全文获取类型
收费全文 | 6844篇 |
免费 | 253篇 |
国内免费 | 27篇 |
专业分类
化学 | 4763篇 |
晶体学 | 74篇 |
力学 | 186篇 |
数学 | 1020篇 |
物理学 | 1081篇 |
出版年
2023年 | 51篇 |
2022年 | 105篇 |
2021年 | 203篇 |
2020年 | 167篇 |
2019年 | 165篇 |
2018年 | 118篇 |
2017年 | 121篇 |
2016年 | 266篇 |
2015年 | 226篇 |
2014年 | 236篇 |
2013年 | 365篇 |
2012年 | 422篇 |
2011年 | 515篇 |
2010年 | 297篇 |
2009年 | 283篇 |
2008年 | 406篇 |
2007年 | 397篇 |
2006年 | 384篇 |
2005年 | 356篇 |
2004年 | 318篇 |
2003年 | 256篇 |
2002年 | 228篇 |
2001年 | 92篇 |
2000年 | 80篇 |
1999年 | 85篇 |
1998年 | 59篇 |
1997年 | 63篇 |
1996年 | 90篇 |
1995年 | 60篇 |
1994年 | 56篇 |
1993年 | 49篇 |
1992年 | 55篇 |
1991年 | 49篇 |
1990年 | 32篇 |
1989年 | 29篇 |
1988年 | 19篇 |
1987年 | 25篇 |
1986年 | 35篇 |
1985年 | 37篇 |
1984年 | 25篇 |
1983年 | 38篇 |
1982年 | 24篇 |
1981年 | 18篇 |
1980年 | 21篇 |
1979年 | 22篇 |
1978年 | 19篇 |
1977年 | 28篇 |
1976年 | 14篇 |
1975年 | 10篇 |
1971年 | 13篇 |
排序方式: 共有7124条查询结果,搜索用时 375 毫秒
71.
Scrimin P Tecilla P Tonellato U Veronese A Crisma M Formaggio F Toniolo C 《Chemistry (Weinheim an der Bergstrasse, Germany)》2002,8(12):2753-2763
Three copies of peptide sequences from the peptaibol family, known to affect the permeability of the lipid bilayer of membranes, were connected to tris(2-aminoethyl)amine (TREN), a tripodal metal ion ligand, to prepare functional peptides capable of modifying the permeability of liposomal membranes. Some of the resulting tripodal polypeptide derivatives are very effective in promoting carboxyfluorescein (CF) leakage from CF-loaded unilamellar vesicles composed of a 70:30 phosphatidylcholine/cholesterol blend. The activity of these novel compounds was shown to be tunable upon metal ion coordination of the TREN subunit; the tripodal apopeptide was far more effective than its ZnII complex. Leakage experiments showed that a minimum number of five amino acids per peptide chain is required to form active systems. A mechanism is proposed in which the ZnII ion changes the conformation of the template from extended to globular and thus acts as an allosteric regulator of the activity of the systems. Molecular modeling studies indicate that when the three peptide chains are connected to the template in the extended conformation, the resulting tripodal polypeptide is able to span across the membrane, thus allowing the formation of permeable channels made of a cluster of molecules. The same change of conformation induces, to some extent, fusion of the membranes of different liposomes. 相似文献
72.
THF-gramicidin hybrids 2-4 with the L-THF amino acid 1 in positions 11 and 12 and compounds 5-8 with the D-THF amino acid ent-1 in positions 10 and 11 were synthesized and their ion channel properties were studied by single-channel-current analysis. The replacement of positions 11 and 12 by the L-THF amino acid 1 gave a strongly reduced channel performance. In contrast, replacement of positions 10 and 11 by the D-THF amino acid ent-1 gave rise to new and interesting channel properties. For the permeability ratios, the ion selectivity shifts from Eisenman I towards Eisenman III selectivity and the channels display ms-dynamics. Most remarkable is the asymmetric compound 8, which inserts selectively into a DPhPC membrane and displays voltage-directed gating dynamics. 相似文献
73.
Study of the development of thermoresistance in human pancreatic carcinoma cell lines using proteome analysis 总被引:3,自引:0,他引:3
In order to find candidate proteins that are potentially associated with the thermoresistant phenotype in combination with drug resistance, we analyzed the differential protein expression in vitro in the human pancreatic cancer cell line EPP85-181-P and classical and atypical multidrug-resistant variants and their thermoresistant counterparts using proteomics. This study identifies sets of proteins that may lead to the development of thermoresistance. These results provide a fundamental basis to elucidate the molecular mechanism of thermoresistance and chemoresistance phenomena that may assist the therapy of inoperable cancers. 相似文献
74.
Silvia Gross Andrea Zattin Vito Di Noto Sandra Lavina 《Monatshefte für Chemie / Chemical Monthly》2006,60(3):583-593
Silica-based inorganic–organic hybrid thin films embedding the organically modified oxohafnium clusters (Hf4O2(OMc)12, OMc=OC(O)–C(CH3)=CH2) were obtained by photo-activated free radical copolymerisation of the methacrylate groups of the cluster with those of the
pre-hydrolysed (methacryloxypropyl)trimethoxysilane (MAPTMS, (CH2=C(CH3)C(O)O)(CH2)3Si(OCH3)3). By this route, a covalent anchoring of the cluster to the forming silica network was achieved. Samples characterized by
two different Si/Hf compositions (18:1, 5:1) were prepared. The surface and in-depth composition of the thin films were investigated
through Fourier transform infrared spectroscopy (FT-IR) and X-ray photoelectron spectroscopy (XPS). XPS depth profiles performed on the thin
layers evidenced a homogenous in depth distribution of the hafnium guest species within the whole silica films and sharp film-substrate
interfaces.
Broad band dielectric spectroscopy (BDS) measurements permitted to investigate the electric response of the obtained films
in the frequency and temperature range of 40 Hz – 1 MHz and 0–160°C. 相似文献
75.
The use of DNA to template the assembly of nanoscale wires and protein-functionalized nanogap contacts is described: Specifically, the use of DNA to template the assembly of gold nanowires between conventionally patterned gold contacts on a silicon wafer substrate. Also described is the use of DNA to template the assembly of protein-functionalized nanogap gold contacts on a silicon wafer substrate. Of particular significance is the finding that suitably modified gold nanoparticles recognize and bind selectively the protein-functionalized nanogap and are localized there. 相似文献
76.
DellaGreca M Iesce MR Previtera L Temussi F Zarrelli A Mattia CA Puliti R 《The Journal of organic chemistry》2002,67(25):9011-9015
Androst-4-ene-3,17-dione (1) and 17alpha-methyltestosterone (2) are dimerized in the solid-state by UV radiation. These substances were selected by a search in the CSD among the steroid enones presenting in the crystalline state an intermolecular short contact between a hydrogen alpha to a carbonyl group and the oxygen of an enone system. Dimerization occurs by transfer of the hydrogen to the oxygen and connection between the two involved carbons. Androst-4-ene-3,17-dione (1) affords dimer 3 and trimer 4, both formed by connection of the C-16 of a molecule with the C-3 of a near one. Irradiation of 17alpha-methyltestosterone (2) gives the isomeric trienones 5 and 6. These compounds are reasonably formed by dehydration of unisolated intermediate products 7 and/or 8 obtained by coupling of two molecules through a linkage between the C-2 and the C-3' carbons. The formation mechanisms of the photoproducts are satisfactory explained on the basis of the molecular arrangement of the monomers in the crystal state. Modeling of the dimeric molecules was done using molecular mechanics calculations. A single-crystal X-ray of the dimer of androst-4-ene-3,17-dione confirms the structural interpretation of spectral data. The conformer found in the solid-state agrees well with the results of molecular mechanics calculations. 相似文献
77.
Hay DN Rickert PG Seifert S Firestone MA 《Journal of the American Chemical Society》2004,126(8):2290-2291
The synthesis and purification of a poly(N-isopropylacrylamide)-lipid conjugate and its use in the preparation of a thermoresponsive lipid mesophase is described. Specifically, poly(N-isopropylacrylamide) with a single carboxyl group at one end was activated with dicyclohexylcarbodiimide/N-hydroxysuccinimide to form an active ester. This N-hydroxysuccinimide ester was then used to form a dimyristoyl-sn-glycero-3-phosphoethanolamine conjugate with poly(N-isopropylacrylamide) via an amide bond, rendering the conjugate amphiphilic. Quaternary phases comprising the conjugate, a phosopholipid, dimyristoylphosphatidylcholine, and a cosurfactant, N,N-dimethyldodecylamine-N-oxide, dispersed in water were found to self-assemble at room temperature to form liquid crystalline gels, adopting an expanded lamellar structure. A modest increase in temperature triggered the reversible conversion of the aggregate to a collapsed lamellar structure, while a modest reduction in temperature resulted in its conversion to a nonlamellar phase. The phases were characterized by polarized optical microscopy and small-angle X-ray scattering (SAXS). 相似文献
78.
The Systems AI/CoI2 (A = Alkali Metal, Tl, Ag) and the Crystal Chemistry of the Double Halides AnCoX(n+2) with X = Cl, Br, I The systems AI/CoI2 (A = Cs, Rb, K, Tl, Na, Ag) were investigated by differencethermal analysis. The systems of NaI and AgI are found to be eutectical. A compound A2CoI4 always exists in the other systems. Cs2CoI4 crystallizes in the β-K2SO4 type with a coordination number (C.N.) for Cs equal to 9/10. Results obtained with single crystal technique reveal for the first time that among the double halides Rb2CoI4 is of the monoclinic Sr2GeS4 type (C. N. for Rb = 6(+2)). The compounds K2CoJ4, Tl2CoJ4, T-K2CoBr4, and T-Tl2CoBr4 are isotypic. Both structure groups are characterized by isolated CoX42? tetrahedra. Reflectance spectra and magnetic susceptibilities can be explained on the basis of crystal field theory. – Our results close presently existing gaps in the knowledge on systems of CoBr2 and CoCl2 too. 相似文献
79.
Hogarth G Holman KT Pateman A Sella A Steed JW Richards I 《Dalton transactions (Cambridge, England : 2003)》2005,(16):2688-2695
The iodine(III) reagent, PhI[double bond, length as m-dash]NTs, acts as a source of the nitrene fragment NTs, which undergoes facile insertion into the metal-sulfur bonds of a range of dithiocarbamate complexes. Addition of two equivalents of PhI=NTs to [M(S(2)CNR2)2] affords sulfido-amido complexes [M{SC(NR2)SNTs}2](M=Ni, Cu), which insert two further nitrene fragments to afford zwitterionic tetraamido complexes [M{TsNSC(NR2)SNTs}2](M=Co, Ni, Cu). Crystallographic studies have been carried out on both types of complex allowing possible resonance hydrids of the new ligand types to be assessed. 相似文献
80.
Density functional molecular cluster calculations are combined with X-ray photoelectron spectroscopy (XPS), quadrupolar mass spectrometry (QMS), and diffuse reflectance infrared Fourier transform (DRIFT) spectroscopy to investigate the interaction of CO2 with alpha-Al2O3 and partially reduced alpha-Al2O3. The electronic structure of the stoichiometric and partially reduced substrate, adsorbate geometries, chemisorption enthalpies, and adsorbate vibrational parameters are computed and discussed. Theoretical results agree quite well with experimental data and previous theoretical investigations. As far as the adsorbate-substrate interaction is concerned, the results of our calculations indicate that CO2 forms bidentate-chelating carbonate species. The bonding scheme of this surface complex implies a significant substrate-->adsorbate transfer of charge (from the occupied dangling bond of a surface Lewis base site into one component of the CO2 2 pi u LUMO) assisted by a definitely weaker adsorbate-->substrate donation (from one component of the CO2 1 pi g HOMO into an empty dangling bond of a surface Lewis acid site). Our estimate of the chemisorption enthalpy (-15 kcal/mol) agrees quantitatively with calorimetric data reported for CO2 adsorbed on high surface area alpha-alumina (-16.0 kcal/mol). [Mao, C.-F.; Vannice, M. A. Appl. Catal. A 1994, 111, 151.] According to XPS and QMS outcomes, theoretical results predict that the interaction of CO2 with partially reduced alpha-Al2O3 gives rise to the reduction of the adsorbate to CO and to the concomitant substrate reoxidation. 相似文献