全文获取类型
收费全文 | 4026篇 |
免费 | 129篇 |
国内免费 | 58篇 |
专业分类
化学 | 2565篇 |
晶体学 | 15篇 |
力学 | 134篇 |
数学 | 735篇 |
物理学 | 764篇 |
出版年
2024年 | 4篇 |
2023年 | 28篇 |
2022年 | 104篇 |
2021年 | 117篇 |
2020年 | 102篇 |
2019年 | 117篇 |
2018年 | 114篇 |
2017年 | 97篇 |
2016年 | 163篇 |
2015年 | 124篇 |
2014年 | 144篇 |
2013年 | 267篇 |
2012年 | 296篇 |
2011年 | 300篇 |
2010年 | 195篇 |
2009年 | 165篇 |
2008年 | 270篇 |
2007年 | 225篇 |
2006年 | 270篇 |
2005年 | 240篇 |
2004年 | 186篇 |
2003年 | 140篇 |
2002年 | 124篇 |
2001年 | 63篇 |
2000年 | 46篇 |
1999年 | 49篇 |
1998年 | 29篇 |
1997年 | 25篇 |
1996年 | 28篇 |
1995年 | 22篇 |
1994年 | 27篇 |
1993年 | 13篇 |
1992年 | 18篇 |
1991年 | 17篇 |
1990年 | 8篇 |
1989年 | 5篇 |
1988年 | 5篇 |
1986年 | 4篇 |
1985年 | 7篇 |
1984年 | 6篇 |
1983年 | 8篇 |
1982年 | 5篇 |
1981年 | 6篇 |
1980年 | 7篇 |
1979年 | 5篇 |
1976年 | 4篇 |
1975年 | 2篇 |
1974年 | 2篇 |
1972年 | 2篇 |
1971年 | 2篇 |
排序方式: 共有4213条查询结果,搜索用时 0 毫秒
71.
Electronic and structural factors controlling the competition between 5-exo-dig and 6-endo-dig cyclizations of sp2-radicals were analyzed using a combination of available experimental data and computation. Although the stereoelectronically favored 5-exo pathways usually has the lower activation energy, formation of a new aromatic ring not only makes the 6-endo process favorable thermodynamically in conjugated systems but also lowers its activation barrier to the extent where the 5-exo/6-endo selectivity is controlled by subtle factors such as the different sensitivity of the two pathways to strain effects in polycyclic systems. In particular, the stronger sensitivity of the 5-exo pathway to strain leads to a crossover in selectivity. The 6-endo cyclization is kinetically favored in smaller (and strained) cycles, whereas the 5-exo cyclization has lower barriers in the larger rings. 相似文献
72.
Sergey I. Vdovenko Igor I. Gerus Natalia V. Lutenko Valery P. Kukhar Jacek Wjcik 《Journal of Molecular Structure》2007,840(1-3):125-132
Spatial structure of six β-substituted enones, with common structure R1O–CR2CH–COCF3, were R1 = C2H5, R2 = H (ETBO); R1 = R2 = CH3 (TMPO); R1 = C2H5, R2 = C6H5 (ETPO); R1 = C2H5, R2 = 4- O2NC6H4 (ETNO); R1 = C2H5, R2 = C(CH3)3 (ETDO) were investigated by 1H and 19F NMR, infrared spectroscopy and AM1 calculations. NMR spectra revealed that enones (MBO), (ETBO) and (TMPO) are exclusively (3E) isomers, whereas in (ETPO), (ETNO) and especially in (ETDO) the percentage of (3Z) isomers is significant and depends on the nature of solvents. Conformational behaviour of studied enones are determined by the rotation around of CC double bond, C–C and C–O single bonds (correspondingly trifluoroacetyl and alkoxy groups), and (EZZ) conformer being the most stable in all cases. IR spectra revealed that with the exception of (ETDO) (EZZ) conformer is most populated in all cases. Bulky substituents like phenyl or tert-butyl group at β-position of enone result in the equilibrium mainly between (EZZ) and (ZZZ) forms, whereas β-hydrogen and β-methyl substituents determine the equilibrium between (EZZ) and (EEZ) or (EZE) conformers. 相似文献
73.
G. S. Lekshmi Tamilselvi Ramasamy Olha Bazaka Igor Levchenko Kateryna Bazaka Raji Govindan Mohandas Mandhakini 《Molecules (Basel, Switzerland)》2022,27(18)
Scaling up the production of functional reduced graphene oxide (rGO) and its composites requires the use of low-cost, simple, and sustainable synthesis methods, and renewable feedstocks. In this study, silver oxide-decorated rGO (AgxO−rGO) composites were prepared by open-air combustion of mustard oil, essential oil-containing cooking oil commercially produced from the seeds of Brassica juncea. Silver oxide (AgxO) nanoparticles (NPs) were synthesized using Coleus aromaticus leaf extract as a reducing agent. Formation of mustard seed rGO and AgxO NPs was confirmed by UV-visible characteristic peaks at 258 nm and 444 nm, respectively. rGO had a flake-like morphology and a crystalline structure, with Raman spectra showing clear D and G bands with an ID/IG ratio of 0.992, confirming the fewer defects in the as-prepared mustard oil-derived rGO (M−rGO). The rGO-AgxO composite showed a degradation efficiency of 81.9% with a rate constant k−1 of 0.9506 min−1 for the sodium salt of benzidinediazo-bis-1-naphthylamine-4-sulfonic acid (known as the azo dye Congo Red) in an aqueous solution under visible light irradiation. The composite also showed some antimicrobial activity against Klebsilla pneomoniae, Escherichia coli, and Staphylococcus aureus bacterial cells, with inhibition zones of ~15, 18, and 14 mm, respectively, for a concentration of 300 µg/mL. At 600 µg/mL concentration, the composite also showed moderate scavenging activity for 2,2-diphenyl-1-picrylhydrazyl of ~30.6%, with significantly lower activities measured for AgxO (at ~18.1%) and rGO (~8%) when compared to control. 相似文献
74.
Dongping Li Yaroslav Ilnytskyy Esmaeel Ghasemi Gojani Olga Kovalchuk Igor Kovalchuk 《Molecules (Basel, Switzerland)》2022,27(18)
Cannabis sativa is one of the oldest cultivated plants. Many of the medicinal properties of cannabis are known, although very few cannabis-based formulations became prescribed drugs. Previous research demonstrated that cannabis varieties are very different in their medicinal properties, likely due to the entourage effect—the synergistic or antagonistic effect of various cannabinoids and terpenes. In this work, we analyzed 25 cannabis extracts containing high levels of delta-9-tetrahydrocannabinol (THC). We used HCC1806 squamous cell carcinoma and demonstrated various degrees of efficiency of the tested extracts, from 66% to 92% of growth inhibition of cancer cells. Inflammation was tested by induction of inflammation with TNF-α/IFN-γ in WI38 human lung fibroblasts. The efficiency of the extracts was tested by analyzing the expression of COX2 and IL6; while some extracts aggravated inflammation by increasing the expression of COX2/IL6 by 2-fold, other extracts decreased inflammation, reducing expression of cytokines by over 5-fold. We next analyzed the level of THC, CBD, CBG and CBN and twenty major terpenes and performed clustering and association analysis between the chemical composition of the extracts and their efficiency in inhibiting cancer growth and curbing inflammation. A positive correlation was found between the presence of terpinene (pval = 0.002) and anti-cancer property; eucalyptol came second, with pval of 0.094. p-cymene and β-myrcene positively correlated with the inhibition of IL6 expression, while camphor correlated negatively. No significant correlation was found for COX2. We then performed a correlation analysis between cannabinoids and terpenes and found a positive correlation for the following pairs: α-pinene vs. CBD, p-cymene vs. CBGA, terpenolene vs. CBGA and isopulegol vs. CBGA. Our work, thus, showed that most of high-THC extracts demonstrate anti-cancer activity, while only certain selected extracts showed anti-inflammatory activity. Presence of certain terpenes, such as terpinene, eucalyptol, cymene, myrcene and camphor, appear to have modulating effects on the activity of cannabinoids. 相似文献
75.
Anna K. Matyukhina Ekaterina N. Zorina-Tikhonova Alexander S. Goloveshkin Konstantin A. Babeshkin Nikolay N. Efimov Mikhail A. Kiskin Igor L. Eremenko 《Molecules (Basel, Switzerland)》2022,27(19)
New CoII substituted malonate field-induced molecular magnets {[Rb6Co3(cpdc)6(H2O)12]∙6H2O}n (1) and [Cs2Co(cpdc)2(H2O)6]n (2) (where cpdc2− stands for cyclopropane-1,1-dicarboxylic acid dianions) were synthesized. Both compounds contain mononuclear bischelate fragments {CoII(cpdc)2(H2O)2}2− where the quasi-octahedral cobalt environment (CoO6) is complemented by water molecules in apical positions. The alkali metal atoms play the role of connectors between the bischelate fragments to form 3D and 2D polymeric structures for 1 and 2, respectively. Analysis of dc magnetic data using the parametric Griffith Hamiltonian for high-spin CoII supported by ab initio calculations revealed that both compounds have an easy axis of magnetic anisotropy. Compounds 1 and 2 exhibit slow magnetic relaxation under an external magnetic field (HDC = 1000 and 1500 Oe, respectively). 相似文献
76.
Ramil F. Fatykhov Igor A. Khalymbadzha Ainur D. Sharapov Anastasia P. Potapova Nataliya N. Mochulskaya Anton N. Tsmokalyuk Alexandra V. Ivoilova Polina N. Mozharovskaia Sougata Santra Oleg N. Chupakhin 《Molecules (Basel, Switzerland)》2022,27(20)
A different type of MnO2-induced oxidative cyclization of dihydrotriazines has been developed. These dihydrotriazines are considered as a “formal” Schiff’s base. This method provided easy access to naphthofuro-fused triazine via the C-C/C-O oxidative coupling reaction. The reaction sequence comprised the nucleophilic addition of 2-naphthol or phenol to 1,2,4-triazine, followed by oxidative cyclization. The scope and limitations of this novel coupling reaction have been investigated. Further application of the synthesized compound has been demonstrated by synthesizing carbazole-substituted benzofuro-fused triazines. The scalability of the reaction was demonstrated at a 40 mmol load. The mechanistic study strongly suggests that this reaction proceeds through the formation of an O-coordinated manganese complex. 相似文献
77.
Artem S. Agarkov Anna A. Nefedova Elina R. Gabitova Alexander S. Ovsyannikov Syumbelya K. Amerhanova Anna P. Lyubina Alexandra D. Voloshina Pavel V. Dorovatovskii Igor A. Litvinov Svetlana E. Solovieva Igor S. Antipin 《Molecules (Basel, Switzerland)》2022,27(22)
A series of new thiazolo[3,2-a]pyrimidines different by aryl substituents in 2 and 5 positions are synthesized and characterized in solution as well as in the crystalline phase using 1H and 13C NMR-, IR-spectroscopies, mass-spectrometry methods, and single crystal X-ray diffraction (SCXRD). The SCXRD study revealed the role of intermolecular H-bonding in the formation of supramolecular architectures (racemic monomers, centrosymmetric racematic dimers, or homochiral 1D chains) of obtained thiazolo[3,2-a]pyrimidines derivatives depending on solvents (aprotic DMSO or protic EtOH) used upon the crystallization process. Moreover, the in vitro study of cytotoxicity toward different tumor cells showed their high or moderate efficiency with moderate cytotoxicity against normal liver cells which allows to consider the obtained thiazolo[3,2-a]pyrimidine derivatives as promising candidates for application as antitumor agents. 相似文献
78.
In this research, we studied, in detail, the behavior of common PNIPAM microgels, obtained through surfactant-free precipitation polymerization, in a number of organic solvents. We showed that many of the selected solvents serve as good solvents for the PNIPAM microgels and that the size and architecture of the microgels depend on the solvent chosen. Expanding the range of solvents used for PNIPAM microgel incubation greatly enhances the possible routes for microparticle functionalization and modification, as well as the encapsulation of water-insoluble species. In this demonstration, we successfully encapsulated water-insoluble Sudan III dye in PNIPAM microgels and prepared the aqueous dispersions of such composite-colored microparticles. 相似文献
79.
Dmitriy S. Yambulatov Irina A. Lutsenko Stanislav A. Nikolaevskii Pavel A. Petrov Ivan V. Smolyaninov Irina K. Malyants Victoria O. Shender Mikhail A. Kiskin Alexey A. Sidorov Nadezhda T. Berberova Igor L. Eremenko 《Molecules (Basel, Switzerland)》2022,27(23)
Three new Pt(II) complexes [(dpp-DAD)PtCl2] (I), [(Mes-DAD(Me)2)PtCl2] (II) and [(dpp-DAD(Me)2)PtCl2] (III) were synthesized by the direct reaction of [(CH3CN)2PtCl2] and corresponding redox-active 1,4-diaza-1,3-butadienes (DAD). The compounds were isolated in a single crystal form and their molecular structures were determined by X-ray diffraction. The purity of the complexes and their stability in solution was confirmed by NMR analysis. The Pt(II) ions in all compounds are in a square planar environment. The electrochemical reduction of complexes I–III proceeds in two successive cathodic stages. The first quasi-reversible reduction leads to the relatively stable monoanionic complexes; the second cathodic stage is irreversible. The coordination of 1,4-diaza-1,3-butadienes ligands with PtCl2 increases the reduction potential and the electron acceptor ability of the DAD ligands. The synthesized compounds were tested in relation to an adenocarcinoma of the ovary (SKOV3). 相似文献
80.
Developing more efficient catalytic processes using abundant and low toxicity transition metals is key to enable their mainstream use in synthetic chemistry. We have rationally designed a new Mn(i)-catalyst for hydroarylation reactions that displays much improved catalytic activity over the commonly used MnBr(CO)5. Our catalyst, MnBr(CO)3(MeCN)2, avoids the formation of the off-cycle manganacycle-(CO)4 species responsible for low catalyst activity, allowing near room temperature hydroarylation of alkenes and alkynes with broad functional group tolerance including late stage functionalisation and diversification of bioactive molecules.A Mn(i)-catalyst for hydroarylation reactions, MnBr(CO)3(MeCN)2, avoids the formation of the off-cycle manganacycle-(CO)4 species responsible for low catalyst activity typical of MnBr(CO)5, leading to mild and broad scope hydroarylation. 相似文献