全文获取类型
收费全文 | 3589篇 |
免费 | 344篇 |
国内免费 | 411篇 |
专业分类
化学 | 1959篇 |
晶体学 | 24篇 |
力学 | 74篇 |
综合类 | 45篇 |
数学 | 126篇 |
物理学 | 2116篇 |
出版年
2024年 | 11篇 |
2023年 | 64篇 |
2022年 | 139篇 |
2021年 | 158篇 |
2020年 | 123篇 |
2019年 | 109篇 |
2018年 | 108篇 |
2017年 | 117篇 |
2016年 | 121篇 |
2015年 | 106篇 |
2014年 | 117篇 |
2013年 | 303篇 |
2012年 | 133篇 |
2011年 | 176篇 |
2010年 | 106篇 |
2009年 | 161篇 |
2008年 | 178篇 |
2007年 | 199篇 |
2006年 | 217篇 |
2005年 | 175篇 |
2004年 | 152篇 |
2003年 | 149篇 |
2002年 | 211篇 |
2001年 | 203篇 |
2000年 | 154篇 |
1999年 | 111篇 |
1998年 | 80篇 |
1997年 | 75篇 |
1996年 | 53篇 |
1995年 | 59篇 |
1994年 | 43篇 |
1993年 | 30篇 |
1992年 | 31篇 |
1991年 | 18篇 |
1990年 | 13篇 |
1989年 | 22篇 |
1988年 | 8篇 |
1987年 | 7篇 |
1986年 | 7篇 |
1985年 | 14篇 |
1984年 | 15篇 |
1983年 | 6篇 |
1982年 | 7篇 |
1981年 | 7篇 |
1980年 | 4篇 |
1979年 | 6篇 |
1978年 | 9篇 |
1977年 | 6篇 |
1976年 | 9篇 |
1975年 | 5篇 |
排序方式: 共有4344条查询结果,搜索用时 505 毫秒
111.
Christian K. Riener Andreas Ebner Alex A. Gall Yuri L. Lyubchenko Hermann J. Gruber 《Analytica chimica acta》2003,479(1):59-75
We have established an easy-to-use test system for detecting receptor-ligand interactions on the single molecule level using atomic force microscopy (AFM). For this, avidin-biotin, probably the best characterized receptor-ligand pair, was chosen. AFM sensors were prepared containing tethered biotin molecules at sufficiently low surface concentrations appropriate for single molecule studies. A biotin tether, consisting of a 6 nm poly(ethylene glycol) (PEG) chain and a functional succinimide group at the other end, was newly synthesized and covalently coupled to amine-functionalized AFM tips. In particular, PEG800 diamine was glutarylated, the mono-adduct NH2-PEG-COOH was isolated by ion exchange chromatography and reacted with biotin succinimidylester to give biotin-PEG-COOH which was then activated as N-hydroxysuccinimide (NHS) ester to give the biotin-PEG-NHS conjugate which was coupled to the aminofunctionalized AFM tip. The motional freedom provided by PEG allows for free rotation of the biotin molecule on the AFM sensor and for specific binding to avidin which had been adsorbed to mica surfaces via electrostatic interactions. Specific avidin-biotin recognition events were discriminated from nonspecific tip-mica adhesion by their typical unbinding force (∼40 pN at 1.4 nN/s loading rate), unbinding length (<13 nm), the characteristic nonlinear force-distance relation of the PEG linker, and by specific block with excess of free d-biotin. The convenience of the test system allowed to evaluate, and compare, different methods and conditions of tip aminofunctionalization with respect to specific binding and nonspecific adhesion. It is concluded that this system is well suited as calibration or start-up kit for single molecule recognition force microscopy. 相似文献
112.
K. Yu. Chegaev A. N. Kravchenko O. V. Lebedev Yu. A. Strelenko P. A. Belyakov 《Chemistry of Heterocyclic Compounds》2002,38(10):1250-1252
N-Trimethylsilyl derivatives of 2,4,6,8-tetraazabicyclo[3.3.0]octane-3,7-diones have been prepared for the first time and the electrophilic substitution reaction of the trimethylsilyl group has been studied. 相似文献
113.
K.B. Helean S.V. Ushakov A. Navrotsky J. Lian J.M. Farmer 《Journal of solid state chemistry》2004,177(6):1858-1866
High-temperature oxide melt solution calorimetry and Rietveld refinements of powder X-ray diffraction data were used to investigate the structure (Fd3m; Z=8) and energetics of a series of RE2Ti2O7 (RE=Sm-Lu) compounds with the pyrochlore structure as well as La2Ti2O7 with a layered perovskite-type structure. All of the RE-titanates were found to be stable in enthalpy with respect to their oxides. In the pyrochlore series, Lu2Ti2O7 was least stable in enthalpy (ΔHf-ox at 298 K=−56.0±4.0 kJ/mol); the most stable materials were Gd-, Eu-, and Sm2Ti2O7 with ΔHf-ox at 298 K=−113.4±2.7, −106.1±4.2, −115.4±4.2 kJ/mol, respectively. In general, as the radius ratio of the A- to B-site cations, RA/RB, decreases, the pyrochlore structure becomes less stable. The trend of ionic radius of the RE3+ cation vs. ΔHf-ox at 298 K is non-linear and approximately parallels the increasing “resistance” to ion-beam-induced amorphization as RA/RB decreases. 相似文献
114.
The fast trace analysis method used to monitor 2,3,7,8-TCDD in stack gas during the incineration of the waste from Seveso is described. The sampling of volatile organic compounds from flue gases, distributed between all three aggregation states, is based on a micromethod developed for the trace analysis of water using a specially dimensioned adsorptive charcoal filter (1.5 mg charcoal). In conjunction with subsequent GC/MS measurements the rapid “fast cycle trace analysis” ensured specific 2,3,7,8-TCDD detection down to 100 pg per m3 flue gas in cycle times of about 1–2 hours. 相似文献
115.
Anand Pal Singh P. Ramos Cabrer E. Alvarez-Parrilla F. Meijide J. Vázquez Tato 《Journal of inclusion phenomena and macrocyclic chemistry》1999,35(1-2):335-348
In order to study its guest binding and the inclusion phenomena, 6-deoxy-6-(aminoethyl)amino--cyclodextrin (CDN) was synthesised and its binding properties examined. The complexation phenomena of sodium cholate (NaC) and sodium deoxycholate (NaDC) with CDN has been monitored by the NMR method using 13C chemical shift data. The method of continuous variation Job's method has been used to determine the stoichiometry of these supramolecular complexes. The Job's plot confirms the 1 : 1 supramolecular complex for NaC: CDN and the 1 : 2 supramolecular complex for NaDC: CDN. The interaction of NaC and NaDC with CDN has been obtained through two-dimensional Rotational Nuclear Overhauser Effect Spectroscopy (ROESY) NMR. Equilibrium constants were also obtained from 13C chemical shift data (C-1, C-3 & C-4) at different pH values (7, 9, & 11). 相似文献
116.
117.
Dr. Victor A. Klushin Dr. Vera P. Kashparova Anastasia A. Chizhikova Dr. Veronica E. Andreeva Dr. Daria V. Chernysheva Anna A. Ulyankina Dr. Olga Yu. Kutsevalova Prof. Dr. Nina V. Smirnova Prof. Dr. Oleg A. Kravchenko Prof. Dr. Valentin P. Ananikov 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(10):3382-3396
Development of sustainable bio-based materials for removal of toxic contaminants from water is a high priority goal. Novel bio-based binary and ternary copolymers with enhanced ion-exchange, adsorption and antibacterial properties were obtained by using plant biomass-derived diallyl esters of furandicarboxylic acid (FDCA) as crosslinking agents and easily available vinyl monomers. The synthesized copolymer materials showed higher sorption capacities for NiII, CoII and CuII compared to the commercial ion-exchange resins, and they maintained their high metal adsorption capacities for over 10 cycles of regeneration. The synthesized copolymer gels containing 1–5 wt % of the crosslinker showed excellent water absorption capacities. The synthesized copolymers with 1 % crosslinker content showed swelling ratios high enough to also act as moisture absorbents. Synthesized copolymers with crosslinker content of 10 wt % performed as contact-active antibacterials by inhibiting the growth of Gram-positive (S. aureus) and Gram-negative bacteria (E. coli, K. pneumonia) in suspension tests. 相似文献
118.
The energy transfer from the upper triplet states of diphenylamine, naphthalene and triphenylene to toluene and hexene-1 is studed. Two mechanisms of dissipation transferred energy in solvents are discussed. 相似文献
119.
We studied the symmetry and spatial uniformity of the orientational order of the biaxial nematic phase in the light of recent experimental observations of phase biaxiality in thermotropic bent-core and calamitic-tetramer nematics. Evidence is presented supporting monoclinic symmetry, instead of the usually assumed orthorhombic symmetry. The use of deuterium nuclear magnetic resonance to differentiate between the possible symmetries is described. The spatial aspects of biaxial order are presented in the context of the cluster model, wherein macroscopic biaxiality can result from the field-induced alignment of biaxial and possibly polar domains. The implications of different symmetries on the alignment of biaxial nematics and on the measurements of biaxial order are discussed in conjunction with the microdomain structure of the biaxial phase. 相似文献
120.
Giulia DArrigo Eleonora Gianquinto Giulia Rossetti Gabriele Cruciani Stefano Lorenzetti Francesca Spyrakis 《Molecules (Basel, Switzerland)》2021,26(6)
Flavonoids are plant bioactives that are recognized as hormone-like polyphenols because of their similarity to the endogenous sex steroids 17β-estradiol and testosterone, and to their estrogen- and androgen-like activity. Most efforts to verify flavonoid binding to nuclear receptors (NRs) and explain their action have been focused on ERα, while less attention has been paid to other nuclear and non-nuclear membrane androgen and estrogen receptors. Here, we investigate six flavonoids (apigenin, genistein, luteolin, naringenin, quercetin, and resveratrol) that are widely present in fruits and vegetables, and often used as replacement therapy in menopause. We performed comparative computational docking simulations to predict their capability of binding nuclear receptors ERα, ERβ, ERRβ, ERRγ, androgen receptor (AR), and its variant ART877A and membrane receptors for androgens, i.e., ZIP9, GPRC6A, OXER1, TRPM8, and estrogens, i.e., G Protein-Coupled Estrogen Receptor (GPER). In agreement with data reported in literature, our results suggest that these flavonoids show a relevant degree of complementarity with both estrogen and androgen NR binding sites, likely triggering genomic-mediated effects. It is noteworthy that reliable protein–ligand complexes and estimated interaction energies were also obtained for some suggested estrogen and androgen membrane receptors, indicating that flavonoids could also exert non-genomic actions. Further investigations are needed to clarify flavonoid multiple genomic and non-genomic effects. Caution in their administration could be necessary, until the safe assumption of these natural molecules that are largely present in food is assured. 相似文献