全文获取类型
收费全文 | 11807篇 |
免费 | 550篇 |
国内免费 | 52篇 |
专业分类
化学 | 9669篇 |
晶体学 | 70篇 |
力学 | 166篇 |
数学 | 1355篇 |
物理学 | 1149篇 |
出版年
2023年 | 123篇 |
2022年 | 394篇 |
2021年 | 601篇 |
2020年 | 381篇 |
2019年 | 355篇 |
2018年 | 257篇 |
2017年 | 220篇 |
2016年 | 480篇 |
2015年 | 406篇 |
2014年 | 476篇 |
2013年 | 722篇 |
2012年 | 867篇 |
2011年 | 942篇 |
2010年 | 595篇 |
2009年 | 472篇 |
2008年 | 770篇 |
2007年 | 703篇 |
2006年 | 673篇 |
2005年 | 494篇 |
2004年 | 471篇 |
2003年 | 348篇 |
2002年 | 313篇 |
2001年 | 127篇 |
2000年 | 98篇 |
1999年 | 77篇 |
1998年 | 74篇 |
1997年 | 64篇 |
1996年 | 79篇 |
1995年 | 58篇 |
1994年 | 49篇 |
1993年 | 43篇 |
1992年 | 36篇 |
1991年 | 40篇 |
1990年 | 30篇 |
1989年 | 40篇 |
1988年 | 26篇 |
1987年 | 30篇 |
1986年 | 37篇 |
1985年 | 60篇 |
1984年 | 40篇 |
1983年 | 33篇 |
1982年 | 45篇 |
1981年 | 38篇 |
1980年 | 32篇 |
1979年 | 20篇 |
1978年 | 13篇 |
1977年 | 21篇 |
1976年 | 16篇 |
1974年 | 11篇 |
1973年 | 8篇 |
排序方式: 共有10000条查询结果,搜索用时 171 毫秒
161.
Alicja Janik Anna Chyra Katarzyna Stadnicka 《Acta Crystallographica. Section C, Structural Chemistry》2007,63(10):o572-o575
The crystal structure of a protected l ‐tyrosine, namely N‐acetyl‐l ‐tyrosine methyl ester monohydrate, C12H15NO4·H2O, was determined at both 293 (2) and 123 (2) K. The structure exhibits a network of O—H...O and N—H...O hydrogen bonds, in which the water molecule plays a crucial role as an acceptor of one and a donor of two hydrogen bonds. Molecules of water and of the protected l ‐tyrosine form hydrogen‐bonded layers perpendicular to [001]. C—H...π interactions are observed in the hydrophobic regions of the structure. The structure is similar to that of N‐acetyl‐l ‐tyrosine ethyl ester monohydrate [Soriano‐García (1993). Acta Cryst. C 49 , 96–97]. 相似文献
162.
Patricia M. Nassar Rose M.Z.Georgetto Naal Silvia H. de Pauli João B.S. Bonilha Laura T. Okano Frank H. Quina 《Journal of colloid and interface science》1997,190(2):461
In aqueous solution, the interaction between sodium dodecyl sulfate (SDS) and poly(ethylene glycol) (PEG) results in the formation of small aggregates or clusters of SDS attached to the PEG polymer chain. Selectivity coefficients for exchange of two monovalent (N-methyl-4-cyanopyridinium cation and Tl+) and two divalent (methylviologen cation and Cu2+) counterions at the surface of SDS–PEG clusters, determined employing photophysical techniques, are similar, but not identical, to those for exchange at the surface of SDS micelles in the absence of PEG. The principal factor affecting ion exchange selectivity in SDS–PEG clusters does not appear to be aggregate size or surface charge density but rather the presence of poly(oxyethylene) subunits at the aggregate surface. 相似文献
163.
164.
Körner A Larsson A Piculell L Wittgren B 《The journal of physical chemistry. B》2005,109(23):11530-11537
A systematic study of the dissolution of dry, polydisperse poly(ethylene oxide) (PEO) samples, obtained from mixtures of low-molecular-weight and high-molecular-weight PEO, was made. During the dissolution process, the individual release of the low- and high-molecular-weight fractions was monitored. The high-molecular-weight/low-molecular-weight ratio controls the release rate, and the fraction of high-molecular-weight polymers dominates the effect on the overall release rate in mixed PEO tablets. Both fractions are released at the same rate during the main part of the dissolution process; however, during the initial dissolution period a fractionation occurs. The release rate is not a unique function of the average molecular weight of the polymer, but also depends on the polydispersity. By contrast, the average dimension of a polymer coil, as given by the intrinsic viscosity, gives a good prediction of the release rate irrespective of the polydispersity or details of the molecular weight distribution. 相似文献
165.
Express detection of nonylphenol in water samples by fluorescence polarization immunoassay 总被引:6,自引:0,他引:6
Yakovleva JN Lobanova AY Shutaleva EA Kourkina MA Mart'ianov AA Zherdev AV Dzantiev BB Eremin SA 《Analytical and bioanalytical chemistry》2004,378(3):634-641
The development of express method for detection of endocrine-disrupting chemicals (EDC) such as alkylphenols is required for ecological monitoring. Several attempts have been made to produce antibodies against 4-nonylphenol (NP) in recent years. This work describes the production of new antibodies against NP and also summarizes the characterization of antibodies obtained earlier. Three approaches used to produce alkylphenol-specific antibodies are compared; these are based on: 1. omega-(4-hydroxyphenyl)nonanoic or omega-(4-hydroxyphenyl)heptanoic acid NP derivatives designed to mimic the linear NP isomer; 2. 4-aminophenol, which potentially mimics various substituted phenolic compounds with different side-chain structures at position 4 of the benzene ring; and 3. a mixture of branched NP isomers, conjugated to the carrier protein via a benzene ring by the Mannich reaction, and expected to be the closest mimic of NP structure by preserving its natural alkyl moiety.Fluorescence polarization immunoassays based on different combinations of antibody and labeled antigen for screening detection of NP were developed and structural aspects of assay sensitivity and specificity were investigated. The assays based on the antisera raised against omega-(4-hydroxyphenyl)nonanoic acid and NP conjugate via Mannich reaction are capable of express detection of NP with detection limit of 7 microg mL(-1 )and assay dynamic range of 18-300 microg mL(-1). 相似文献
166.
A new method of synthesizing the alkaloid aspidospermidine (1), based on building ring E on the pyridocarbazole [ABCD] ring structure, is reported. The preparation of the pyridocarbazole framework of Aspidosperma alkaloids is a new three-step synthetic application of 2-(1,3-dithian-2-yl)indoles. A tandem conjugate addition-alkylation reaction starting from indolyldithiane (4), 3-methylenelactam 6, and EtI yields the adduct 17. Treatment of lactam 17 with DIBALH leads to formation of the naphthyridoindole 18. Compound 18 isomerizes in aqueous AcOH to yield pyridocarbazole 3. Finally, closure of ring E and subsequent reduction of the dithiane ring produces aspidospermidine. Pyridocarbazoles 2 and 10 were prepared as models. 相似文献
167.
Weronika Gruszka Anna Lykkeberg Gary S. Nichol Michael P. Shaver Antoine Buchard Jennifer A. Garden 《Chemical science》2020,11(43):11785
Heterometallic cooperativity is an emerging strategy to elevate polymerisation catalyst performance. Here, we report the first heterotrimetallic Na/Zn2 and K/Zn2 complexes supported by a ProPhenol ligand, which deliver “best of both” in cyclic ester ring-opening polymerisation, combining the outstanding activity (Na/K) and good control (Zn2) of homometallic analogues. Detailed NMR studies and density-functional theory calculations suggest that the Na/Zn2 and K/Zn2 complexes retain their heterometallic structures in the solution-state. To the best of our knowledge, the K/Zn2 analogue is the most active heterometallic catalyst reported for rac-lactide polymerisation (kobs = 1.7 × 10−2 s−1), giving activities five times faster than the Na/Zn2 complex. These versatile catalysts also display outstanding performance in ε-caprolatone and δ-valerolactone ring-opening polymerisation. These studies provide underpinning methodologies for future heterometallic polymerisation catalyst design, both in cyclic ester polymerisation and other ring-opening (co)polymerisation reactions.Cooperative heterotrimetallic Na/Zn2 and K/Zn2 complexes combine the excellent activities and control of the homometallic analogues, giving “best of both” in cyclic ester ring-opening polymerisation. 相似文献
168.
Ogrin D van Poppel LH Bott SG Barron AR 《Dalton transactions (Cambridge, England : 2003)》2004,(21):3689-3694
The reaction of AlMe(3) and [((t)Bu)(2)Al(micro-OPh)](2) with pyrazine (pyz), 4,4'-bipyridine (4-4'-bipy), 1,2-bis(4-pyridyl)ethane (bpetha) and 1,2-bis(4-pyridyl)ethylene (bpethe) yields (Me(3)Al)(2)(micro-pyz)(1), (Me(3)Al)(2)(micro-4,4'-bipy)(2), (Me(3)Al)(2)(micro-bpetha)(3), (Me(3)Al)(2)(micro-bipethe)(4), Al((t)Bu)(2)(OPh)(pyz)(5), [((t)Bu)(2)Al(OPh)](2)(micro-4,4-bipy)(6a), [((t)Bu)(2)Al(OPh)](2)(micro-bpetha)(7a), [((t)Bu)(2)Al(OPh)](2)(micro-bipethe)(8a). Compounds 1-4, 6a and 7a have been confirmed by X-ray crystallography. In solution compounds 1-4 undergo a rapid ligand-dissociation equilibrium resulting in a time-average spectrum in the (1)H NMR. In contrast, the solution equilibria for compounds 5-8a are sufficiently slow such that the mono-aluminium compounds may be observed by (1)H NMR spectroscopy: Al((t)Bu)(2)(OPh)(4,4-bipy)(6b), Al((t)Bu)(2)(OPh)(bpetha)(7b) and Al((t)Bu)(2)(OPh)(bpethe)(8b). The inability to isolate [((t)Bu)(2)Al(OPh)](2)(micro-pyz) and the relative stability of each complex is discussed with respect to the steric interactions across the bridging ligand (L) and the electronic effect on one Lewis acid-base interaction by the second Lewis acid-base interaction on the same ligand. 相似文献
169.
Laura Marcu Javier A. Jo Pramod V. Butte William H. Yong Brian K. Pikul Keith L. Black Reid C. Thompson 《Photochemistry and photobiology》2004,80(1):98-103
Fluorescence spectroscopy of the endogenous emission of brain tumors has been researched as a potentially important method for the intraoperative localization of brain tumor margins. We investigated the use of time‐resolved, laser‐induced fluorescence spectroscopy for demarcation of primary brain tumors by studying the time‐resolved spectra of gliomas. The fluorescence of human brain samples (glioblastoma multiforme, cortex and white matter: six patients, 23 sites) was induced ex vivo with a pulsed nitrogen laser (337 nm, 3 ns). The time‐resolved spectra were detected in a 360–550 nm wavelength range using a fast digitizer and gated detection. Parameters derived from both the spectral‐ (intensities from narrow spectral bands) and the time domain (average lifetime) measured at 390 and 460 nm were used for tissue characterization. We determined that high‐grade gliomas are characterized by fluorescence lifetimes that varied with the emission wavelength (>3 ns at 390 nm, <1 ns at 460 nm) and their emission is overall longer than that of normal brain tissue. Our study demonstrates that the use of fluorescence lifetime not only improves the specificity of fluorescence measurements but also allows a more robust evaluation of data collected from brain tissue. Combined information from both the spectraland the time domain can enhance the ability of fluorescencebased techniques to diagnose and detect brain tumor margins intraoperatively. 相似文献
170.
Summary Theortho-metallated complex [RhP3Pt] [P=P(OPh)3, P=P(OC6H4)(OPh)2] was obtained in the reaction of [RhP4]ClO4 with KOH. It reacts easily with proton donors HX (X=ClO4, F, Cl, SCN, or acetylacetonate) to produce complexes [RhP3X] when X is a strong donor. If X is a weaker donor (X=ClO4 or F), pentacoordinate compounds of the type [PhP4X] are formed. [RhP3P] reacts with acetylacetone (Hacac) to produce [Rh(acac)P2]. 相似文献