全文获取类型
收费全文 | 776篇 |
免费 | 37篇 |
国内免费 | 8篇 |
专业分类
化学 | 699篇 |
晶体学 | 1篇 |
力学 | 4篇 |
数学 | 57篇 |
物理学 | 60篇 |
出版年
2024年 | 1篇 |
2023年 | 4篇 |
2022年 | 13篇 |
2021年 | 43篇 |
2020年 | 32篇 |
2019年 | 27篇 |
2018年 | 22篇 |
2017年 | 14篇 |
2016年 | 24篇 |
2015年 | 22篇 |
2014年 | 30篇 |
2013年 | 46篇 |
2012年 | 54篇 |
2011年 | 54篇 |
2010年 | 52篇 |
2009年 | 39篇 |
2008年 | 50篇 |
2007年 | 53篇 |
2006年 | 41篇 |
2005年 | 52篇 |
2004年 | 35篇 |
2003年 | 26篇 |
2002年 | 22篇 |
2001年 | 6篇 |
2000年 | 11篇 |
1999年 | 6篇 |
1998年 | 6篇 |
1997年 | 7篇 |
1996年 | 4篇 |
1995年 | 3篇 |
1994年 | 1篇 |
1992年 | 6篇 |
1991年 | 2篇 |
1990年 | 2篇 |
1989年 | 2篇 |
1988年 | 1篇 |
1987年 | 3篇 |
1983年 | 1篇 |
1981年 | 1篇 |
1980年 | 1篇 |
1976年 | 1篇 |
1974年 | 1篇 |
排序方式: 共有821条查询结果,搜索用时 62 毫秒
761.
Gulías M Collado A Trillo B López F Oñate E Esteruelas MA Mascareñas JL 《Journal of the American Chemical Society》2011,133(20):7660-7663
We report a ruthenium-catalyzed (2 + 2) intramolecular cycloaddition of allenes and alkenes. We have found that the use of the ruthenium complex RuH(2)Cl(2)(P(i)Pr(3))(2), which has previously gone unnoticed in catalytic applications, is crucial for the observed reactivity. The reaction proceeds under mild conditions and is fully diastereoselective, providing a practical entry to a variety of bicyclo[3.2.0]heptane skeletons featuring cyclobutane rings. 相似文献
762.
Ortega P Macarena Cobaleda B Hernández-Ros JM Fuentes-Paniagua E Sánchez-Nieves J Tarazona MP Copa-Patiño JL Soliveri J de la Mata FJ Gómez R 《Organic & biomolecular chemistry》2011,9(14):5238-5248
A new family of amine- and ammonium-terminated hyperbranched polycarbosilanes (PCS) and dendrimers has been synthesized. The functionalization of a polycarbosilane matrix was carried out with peripheral allyl groups by two strategies in the case of PCS: 1) hydrosilylation of allyl amines with PCS containing terminal Si-H bonds, or 2) hydrosilylation of PCS-allyl with an aminosilane. Dendrimers with terminal amine groups were synthesized by hydrosilylation of allydimethylamine. Quaternized systems with MeI are soluble and stable in water or other protic solvent. The antibacterial properties of the ammonium-terminated hyperbranched polycarbosilanes and dendrimers have been evaluated showing that they act as potent biocides against Gram-positive and Gram-negative bacterial strains. 相似文献
763.
The condensation of carbamoyl nitroso compounds, obtained by oxidation of N-hydroxyureas, with amines unexpectedly afforded semicarbazones (aka carbamoyl hydrazones). Although the substitution of the nitrosyl moiety might compete to afford the corresponding urea, an excess of amine led to the semicarbazone as the major product, which is presumably formed via isomerization of an initially generated acyl azo compound. 相似文献
764.
An analytical method for the determination of UV filters in soil and sediment has been developed and validated considering benzophenones (BP) and salicylates as target analytes. Soil and sediment samples were extracted with ethyl acetate-methanol (90:10, v/v) assisted with sonication, performing a simultaneous clean-up step. Quantification of these compounds was carried out by gas chromatography-mass spectrometry (GC-MS) after derivatization of the extracts with N,O-bis(trimethylsilyl)trifluoroacetamide (BSTFA). Recoveries from spiked soil samples ranged from 89.8% to 104.4% and they were between 88.4% and 105.3% for spiked sediment samples. The effect of the residence time and soil moisture content on the recovery of these compounds was also studied. The precision, expressed as relative standard deviation, was in all cases below 6.1% and the limits of detection (S/N=3) varied from 0.07 to 0.10 ng g(-1) and from 0.11 to 0.28 ng g(-1) for soils and sediments, respectively. The validated method was applied to the analysis of five benzophenone and two salicylate UV filters in soil and sediment samples collected in different areas of Spain. 相似文献
765.
The fragmentation mechanisms of progesterone have been studied by triple quadrupole tandem mass spectrometry (MSMS) and density functional theory (DFT). Mechanisms leading to major product ions are proposed. The data suggest that progesterone fragments preferentially via hydrogen and other rearrangements lead to neutral losses. These fragmentations are quite complex and are preceded by σ-bond cleavages in most cases. Four major pathways for progesterone fragmentation are proposed involving: (1) cleavage of ring B at C9-C10, (2) cleavage of C6-C7 bond in ring B through m/z 191, (3) two types of cleavages of ring D, and (4) ketene elimination in ring A. Pathways (1)-(3) proceed via charge-remote fragmentations while pathway (4) proceeds via charge-site initiated mechanism. The geometry of product ions in these pathways were optimized using DFT at the B3LYP/6-311G(d,p) level of theory from which the free energies of the pathways were calculated. The effect that the choice of basis sets and density functionals has on the results was tested by performing additional calculations using B3LYP/6-31G(d) and B3PW91/6-311G(d,p). 相似文献
766.
767.
Santos J Illescas BM Martín N Adrio J Carretero JC Viruela R Ortí E Spänig F Guldi DM 《Chemistry (Weinheim an der Bergstrasse, Germany)》2011,17(10):2957-2964
The synthesis of the first fully conjugated tetrathiafulvalene–tetracyano‐p‐quinodimethane ((TTF)–TCNQ)‐type system has been carried out by means of a Julia–Kocienski olefination reaction. In particular, a tetracyanoanthraquinodimethane (TCAQ) formyl derivative and two new sulfonylmethyl‐exTTFs (exTTF=2‐[9‐(1,3‐dithiol‐2‐ylidene)anthracen‐10(9H)‐ylidene]‐1,3‐dithiole)—prepared as new building blocks—were linked. A variety of experimental conditions reveal that the use of sodium hexamethyldisilazane (NaHMDS) as base in THF afforded the E olefins with excellent stereoselectivity. Theoretical calculations at the B3LYP/6‐31G** level point to highly distorted exTTF and TCAQ that form an almost planar stilbene unit between them. Although calculations predicted appreciable electronic communication between the donor and the acceptor, cyclic voltammetric studies did not substantiate this effect. It was only in photophysical assays that the electronic communication emerged in the form of a charge‐transfer (CT) absorption and emission. Once photoexcited (i.e., the locally excited state or excited charge‐transfer state), an ultrafast, subpicosecond charge separation leads to a radical ion pair state in which the spectroscopic features of the radical cation of exTTF as well as the radical anion of TCAQ are discernable. The radical ion pair is metastable and undergoes a fast ((1.0±0.2) ps) charge recombination to reconstitute the electronic ground state. Such ultrafast charge separation and recombination processes come as a consequence of the very short vinyl linkage between the two electroactive units. 相似文献
768.
María José Castro-Castro Dolors Dot-Bach Beatriz Candás-Estébanez Ruth Cano-Corres Xavier Fuentes-Arderiu 《Accreditation and quality assurance》2011,16(12):643-647
In the clinical laboratory, one of the most objective ways to perform the final review of patients’ measured values is the
use of computerized plausibility control (i.e., set of procedures used to decide whether a patient’s measured value is valid according to established clinical and
biological criteria). This study is focused on the estimation of alert and change limits to be applied to detect doubtful
patients’ measured values. These limits are useful to improve the final review of patients’ measured values since these limits
are produced objectively and are selected according to the clinical laboratory needs, letting the clinical laboratory professional
staff to save time and effort. 相似文献
769.
The interaction between carboxylic acid-stabilised gold nanoparticles (AuNP) and pH-responsive microgels is shown. The microgel particles are a copolymer of N-[3-(dimethylamino)propyl]methacrylamide (DMAPMA) and N-isopropylacrylamide (NIPAM). The microgel properties are presented by their hydrodynamic diameter and electrophoretic mobility in response to pH. These microgel particles are pH-responsive under neutral conditions decreasing in diameter beyond pH 7. The dispersion characteristics of AuNP adsorbed onto the microgel network are shown with respect to adsorbed amount and the pH-responsive properties of the AuNP. This data is presented between pH 3 and 6 where the microgel properties remain constant. Asymmetric adsorption of AuNP onto poly(DMAPMA-co-NIPAM) microgels is achieved by adsorption of nanoparticles, from the aqueous phase, onto microgel-stabilised oil-in-water emulsions. These asymmetrically modified microgels display very different dispersion behaviour, in response to pH, due to their dipolar nature. 相似文献
770.
Parajón-Costa BS Baran EJ 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2011,78(1):133-135
The FTIR and FT-Raman spectra of the oxovanadium(IV) complex of 3-hydroxy-2-methyl-4-pyrone (maltol) bis(maltolato)oxovanadium(IV) were recorded and briefly discussed by comparison with the spectra of uncoordinated maltol and with some related species. 相似文献