全文获取类型
收费全文 | 11767篇 |
免费 | 321篇 |
国内免费 | 77篇 |
专业分类
化学 | 8425篇 |
晶体学 | 116篇 |
力学 | 245篇 |
数学 | 1547篇 |
物理学 | 1832篇 |
出版年
2023年 | 61篇 |
2022年 | 59篇 |
2021年 | 116篇 |
2020年 | 157篇 |
2019年 | 147篇 |
2018年 | 120篇 |
2017年 | 111篇 |
2016年 | 224篇 |
2015年 | 230篇 |
2014年 | 288篇 |
2013年 | 512篇 |
2012年 | 670篇 |
2011年 | 862篇 |
2010年 | 420篇 |
2009年 | 361篇 |
2008年 | 773篇 |
2007年 | 779篇 |
2006年 | 818篇 |
2005年 | 827篇 |
2004年 | 726篇 |
2003年 | 593篇 |
2002年 | 558篇 |
2001年 | 153篇 |
2000年 | 142篇 |
1999年 | 131篇 |
1998年 | 154篇 |
1997年 | 170篇 |
1996年 | 187篇 |
1995年 | 110篇 |
1994年 | 123篇 |
1993年 | 116篇 |
1992年 | 96篇 |
1991年 | 84篇 |
1990年 | 62篇 |
1989年 | 62篇 |
1988年 | 63篇 |
1987年 | 66篇 |
1986年 | 53篇 |
1985年 | 97篇 |
1984年 | 95篇 |
1983年 | 65篇 |
1982年 | 72篇 |
1981年 | 90篇 |
1980年 | 94篇 |
1979年 | 64篇 |
1978年 | 49篇 |
1977年 | 46篇 |
1976年 | 40篇 |
1975年 | 42篇 |
1974年 | 37篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
71.
72.
Deprotonation of 1,2-C(70)H(2) with TBAOH, followed by alkylation with methyl bromoacetate, results in formation of a C1-monoalkylated 1,2-dihydro-C(70) derivative. The position of the alkyl group (C1) was established by NMR spectroscopy and comparison with literature spectra of C2-monoalkylated analogs. Presumably, C1-alkylation is the major process due to selective deprotonation of 1,2-C(70)H(2) at C1. Substitution of benzyl bromide for methyl bromoacetate results in rapid dialkylation, unless the amount of base is carefully controlled, in which case C1-monobenzylation is the major process. This methodology for alkylation at C1 is complimentary to methods for the C2-monoalkylation of C(70) with Zn and methyl bromoacetate. 相似文献
73.
Qin W Baruah M Van der Auweraer M De Schryver FC Boens N 《The journal of physical chemistry. A》2005,109(33):7371-7384
The photophysical properties of seven new 8-(p-substituted)phenyl analogues of 4,4-difluoro-3,5-dimethyl-8-(aryl)-4-bora-3a,4a-diaza-s-indacene (derivatives of the well-known fluorophore BODIPY) in several solvents have been studied by means of absorption and steady-state and time-resolved fluorimetry. For each compound, the fluorescence quantum yield and lifetime are lower in solvents with higher polarity owing to an increase in the rate of nonradiative deactivation. Increasing the electron withdrawing strength of the p-substituent on the phenyl group in position 8 also leads to lower fluorescence quantum yields and lifetimes. When the p-substituent on the phenyl group in position 8 is a tertiary amine [8-(4-piperidinophenyl), 8-(4-N,N-dimethylaminophenyl), and 8-(4-morpholinophenyl)], the low quantum yields of these compounds in more polar solvents can be rationalized by the inversion of the energy levels of an apolar, highly fluorescent and a polar, nonfluorescent excited state, where charge transfer from the tertiary amine to the BODIPY unit occurs. These amine analogues can be protonated at low pH in aqueous solution. Fluorescence titrations yielded pK(a) values of their conjugate ammonium salts which are in agreement with the electron donating tendency of the amine group: piperidino (4.15) > dimethylamino (2.37) > morpholino (1.47), with the pK(a) values in parentheses. The rate constant of radiative deactivation (k(f)) is the same for all compounds in all solvents studied (k(f) = 1.4 x 10(8) s(-1)). 相似文献
74.
M. Jonathan Fray Paul Allen Paul R. Bradley Clare E. Challenger Michael Closier Tim J. Evans Mark L. Lewis John P. Mathias Carly L. Nichols Yvonne M. Po-Ba Hayley Snow Mark H. Stefaniak Hannah V. Vuong 《Tetrahedron》2006,62(29):6869-6875
The synthesis of ten substituted aminomethylene tetrahydro-isoquinolines is described, proceeding in eight steps from 5-hydroxyisoquinoline via reductive amination of N-Boc tetrahydro-isoquinoline 5-carboxaldehyde. Likewise, reductive amination was used to prepare four substituted dihydro-isoindoles from the corresponding aldehyde. The dihydro-isoindole ring system was conveniently accessed via a 2+2+2 cycloaddition reaction. 相似文献
75.
Malkinson JP Anim MK Zloh M Searcey M Hampshire AJ Fox KR 《The Journal of organic chemistry》2005,70(19):7654-7661
[reaction: see text] In this article, the first solid-phase-based total synthesis of TANDEM, a synthetic analogue of triostin A, is described. In initial studies, the synthesis incorporated depsipeptide formation, introduction of chromophores, and disulfide bond formation on the solid phase, prior to a final solution-phase macrolactamization, to give the target molecule. Although pure TANDEM was obtained in an overall yield comparable to those for all syntheses to date, the yield of the final cyclization was low (11%). A more efficient approach involved removal from the solid phase prior to disulfide bond formation. The resulting linear peptide underwent macrolactamization under mild conditions and high dilution. Final disulfide bond formation was essentially quantitative and gave the target molecule, TANDEM, in an overall yield of 18%. The final compound was assessed for its ability to bind to 5'-TpA sequences on DNA by DNase I footprinting. This efficient synthesis sets the stage for a study of the structure-activity relationship of TANDEM and the natural product triostin A, with analogues containing "point mutations" at every site within the cyclic compounds. 相似文献
76.
A. Bismarck M. Pfaffernoschke M. Selimović J. Springer 《Colloid and polymer science》1998,276(12):1110-1116
The grafting method that has successfully been applied to methacrylic acid and liquid crystalline monomers was expanded to
prepare amphoteric carbon fiber surfaces using 2-(N,N-dimethylamino)ethyl methacrylate as monomer. The obtained carbon fiber surfaces were characterized by contact angle and ζ-potential
measurements. The expected basic behavior was not observed, instead an amphoteric character of the modified carbon fiber surface
was found. The fiber surfaces display a basic character in the acidic pH-range, while they are acidic in the alkaline part
of the pH-scale.
An important influence is derived from the amount of initiator used to graft the monomers onto the fibers. The smaller the
initiator concen-tration used during polymerization, the larger the amount of amino functionalities introduced to the carbon
fiber surface.
The wetting behavior versus water depends on the overall conformation of the immobilized polymer. During immersion into water
the polymer acts hydrophobic, while during emersion, a hydrophilic character is observed, probably derived from conformational
changes and swelling during the contact angle measure-ments in water.
Received: 9 June 1998 Accepted: 13 August 1998 相似文献
77.
Applied Biochemistry and Biotechnology - 相似文献
78.
Applied Biochemistry and Biotechnology - 相似文献
79.
80.
Yan B Collins N Wheatley J Irving M Leopold K Chan C Shornikov A Fang L Lee A Stock M Zhao J 《Journal of combinatorial chemistry》2004,6(2):255-261
We have developed a high-throughput purification system to purify combinatorial libraries at a 50-100-mg scale with a throughput of 250 samples/instrument/day. We applied an accelerated retention window method to shorten the purification time and targeted one fraction per injection to simplify data tracking, lower QC workload, and simplify the postpurification processing. First, we determined the accurate retention time and peak height for all compounds using an eight-channel parallel LC/UV/MS system, and calculated the specific preparative HPLC conditions for individual compounds. The preparative HPLC conditions include the compound-specific gradient segment for individual compounds with a fixed gradient slope and the compound-specific UV or ELSD threshold for triggering a fraction collection device. A unique solvent composition or solvent strength was programmed for each compound in the preparative HPLC in order to elute all compounds at the same target time. Considering the possible deviation of the predicted retention time, a 1-min window around the target time was set to collect peaks above a threshold based on UV or ELSD detection. Dual column preparative instruments were used to maximize throughput. We have purified more than 500 000 druglike compounds using this system in the past 3 years. We report various components of this high-throughput purification system and some of our purification results. 相似文献