionalized imidazo[4,5-b]pyridines and oxazolo-[5,4-b]pyridines. 相似文献
23.
For an arbitrary poset P, subposets {P
i
: 1ik} form a transitive basis of P if P is the transitive closure of their union. Let u be the minimum size of a covering of P by chains within posets of the basis, s the maximum size of a family of elements with no pair comparable in any basis poset, and a the maximum size of an antichain in P. Define a dense covering to be a collection D of chains within basis posets such that each element belongs to a chain in D within each basis poset and is the top of at least k-1 chains and the bottom of at least k-1 chains in D. Dense coverings generalize ordinary chain coverings of poset. Let d=min {|D|–(k–1)|P|}. For an arbitrary poset and transitive basis, a convenient network model for dense coverings yields the following: Theorem 1: da, with equality iff P has a minimum chain decomposition in which every pair of consecutive elements on each chain are comparable in some basis poset. Theorem 2: usda. Theorem 3: s=d iff s=a. The most interesting special case is where the transitive basis expresses P as the product of two posets, in which case u and s measure the minimum and maximum sizes of unichain coverings and semiantichains. 相似文献
24.
25.
Hans Zimmer R. Palmer-Sungail Douglas Ho Adel Amer 《Journal of heterocyclic chemistry》1993,30(1):161-167
The reaction pathway towards formation of 4-aroyl-3-hydroxy-2(5H)-furanones 1 from the base catalyzed reaction between an acetophenone, diethyl oxalate and formaldehyde was investigated. If methoxide was used as base, a transesterification was found to occur in the first step, while a side reaction, namely the retro Claisen reaction, was in competition with the desired lactone formation in the second step. The nature of the solvent and the acidic character of 1 as well as the basicity of the aminoarylene were found to have a profound influence on the course of the reaction of 1 with aminoarylenes. 相似文献
26.
Li C Lee D Graf TN Phifer SS Nakanishi Y Burgess JP Riswan S Setyowati FM Saribi AM Soejarto DD Farnsworth NR Falkinham JO Kroll DJ Kinghorn AD Wani MC Oberlies NH 《Organic letters》2005,7(25):5709-5712
[chemical reaction: see text]. Three new ent-trachylobane diterpenoids (1-3) were isolated and structures elucidated from Mitrephora glabra Scheff. (Annonaceae). Mitrephorone A (1) possesses a hexacyclic ring system with adjacent ketone moieties and an oxetane ring, both of which are unprecedented among trachylobanes. All compounds were evaluated for cytotoxicity against a panel of cancer cells, where 1 displayed the most potent and broadest activity, and against a battery of antimicrobial assays, where all compounds were approximately equipotent. 相似文献
27.
Abstract— A labile intermediate in the photolytic rearrangement of the antibacterial drug, metronidazole, was identified by isolating the product of photolysis of metronidazole benzoate in methanol. The intermediate, 1-hydroxyethyl-2-methyl-4-hydroxyimino-5-oxo-imidazole, was shown to act as a bidentate chelating agent for copper(II) ions, whereas metronidazole forms a weak monodentate complex. The intermediate may be relevant to the bioactivation mechanism of metronidazole. 相似文献
28.
Douglas R. Hurst Kristen L. French April J. Angel Angela R. Williams Mary E. Rampey Tina S. Guion Kam W. Chan Camille M. Kassis Shannon L. Studer Martinez Charles F. Beam 《Journal of heterocyclic chemistry》1998,35(6):1357-1359
Several acetoacetanilides were trilithiated in excess lithium diisopropylamide, and the resulting polylithiated intermediates were regioselectively condensed with lithiated methyl salicylates followed by acid cyclization to substituted 4-oxo-N-aryl-4H-1-benzopyran-2-acetamides (benzopyranone-2-acetamides). 相似文献
29.
30.
A regressive function (also called a regression or contractive mapping) on a partial order P is a function mapping P to itself such that (x)x. A monotone k-chain for is a k-chain on which is order-preserving; i.e., a chain x
1<...ksuch that (x
1)...(xk). Let P
nbe the poset of integer intervals {i, i+1, ..., m} contained in {1, 2, ..., n}, ordered by inclusion. Let f(k) be the least value of n such that every regression on P
nhas a monotone k+1-chain, let t(x,j) be defined by t(x, 0)=1 and t(x,j)=x
t(x,j–1). Then f(k) exists for all k (originally proved by D. White), and t(2,k) < f(K) <t( + k, k) , where k 0 as k. Alternatively, the largest k such that every regression on P
nis guaranteed to have a monotone k-chain lies between lg*(n) and lg*(n)–2, inclusive, where lg*(n) is the number of appliations of logarithm base 2 required to reduce n to a negative number. Analogous results hold for choice functions, which are regressions in which every element is mapped to a minimal element. 相似文献