全文获取类型
收费全文 | 2728篇 |
免费 | 103篇 |
国内免费 | 10篇 |
专业分类
化学 | 2148篇 |
晶体学 | 20篇 |
力学 | 55篇 |
数学 | 296篇 |
物理学 | 322篇 |
出版年
2023年 | 11篇 |
2022年 | 31篇 |
2021年 | 124篇 |
2020年 | 63篇 |
2019年 | 69篇 |
2018年 | 67篇 |
2017年 | 58篇 |
2016年 | 105篇 |
2015年 | 82篇 |
2014年 | 111篇 |
2013年 | 201篇 |
2012年 | 209篇 |
2011年 | 232篇 |
2010年 | 136篇 |
2009年 | 118篇 |
2008年 | 175篇 |
2007年 | 154篇 |
2006年 | 125篇 |
2005年 | 146篇 |
2004年 | 106篇 |
2003年 | 72篇 |
2002年 | 82篇 |
2001年 | 29篇 |
2000年 | 36篇 |
1999年 | 24篇 |
1998年 | 17篇 |
1997年 | 23篇 |
1996年 | 25篇 |
1995年 | 15篇 |
1994年 | 12篇 |
1993年 | 14篇 |
1992年 | 8篇 |
1991年 | 10篇 |
1990年 | 9篇 |
1989年 | 9篇 |
1987年 | 11篇 |
1986年 | 11篇 |
1985年 | 4篇 |
1984年 | 9篇 |
1983年 | 6篇 |
1982年 | 6篇 |
1981年 | 13篇 |
1980年 | 8篇 |
1979年 | 7篇 |
1978年 | 7篇 |
1977年 | 3篇 |
1976年 | 6篇 |
1975年 | 10篇 |
1974年 | 10篇 |
1971年 | 3篇 |
排序方式: 共有2841条查询结果,搜索用时 31 毫秒
1.
2.
Francesco Segatta David M. Rogers Naomi T. Dyer Ellen E. Guest Zhuo Li Hainam Do Artur Nenov Marco Garavelli Jonathan D. Hirst 《Molecules (Basel, Switzerland)》2021,26(2)
A fully quantitative theory of the relationship between protein conformation and optical spectroscopy would facilitate deeper insights into biophysical and simulation studies of protein dynamics and folding. In contrast to intense bands in the far-ultraviolet, near-UV bands are much weaker and have been challenging to compute theoretically. We report some advances in the accuracy of calculations in the near-UV, which were realised through the consideration of the vibrational structure of the electronic transitions of aromatic side chains. 相似文献
3.
A Mechanistic Study on the Oxidative Degradation of Dibenzazepine Derivatives by Manganese(III) Complexes in Acidic Sulfate Media 下载免费PDF全文
The oxidative degradation of tricyclic antidepressants (TCA) was studied in the presence of a large excess of the oxidizing agent manganese(III) and its reduced form manganese(II) sulfate in acidic media. The products were detected and identified using UV–vis, ESI‐MS, IR, and EPR methods. The mechanism of the reaction was studied for the following two classes of TCA: 10,11‐dihydro‐5H‐dibenz[b, f]azepines and dibenz[b, f]azepines. The oxidative degradation between dibenz[b, f]azepines and the manganese(III) ions resulted in the formation of substituted acridine with the same substituent as in the origin dibenz[b, f]azepine derivative. The pseudo–first‐order rate constants (kobs) were determined for the degradation process. The dependences of the observed rate constants on the [MnIII] with a zero intercept were linear. The reaction between 10,11‐dihydro‐5H‐dibenz[b, f]azepines, and the manganese(III) sulfate ion resulted in oxidative dehydrogenation, which proceeded via the formation of the following two intermediates: a free organic radical and a dimer. Further oxidation of the second intermediate led to a positively charged radical dimer as the single final product. Linear dependences of the pseudo–first‐order rate constants (kobs) on the [MnIII] with a zero intercept were established for the degradation of 10,11‐dihydro‐5H‐dibenz[b, f]azepines. The observed rate constants were dependent on the [H+] and independent of the [TCA] within the excess concentration range of the manganese(III) complexes used in the isolation method. The radical product of the degradation of 10,11‐dihydro‐5H‐dibenz[b, f]azepines was not stable in the aqueous solution and was subsequently transformed to a nonradical dimer in the next slower step. The observed rate constants were independent of the [MnIII], independent of the [H+] and increased slightly with increasing TCA concentrations when TCA was used in excess. The mechanistic consequences of all of these results are discussed. 相似文献
4.
Prof. Piotr Bałczewski Dr. Emilia Kowalska Dr. Ewa Różycka-Sokołowska Dr. Joanna Skalik Dr. Krzysztof Owsianik Dr. Marek Koprowski Dr. Bernard Marciniak Dr. Dariusz Guziejewski Prof. Witold Ciesielski 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(62):14148-14161
The highly substituted mono-aryl/alkylthio-(hetero)acenes prepared in this study have been found to be thermally more stable (Tdecomp.=331–354 °C) than the known di-aryl/alkylthio-substituted acenes by an average of 25 °C. They are also much more photostable at 254 and 365 nm (in both argon and air) than the parent anthracene and other reported anthracenes. The most photostable aryl/alkylthio-anthracenes at 254 nm were found to be 60–70 (in air) and 130 (in argon) times more stable in solution than the unsubstituted anthracene, and much more stable than known EDG/EWG-substituted anthracenes (EDG=electron-donating group, EWG=electron-withdrawing group) with an extended aromatic core. Furthermore, the acenes showed significantly higher photostability at 365 nm in both air and argon. The anthracenes were obtained by the novel thio-Friedel–Crafts/Bradsher cyclization reaction of hitherto unknown [o-(1,3-dithian-2-yl)aryl](aryl)methyl thioethers. The developed approach provides a general access to mono-aryl/alkylthio-substituted (hetero)acene frameworks containing at least three fused (hetero)aromatic rings. The characteristic feature of this approach, which leads to highly substituted acenes, is that the substituents, unlike in other methods, may be introduced at an early stage of the synthesis. DFT and TD-DFT calculations confirmed the stabilizing role of the aryl/alkylthio substituent in the mono-aryl/alkylthio-substituted anthracenes, which are the most stable anthracenes prepared to date. Their high photostability is mainly due to the quenching of singlet oxygen by the acene and the quenching of the acene S1 state by molecular oxygen. 相似文献
5.
In this study, stoichiometric protonation constants of L-tyrosine, L-cysteine, L-tryptophane, L-lysine, and L-histidine, and
their methyl and ethyl esters in water and ethanol–water mixtures of 30, 50, and 70% ethanol (v/v), were determined potentiometrically
using a combined pH electrode system calibrated as the concentration of hydrogen ion. Titrations were performed at 25∘C and the ionic strength of the medium was maintained at 0.10 mol⋅L−1 using sodium chloride. Protonation constants were calculated by using the BEST computer program. The effect of solvent composition
on the protonation constants is discussed. The log10 K2 values of esters generally decreased with increasing ethanol content. However, the log10 K1 values of the esters of L-tyrosine, L-cysteine, and L-tryptophane were found to increase with increasing ethanol content
in contrast those of L-lysine and L-histidine esters. 相似文献
6.
7.
Jacek Doskocz Jadwiga Sołoducho Joanna Cabaj Mieczysław Łapkowski Sylwia Golba Krystyna Palewska 《Electroanalysis》2007,19(13):1394-1401
A convenient and higher yielding synthetic route to N‐alkyl‐bis(thiophene)phenothiazine derivatives is reported and their aggregation, electrochemical properties and polymerization are characterized. The key step in the synthesis of this group of compounds has been the Stille type coupling reaction between the N‐alkyldibromophenothiazine and tin derivatives of thiophene as the best way for preparation of conjugated N‐alkylphenothiazine derivatives. For this group of compounds we also present an electrochemical polymerization effect and widely adopted approach to prepare structurally ordered thin, electroconducting films by Langmuir–Blodgett technique. 相似文献
8.
9.
Do W. Lee Eun Y. Seo Sung I. Cho Chae S. Yi 《Journal of polymer science. Part A, Polymer chemistry》2004,42(11):2747-2755
Pyridine‐2‐carboximidates [methyl ( 1a ), ethyl ( 1b ), isopropyl ( 1c ), cyclopentyl ( 1d ), cyclohexyl ( 1e ), n‐octyl ( 1f ), and benzyl ( 1g )] were prepared from the reaction of 2‐cyanopyridine with the corresponding alcohols. Cyclopentyl‐substituted 1d was found to be a highly effective ligand for copper‐catalyzed atom transfer radical polymerization (ATRP) of methyl methacrylate (MMA). For example, the observed rate constant for a CuBr/ 1d catalytic system was found to be nearly twice as high as the cyclohexyl‐substituted CuBr/ 1e catalytic system [kobs = (1.19 vs 0.56) × 10?4 s?1). The effects of the solvents, temperature, catalyst/initiator, and solvent/monomer ratio on the ATRP of MMA were studied systematically for the CuBr/ 1d catalytic system. The optimum condition for the ATRP of MMA was found to be a 1:2:1:400 [CuBr]o/[ 1d ]o/[ethyl 2‐bromoisobutyrate]o/[MMA]o ratio at 60 °C in veratrole solution, which yielded well‐defined poly(MMA) with a narrow molecular weight distribution of 1.14. The catalytically active copper complex 2d was isolated from the reaction of CuBr with 1d . Narrow molecular weight distributions as low as 1.06 were achieved for the CuBr/ 1d catalytic system by employing 10% of the deactivator CuBr2. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2747–2755, 2004 相似文献
10.
Marcelo Do Amaral Steven Van Es Jos M. Asua 《Journal of polymer science. Part A, Polymer chemistry》2004,42(16):3936-3946
The production of high‐solid‐content, low‐viscosity latexes is an active field in both industry and academia. The viscosity of polymer dispersions has a clear dependence on the particle size distribution (PSD). An example is the rule of thumb that a bimodal PSD enables the reduction of the viscosity with respect to monomodal systems. Despite important progress in theoretical work, not much has been done to quantitatively predict the low shear viscosity of aqueous polymer dispersions as a function of the complex PSD. In this work, the capability of a low‐shear‐viscosity equation to quantitatively account for the influence of both the PSD and the physicochemical characteristics of the dispersions is experimentally assessed. An analysis, consistent with theoretical concepts, of the data with semiempirical correlations is proposed. Next, with values of the parameters of the viscosity equation obtained experimentally, the effect of a latex with a 70% solid content on the low shear viscosity is examined. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 3936–3946, 2004 相似文献