全文获取类型
收费全文 | 907篇 |
免费 | 46篇 |
专业分类
化学 | 748篇 |
晶体学 | 15篇 |
力学 | 15篇 |
数学 | 68篇 |
物理学 | 107篇 |
出版年
2024年 | 4篇 |
2023年 | 5篇 |
2022年 | 14篇 |
2021年 | 23篇 |
2020年 | 28篇 |
2019年 | 19篇 |
2018年 | 16篇 |
2017年 | 24篇 |
2016年 | 31篇 |
2015年 | 27篇 |
2014年 | 37篇 |
2013年 | 62篇 |
2012年 | 66篇 |
2011年 | 54篇 |
2010年 | 39篇 |
2009年 | 50篇 |
2008年 | 57篇 |
2007年 | 44篇 |
2006年 | 61篇 |
2005年 | 43篇 |
2004年 | 40篇 |
2003年 | 36篇 |
2002年 | 20篇 |
2001年 | 7篇 |
2000年 | 7篇 |
1999年 | 2篇 |
1998年 | 3篇 |
1997年 | 7篇 |
1996年 | 6篇 |
1995年 | 8篇 |
1994年 | 10篇 |
1993年 | 11篇 |
1992年 | 7篇 |
1991年 | 9篇 |
1990年 | 10篇 |
1989年 | 9篇 |
1988年 | 7篇 |
1987年 | 4篇 |
1986年 | 7篇 |
1985年 | 5篇 |
1984年 | 8篇 |
1983年 | 3篇 |
1982年 | 6篇 |
1981年 | 5篇 |
1977年 | 2篇 |
1976年 | 2篇 |
1973年 | 1篇 |
1972年 | 3篇 |
1971年 | 1篇 |
1968年 | 1篇 |
排序方式: 共有953条查询结果,搜索用时 26 毫秒
21.
Carbon–hydrogen bond dissociation enthalpies (BDEs) were computed for all haloethenes, C2H4−nXn (n=0–3, X=F, Cl, Br, I), at the B3LYP/6-311+G(3df,2p) level using isodesmic reactions. It was found that C–H bond strengths in the monohaloethenes varied substantially, by as much as 18 kJ mol−1, dependent upon the bond's stereochemical position relative to the halogen. BDEs in the dihaloethanes varied in the order CX2CH–H>(E)-CHXCX–H>(Z)-CHXCX–H. Trends in the computed bond enthalpies were discussed and explained on the basis of relative steric repulsions and hyperconjugative delocalization interactions, as determined from Natural Bond Orbital analysis. 相似文献
22.
Srinivas Reddy Dubbaka 《Tetrahedron》2005,61(6):1523-1530
2-Methylprop-2-ene-1-sulfonyl fluorides can be easily prepared via the ene reaction of methallylsilanes and SO2. In the presence of a base, aldehydes and 2-methylprop-2-ene-1-sulfonyl fluorides give 1,3-(E) and (Z)-dienes. Their (Z)→(E) isomerization by classical means fails or leads to their polymerization. It is shown that SO2 can isomerize 1-aryl-3-methyl-1,3-dienes at low temperature, without formation of sulfolenes (cheletropic addition/elimination). Preliminary mechanistic studies suggest that SO2 adds to 1,3-dienes forming 1,4-diradical intermediates that are responsible for the (Z)→(E) isomerizations. 相似文献
23.
The ene reaction of sulfur dioxide with enoxysilanes or with allylsilanes generates silyl sulfinates that can be brominated (Br(2) or NBS) or chlorinated (NCS or Cl(2)) to produce the corresponding sulfonyl halides. They react with primary and secondary amines or alcohols to give the corresponding sulfonamides and sulfonic esters, respectively. The hetero-Diels-Alder addition of sulfur dioxide to 1-oxy- or 1,3-dioxy-1,3-dienes generates zwitterions that add to enoxysilanes or allylsilanes giving silyl sulfinates that can be converted in situ into polyfunctional sulfonamides or sulfonic esters. This realizes quick access to libraries of complicated sulfonamides and sulfonic esters applying one-pot, three- and four-component methods. 相似文献
24.
Transition-metal-catalyzed carbon-carbon bond-forming reactions are among the most powerful methods in organic synthesis and play a crucial role in modern materials science and medicinal chemistry. Recent developments in the area of ligands and additives permit the cross-coupling of a large variety of reactants, including inexpensive and readily available sulfonyl chlorides. Their desulfitative carbon-carbon cross-coupling reactions (Negishi, Stille, carbonylative Stille, Suzuki-Miyaura, and Sonogashira-Hagihara-type cross-couplings and Mizoroki-Heck-type arylations) are reviewed together with carbon-carbon cross-coupling reactions with other organosulfur compounds as electrophilic reagents. 相似文献
25.
Gantasala N. Srinivas 《Journal of organometallic chemistry》2006,691(11):2503-2511
η2 π-Complexes of Ge2H2 with the organometallic fragments V(PH3)2(I)(CO)2, Cr(CO)4, Co(PH3)2(Cl) and M(PH3)2 (M = Ni, Pd, Pt) have been studied at the B3LYP level using the SBKJC relativistic effective core potentials and their associated basis sets on metals and iodine, and the 6-31G(d) basis set on all other elements. The transition metal fragments of V, Cr, Co, Ni, Pd and Pt were chosen based on known alkyne compounds. All the complexes are local minima for both the HGeGeH and GeGeH2 isomers of the Ge2H2 ligand. The complexes containing GeGeH2 isomer as a ligand are lower in energy than those with the HGeGeH ligand (except in the V complex in which the difference is only 1.0 kcal/mol). There is a net charge transfer from ligand to metal in complexes V-Co and from metal to ligand in late transition metal complexes (Ni-Pt). 相似文献
26.
Matthew N. Idso Ajay Suresh Akhade Mario L. Arrieta-Ortiz Bert T. Lai Vivek Srinivas James P. Hopkins Jr. Ana Oliveira Gomes Naeha Subramanian Nitin Baliga James R. Heath 《Chemical science》2020,11(11):3054
Antibiotic resistant infections are projected to cause over 10 million deaths by 2050, yet the development of new antibiotics has slowed. This points to an urgent need for methodologies for the rapid development of antibiotics against emerging drug resistant pathogens. We report on a generalizable combined computational and synthetic approach, called antibody-recruiting protein-catalyzed capture agents (AR-PCCs), to address this challenge. We applied the combinatorial protein catalyzed capture agent (PCC) technology to identify macrocyclic peptide ligands against highly conserved surface protein epitopes of carbapenem-resistant Klebsiella pneumoniae, an opportunistic Gram-negative pathogen with drug resistant strains. Multi-omic data combined with bioinformatic analyses identified epitopes of the highly expressed MrkA surface protein of K. pneumoniae for targeting in PCC screens. The top-performing ligand exhibited high-affinity (EC50 ∼50 nM) to full-length MrkA, and selectively bound to MrkA-expressing K. pneumoniae, but not to other pathogenic bacterial species. AR-PCCs that bear a hapten moiety promoted antibody recruitment to K. pneumoniae, leading to enhanced phagocytosis and phagocytic killing by macrophages. The rapid development of this highly targeted antibiotic implies that the integrated computational and synthetic toolkit described here can be used for the accelerated production of antibiotics against drug resistant bacteria.Antibody-recruiting protein-catalyzed capture agent (AR-PCCs) are a new class of all-synthetic and highly targeted antibiotics that recruit endogenous immune responses to eliminate drug-resistant microbes. 相似文献
27.
Yao M Mantha S Shah VR Vachharajani NN Arnold ME Pursley JM Srinivas NR 《Biomedical chromatography : BMC》2002,16(3):175-182
A high performance liquid chromatographic-mass spectrometric (LC/MS) assay was developed and validated for the determination of BMS-204352 in dog K(3)EDTA plasma. A 0.5 mL aliquot of control plasma was spiked with BMS-204352 and internal standard (IS) and buffered with 1 mL of 5 mM ammonium acetate. The mixture was then extracted with 3 mL of toluene. After separation and evaporation of the organic phase to dryness using nitrogen at 40 degrees C, the residue was reconstituted in the mobile phase and 25 microL of the sample were injected onto a Hypersil C(18) column (2 x 50 mm; 3 microm) at a flow rate of 0.5 mL/min. The mobile phase was consisted of two solvent mixtures (A and B). Solvent A was composed of 5 mM ammonium acetate and 0.1% triethylamine in 75:25 v/v water:methanol, pH adjusted to 5.5 with glacial acetic acid, and solvent B was 5 mM ammonium acetate in methanol. A linear gradient system was used to elute the analytes. The mass spectrometer was programmed to admit the de-protonated molecules at m/z 352.7 (IS) and m/z 357.9 (BMS-204352). Standard curves of BMS-204352 were linear (r(2) > or = 0.998) over the concentration range of 0.5-1000 ng/mL. The mean predicted quality control (QC) concentrations deviated less than 5.1% from the corresponding nominal values (ie 4, 80, 400 and 2000 ng/mL); the within- and between-assay precision of the assay were within 5.5% relative standard deviation. Stability of BMS-204352 was confirmed after at least three freeze/thaw cycles and BMS-204532 was stable in dog plasma when stored frozen at or below -20 degrees C for at least 16 weeks in spiked QC samples and for at least 4 1/2 weeks for in vivo study samples. BMS-204352 and IS were stable in the injection solvent at room temperature for at least 24 h. The assay was applied to delineate the pharmacokinetic disposition of BMS-204352 in dogs following a single intravenous dose administration. In conclusion, the assay is accurate, precise, specific, sensitive and reproducible for the pharmacokinetic analysis of BMS-204532 in dog plasma. 相似文献
28.
Korupoju SR Mangayarkarasi N Zacharias PS Mizuthani J Nishihara H 《Inorganic chemistry》2002,41(16):4099-4101
New homo trinuclear Zn(II) complexes [Zn(3)L(1)(micro-OAc)](ClO(4))(2).3CHCl(3).H(2)O, 1, and [Zn(3)L(1)(micro-OAc)].ClO(4).PF(6).5CH(3)OH.H(2)O, 2, and hetero trinuclear complex [Zn(2)CuL(1)(micro-OAc)](ClO(4))(2).3CHCl(3).H(2)O,3, of optically active hexaaza triphenolic macrocycle H(3)L(1) were synthesized and crystallographically characterized. The cation [Zn(3)L(1)(micro-OAc)](+) structure of 1 and 2 closely resembles the trinuclear Zn(II) active site of P1 nuclease. The distorted tetrahedral geometry of Zn3 was successfully reproduced at Cu1 in complex 3. The complexes 2 and 3 cleave CT DNA at 37 and 50 degrees C. 相似文献
29.
Nirmal Kumar S. Appari Srinivas Kuncharam Bhanu Vardhan Reddy 《Catalysis Surveys from Asia》2021,25(4):362-388
Catalysis Surveys from Asia - Sulfur poisoning of catalyst is a well-known phenomenon observed during the production of syngas (CO?+?H2). The presence of traces of sulfur... 相似文献
30.
Komuraiah Buduma Niranjana Kumar A Satya Srinivas KVN Kotesh Kumar J Srinivas Chinde Anand Kumar Domatti Yogesh Kumar Paramjit Grover Ashok Tiwari Feroz Khan 《Journal of heterocyclic chemistry》2021,58(11):2078-2089
Design, synthesis, and bioactivity evaluation of novel mannich bases ( 2a-2j ) and triazole-chalcone derivatives ( 7a-7k ) of Eugenol 1 were reported. Among all the derivatives tested for antiproliferative activity, di-amine manich derivative 2b (32.92 μM), and 4-methoxy chalcone triazole derivative 7d (33.05 μM) significantly inhibited HepG2 cell lines when compared to the standard doxorubicin (37.29 μM). Whereas most of the compounds such as diethylamine 2a (17.75 μM), (aminomethyl) methane diamine 2b (17.02 μM), and bis (chloromethyl) amine 2c (20.12 μM) showed moderate to better inhibition towards MCF-7 cell lines. The synthesized analogues were also tested for antidiabetic and antiobesity potentials. Compounds 2f (55.50%), 2c (54.34%), 7g (55.5%), and 2a (55.5%) have shown moderate inhibitory potentials toward intestinal α-glucosidase enzyme when compared to the standard Acarbose (72.86%). Likewise, compounds 7d (82.95%), 7f (76.19%), 7g (74.81%), 7e (74.81%), and 2g (72.50%) have shown significant to moderate inhibitory potentials toward Pancreatic lipase enzyme when compared to the standard orlistat (91.10%). ROS induces life-threatening diseases like diabetes, cancer, etc., and antioxidants play a major role in controlling their production. Compounds 2c (99.81%), 2i (99.80%), 2d (99.26%), 2g (98.79%), and 2f (98.42%) have shown significant antioxidant profiles in ABTS assay when compared to the standard Trolox (99.07%). Further, In silico Molecular docking and pharmacokinetic screening of the eugenol derivatives complemented the in vitro results indicating the drug likeness of the obtained active compounds. 相似文献