全文获取类型
收费全文 | 2958篇 |
免费 | 66篇 |
国内免费 | 11篇 |
专业分类
化学 | 1763篇 |
晶体学 | 19篇 |
力学 | 92篇 |
数学 | 676篇 |
物理学 | 485篇 |
出版年
2021年 | 34篇 |
2020年 | 30篇 |
2019年 | 33篇 |
2016年 | 54篇 |
2015年 | 63篇 |
2014年 | 50篇 |
2013年 | 131篇 |
2012年 | 102篇 |
2011年 | 124篇 |
2010年 | 72篇 |
2009年 | 70篇 |
2008年 | 108篇 |
2007年 | 81篇 |
2006年 | 65篇 |
2005年 | 68篇 |
2004年 | 59篇 |
2003年 | 39篇 |
2002年 | 52篇 |
2001年 | 33篇 |
2000年 | 46篇 |
1999年 | 51篇 |
1998年 | 39篇 |
1997年 | 41篇 |
1996年 | 34篇 |
1995年 | 41篇 |
1994年 | 30篇 |
1993年 | 31篇 |
1992年 | 36篇 |
1991年 | 26篇 |
1990年 | 24篇 |
1989年 | 25篇 |
1988年 | 35篇 |
1987年 | 36篇 |
1986年 | 32篇 |
1985年 | 59篇 |
1984年 | 45篇 |
1983年 | 34篇 |
1982年 | 35篇 |
1981年 | 42篇 |
1980年 | 41篇 |
1979年 | 37篇 |
1978年 | 29篇 |
1977年 | 45篇 |
1976年 | 36篇 |
1975年 | 31篇 |
1974年 | 24篇 |
1971年 | 22篇 |
1967年 | 24篇 |
1933年 | 20篇 |
1930年 | 21篇 |
排序方式: 共有3035条查询结果,搜索用时 0 毫秒
61.
The coordinative properties of the acceptor ligand CS are discussed on the basis of the new thiocarbonyl complexes CpCr(CO)(CS)(NO) (I), [CpCr(CS)(NO)2]PF6 (II), CpCr(CS)(L)(NO) (L = pyridine (III) or trimethylphosphane (IV) and related carbonyl complexes. The IR and NMR spectra (1H, 13C, 31P) of the complexes indicate ligand—ligand interactions between CS and both the nitrosyl group and the cyclopentadienyl ring. An attempt is made to compare CS with other sulphur-containing acceptor ligands such as NS (in CpCr(CO)2(NS)) and CS2 (in CpCr(CS2)(PMe3)(NO)). 相似文献
62.
Oskar Friedrich Olaj Gerhard Zifferer Herbert Rhemann 《Monatshefte für Chemie / Chemical Monthly》1985,116(12):1395-1412
A formalism has been worked out which allows to transform any non-punctiform segment-segment potential of isolated polymer segments ε of fairly short-ranged character into the pair-potentialU operating between linear polymer chains with a certain reference to the arguments as they have been originally put forward byFlory andKrigbaum. Although no restrictions are made in the derivation as to the repulsive or attractive contribution of the segment-segment potential ε because of some known general deficiencies of theFlory-Krigbaum treatment for exclusively repulsive interaction, the resulting equations are primarily intended to describe the thermodynamic situation at and close to the θ-point where repulsion and attraction—though working at different ranges of segment separation—cancel. As the equation derived is somewhat complicated two different approximate forms have been developed: The first one is based on aTaylor series expansion retaining terms up to the fourth order which allows to characterizeU by the second and the fourth moment of the pair segment-segment distribution function, β and γ (β being the so-called binary cluster integral of segment-segment interaction, which is considered to be zero for θ-conditions). In this caseU may be represented by an expression of the general form $$U/kT = A(1 - BR^2 )\exp \{ - bR^2 \} .$$ The second method is based on a separate integration over the repulsive and attractive ranges of ε giving the repulsive (U +) and the attractive (U ?) part ofU finally after some approximations leading to an equation of the general form $$U/kT = (U_ + + U_ - )/kT = A_1 \exp \{ - b_1 R^2 \} - A_2 \exp \{ - b_2 R^2 \} .$$ In both cases the knowledge of the exact form of ε is dispensable, only β and γ—or for the second case their repulsive (β+ and γ+) and attractive (β? and γ?) parts have to be known. It is shown that the approximations are in excellent accordance with the exact form so that they may be conveniently used to describe pair potentials of polymer chains and to analyze pair potentials of segment-segment interactions under the limitations and conditions indicated. 相似文献
63.
Karim Fahmy Olaf Weidlich Martin Engelhard Jörg Tittor Dieter Oesterhelt Friedrich Siebert † 《Photochemistry and photobiology》1992,56(6):1073-1083
Abstract— In order to assign the proton acceptor for Schiff base deprotonation in bacteriorhodopsin to a specific Asp residue, the photoreaction of the Asp85 → Glu mutant, as expressed in Halobacterium sp . GRB, was investigated by static low-temperature and time-resolved infrared difference spec-troscopy. Measurements were also performed on the mutant protein labeled with [4-13 C]Asp which allowed discrimination between Asp and Glu residues. 14,15-di13 C-retinal was incorporated to distinguish amide-II absorbance changes from changes of the ethylenic mode of the chromophore. In agreement with earlier UV-VIS measurements, our data show that from both the 540 and 610 nm species present in a pH-dependent equilibrium, intermediates similar to K and L can be formed. The 14 ms time-resolved spectrum of the 540 nm species shows that a glutamic acid becomes protonated in the M-like intermediate, whereas the comparable difference spectrum of the 610 nm species demonstrates that in the initial state a glutamic acid is already protonated. In conjunction with earlier observations of protonation of an Asp residue in wild-type M, the data provide direct evidence that the proton acceptor in the deprotonation reaction of the Schiff base is Asp85. 相似文献
64.
65.
Friedrich Wesseley 《Nachrichten aus der Chemie》1967,15(20):374-375
66.
67.
Lei Ji Stefan Riese Alexander Schmiedel Marco Holzapfel Maximillian Fest Jrn Nitsch Basile F. E. Curchod Alexandra Friedrich Lin Wu Hamad H. Al Mamari Sebastian Hammer Jens Pflaum Mark A. Fox David J. Tozer Maik Finze Christoph Lambert Todd B. Marder 《Chemical science》2022,13(18):5205
Reversible conversion between excited-states plays an important role in many photophysical phenomena. Using 1-(pyren-2′-yl)-o-carborane as a model, we studied the photoinduced reversible charge-transfer (CT) process and the thermodynamic equilibrium between the locally-excited (LE) state and CT state, by combining steady state, time-resolved, and temperature-dependent fluorescence spectroscopy, fs- and ns-transient absorption, and DFT and LR-TDDFT calculations. Our results show that the energy gaps and energy barriers between the LE, CT, and a non-emissive ‘mixed’ state of 1-(pyren-2′-yl)-o-carborane are very small, and all three excited states are accessible at room temperature. The internal-conversion and reverse internal-conversion between LE and CT states are significantly faster than the radiative decay, and the two states have the same lifetimes and are in thermodynamic equilibrium.Reversible conversion between excited-states is key to many photophysical phenomena. We studied the equilibrium between LE and CT states by time-resolved and temperature-dependent fluorescence, fs- and ns-transient absorption, and LR-TDDFT calculations. 相似文献
68.
69.
Ranjit Joshi Jörg Friedrich Santosh Krishna-Subramanian 《Plasma Chemistry and Plasma Processing》2013,33(5):921-940
Ultra-high molecular weight polyethylene membranes were modified and subsequently polymer coated using the underwater plasma produced by glow discharge electrolysis. This plasma pretreatment generated various O-functional groups among them OH groups have dominated. This modified inner (pore) surface of membranes showed complete wetting and strong adhesion to a hydrogel copolymerized by glow discharge electrolysis also. The deposited hydrogel consists of plasma polymerized acrylic acid crosslinked by copolymerization with the bifunctional N,N′-methylenebis(acrylamide). Tuning the hydrogel hydrophilicity and bio-compatibility poly(ethylene glycol) was chemically inserted into the copolymer. Such saturated polymer could only be inserted on a non-classic way by (partial) fragmentation and recombination thus demonstrating the exotic properties of the underwater plasma. The modification of membrane was achieved by squeezing the reactive plasma solution into the pores by plasma-induced shock waves and supported by intense stirring. The deposited copolymer hydrogel has filled all pores also in the inner of membrane as shown by scanning electron microscopy of cross-sections. The copolymer shows the characteristic units of acrylic acid and ethylene glycol as demonstrated by infrared spectroscopy. A minimum loss in carboxylic groups of acrylic acid during the plasma polymerization process was confirmed by X-ray photoelectron spectroscopy. Additional cell adhesion tests on copolymer coated polyethylene using IEC-6 cells demonstrated the bio-compatibility of the plasma-deposited hydrogel. 相似文献
70.