全文获取类型
收费全文 | 549篇 |
免费 | 19篇 |
专业分类
化学 | 467篇 |
晶体学 | 3篇 |
力学 | 2篇 |
数学 | 36篇 |
物理学 | 60篇 |
出版年
2024年 | 2篇 |
2023年 | 7篇 |
2022年 | 21篇 |
2021年 | 23篇 |
2020年 | 13篇 |
2019年 | 20篇 |
2018年 | 8篇 |
2017年 | 11篇 |
2016年 | 36篇 |
2015年 | 24篇 |
2014年 | 22篇 |
2013年 | 46篇 |
2012年 | 27篇 |
2011年 | 33篇 |
2010年 | 24篇 |
2009年 | 25篇 |
2008年 | 45篇 |
2007年 | 28篇 |
2006年 | 30篇 |
2005年 | 22篇 |
2004年 | 18篇 |
2003年 | 14篇 |
2002年 | 15篇 |
2001年 | 5篇 |
2000年 | 4篇 |
1999年 | 6篇 |
1998年 | 2篇 |
1997年 | 5篇 |
1996年 | 3篇 |
1995年 | 3篇 |
1994年 | 3篇 |
1993年 | 4篇 |
1992年 | 1篇 |
1991年 | 1篇 |
1990年 | 1篇 |
1989年 | 1篇 |
1988年 | 3篇 |
1985年 | 2篇 |
1984年 | 1篇 |
1983年 | 1篇 |
1982年 | 1篇 |
1981年 | 2篇 |
1980年 | 2篇 |
1977年 | 1篇 |
1973年 | 1篇 |
1934年 | 1篇 |
排序方式: 共有568条查询结果,搜索用时 15 毫秒
11.
Giusy Rita Caponio Miriam Cofano Tamara Lippolis Isabella Gigante Valentina De Nunzio Graziana Difonzo Mirella Noviello Luigi Tarricone Giuseppe Gambacorta Gianluigi Giannelli Maria De Angelis Maria Notarnicola 《Molecules (Basel, Switzerland)》2022,27(20)
Grape pomace (GP)—the major by-product of winemaking processes—still contains bioactive molecules with known beneficial properties for human health, such as an antiradical scavenging activity or an antiproliferative activity of tumors. In vitro studies have demonstrated that GP polyphenols specifically influence colon cancer cell proliferation. In addition to previously published work, we tested the phenolic compounds of Aglianico GP following an in vitro simulated gastrointestinal digestion on colorectal cancer cell lines at different degrees of differentiation. Our experiments, using HT29 and SW480 cells, confirmed the anti-proliferative effect of GP gastrointestinal digested extract and provided intriguing insights on the way it influences the cancer cell features (i.e., viability, proliferation, and apoptosis). We observed that Aglianico GP extract showed a great ability to affect cell proliferation and apoptosis. Interestingly, both HT29 and SW480 cells produced a significant increase in Bax, and a significant increase in the Bax/Bcl-2 ratio and caspase-3. The gastrointestinal digested GP extract was previously characterized both for antioxidant activity and phenolic composition. As a result, the TPC and the antioxidant activity reached high values in the Aglianico GP digested extract, and the main compounds assessed by UHPLC-DAD were anthocyanins, phenolic acids, and flavonoids. This work shed light on the use of digested GP extract as a dietary ingredient, a very sustainable source of nutritional compounds with potential health benefits for colon cancer cell proliferation. 相似文献
12.
Tanja Vidaković-Koch Tamara Miličić Luka A. Živković Hoon Seng Chan Ulrike Krewer Menka Petkovska 《Current Opinion in Electrochemistry》2021
The nonlinear frequency response analysis (NFRA) can be seen as an extension of electrochemical impedance spectroscopy. NFRA gives a full and detailed representation of the system response and can establish a connection between model parameters and the experimentally observed phenomena. In this article, different theoretical NFRA approaches and the most recent application examples are discussed. A simple electrochemical example is used to showcase the benefits and disadvantages of analyzing the system response by using different approaches. In addition, it was shown how to extract experimental harmonic values and analyze them. 相似文献
13.
14.
Shahan Zeb Khan Muhammad Kashif Amir Imdad Ullah Asma Aamir John M. Pezzuto Tamara Kondratyuk Francine Bélanger‐Gariepy Akbar Ali Sajid Khan Zia‐ur‐Rehman 《应用有机金属化学》2016,30(6):392-398
Two new heteroleptic palladium(II) complexes have been synthesized by reacting equimolar quantities of palladium(II) chloride, sodium 4‐(2‐methoxyphenyl)piperazine‐1‐carbodithioate and diphenyl‐p‐tolylphosphine ( 1 ) or tri‐p‐tolylphosphine ( 2 ). Complexes 1 and 2 have been characterized using elemental analysis, Fourier transform infrared spectroscopy, multinuclear NMR (1H, 13C and 31P) spectroscopy and single‐crystal X‐ray analysis. The latter technique confirms a pseudo square‐planar geometry in which two adjacent positions are occupied by bidentate dithiocarbamate while chloro and substituted triphenylphosphine are present at the remaining two positions. The anticancer activity of both complexes against five different cancer cell lines (LU – human lung carcinoma, established at UIC, Department of Surgical Oncology; MCF7 – human breast adenocarcinoma, ATCC number HTB‐22?; MDA‐MB‐231 – human breast adenocarcinoma, ATCC number HTB‐26?; Hepa‐1c1c7 – mouse liver hepatoma, ATCC number CRL‐2026?; PC‐3 – human prostate adenocarcinoma, ATCC number CRL‐1435?) was determined by MTT assay, revealing 2 has higher activity than 1 . A drug–calf thymus DNA binding study with UV–visible spectroscopy reveals a higher DNA binding affinity of 2 (3.511 × 104 M?1) than 1 (4.213 × 103 M?1). Density functional theory studies confirm the relatively more stable nature of 2 than 1 . Copyright © 2016 John Wiley & Sons, Ltd. 相似文献
15.
Jovica Stojanovi Tamara ?or?evi Ljiljana Karanovi 《Acta Crystallographica. Section C, Structural Chemistry》2008,64(11):i91-i94
During an investigation of the insufficiently known system M1O–M2O–X2O5–H2O (M1 = Cd2+, Sr2+ and Ba2+; M2 = Cu2+, Ni2+, Co2+, Zn2+ and Mg2+; X = P5+, As5+ and V5+), single crystals of the novel compound dicadmium copper(II) bis[phosphate(V)], Cd2Cu(PO4)2, were obtained. This compound belongs to a small group of compounds adopting a Cu3(PO4)2‐type structure and having the general formula M12M2(XO4)2 (M1/M2 = Cd2+, Cu2+, Mg2+ and Zn2+; X = As5+, P5+ and V5+). The crystal structure is characterized by the interconnection of infinite [Cu(PO4)2]n chains and [Cd2O10]n double chains, both extending along the a axis. Exceptional characteristics of this structure are its novel chemical composition and the occurrence of double chains of CdO6 polyhedra that were not found in related structures. In contrast to the isomorphous compounds, where the M1 cations are coordinated by five O atoms, the Cd atom is coordinated by six. The dissimilarity in the geometry of M1 coordination between Cd2Cu(PO4)2 and the isomorphous compounds is mostly due to the larger ionic radius of the Cd cation in comparison with the Cu, Mg and Zn cations. Sharing a common edge, two CdO6 polyhedra form Cd2O10 dimers. Each such dimer is bonded to another dimer sharing common vertices, forming [Cd2O10]n double chains in the [100] direction. The Cu atoms, located on an inversion centre (site symmetry ), form isolated CuO4 squares interconnected by PO4 tetrahedra, forming [Cu(PO4)2]n chains similar to those found in related structures. Conversely, the [Cd2O10]n double chains, which were not found in related structures, are an exclusive feature of this structure. 相似文献
16.
Frontispiece: Synthesis of Calcium(II) Amidinate Precursors for Atomic Layer Deposition through a Redox Reaction between Calcium and Amidines 下载免费PDF全文
17.
Andrew A. Tolmachev Sergei P. Ivonin Alexandra A. Chaikovskaya Tamara N. Kudrya Tat'jana E. Terekovskaya 《Phosphorus, sulfur, and silicon and the related elements》2013,188(1-4)
Abstract C-phosphorylation of pyrrole, furan, thiophene derivatives and their benzanalogs by phosphorus tribromide has been studied. Perspective methods for involving trivalent phosphorus residues at a different position of the rings have been developed. Unknown early the heterocycle's derivatives with tri- and tetracoordinated phosphorus substituents (1–5) and novel types of phosphoruscontaining heterocycles (6,7) have been obtained. 相似文献
18.
The Comparative Molecular Field Analysis (CoMFA) was developed to investigate a three-dimensional quantitative structure activity relationship (3D-QSAR) model of ligands for the sigma 1 receptor. The starting geometry of sigma-1 receptor ligands was obtained from the Tripos force field minimizations and conformations were decided from DISCOtech using the SYBYL 6.8. program. The structures of 48 molecules were fully optimized at the ab initio HF/3-21G* and semiempirical AM1 calculations using GAUSSIAN 98. The electrostatic charges were calculated using several methods such as semiempirical AM1, density functional B3LYP/3-21G*, and ab initio HF/3-21G*, MP2/3-21G* calculations within GAUSSIAN 98. Using the optimized geometries, the CoMFA results derived from the HF/3-21G method were better than those from AM1. The best CoMFA was obtained from HF/3-21G* optimized geometry and charges (R2 = 0.977). Using the optimized geometries, the CoMFA results derived from the HF/3-21G methods were better than those from AM1 calculations. The training set of 43 molecules gave higher R2 (0.989-0.977) from HF/3-21G* optimized geometries than R2 (0.966-0.911) values from AM1 optimized geometries. The test set of five molecules also suggested that HF/3-21G* optimized geometries produced good CoMFA models to predict bioactivity of sigma 1 receptor ligands but AM1 optimized geometries failed to predict reasonable bioactivity of sigma 1 receptor ligands using different calculations for atomic charges. 相似文献
19.
Tamara Brider Gary Gellerman 《Tetrahedron letters》2012,53(42):5611-5615
A new approach for a short synthesis of novel medicinally-important mono-, bis- and tris-1,8-naphthalimide peptidyl derivatives is described. The method generates efficiently 1,8-naphthalimides with variable spacer lengths and charged, polar or hydrophobic residues at desired positions, which can increase binding affinity, conformational stability, intracellular transport and/or biological activity. The synthetic routes reported in this work are both general and applicable, and significantly expand the scope of potential 1,8-naphthalimide anticancer candidates. 相似文献
20.
The New Data for the Reaction of Arylenedioxy Trihalogenophosphoranes with Alkyl- and Arylacetylenes
Vladimir F. Mironov Alfiya A. Shtyrlina Ravil R. Petrov Tamara A. Baronova Fedor F. Alekseev Elena N. Varaksina 《Phosphorus, sulfur, and silicon and the related elements》2013,188(6-7):1381-1385
The new data concerning the reaction between substituted arylenedioxy trihalogenophosphoranes and monoalkyl- or arylacetylenes are summarized. The reaction leads to formation of six-membered heterocycles-2-oxo-4-R-benzo[ e ]-1,2-oxaphosphorin-3-enes. The substituent effects in the phosphorane and acetylene molecules on the ipso -substitution and halogenation regiochemistry are discussed. The ipso -substitution of tert -butyl group on chlorine and the exchange of bromine on chlorine and iodine on hydrogen have been observed, along with formation of benzophosphorines. The interaction of tetrachloro- ortho -benzoquinone with phosphorus trichloride and arylacetylenes is proposed as a new modification of the reaction leading to the formation of benzo[ e ]-1,2-oxaphosphorines. The structures of some benzo[ e ]-1,2-oxaphosphorines are determined by the single crystal X-ray diffraction. 相似文献