全文获取类型
收费全文 | 4001篇 |
免费 | 117篇 |
国内免费 | 11篇 |
专业分类
化学 | 3007篇 |
晶体学 | 29篇 |
力学 | 39篇 |
数学 | 444篇 |
物理学 | 610篇 |
出版年
2023年 | 24篇 |
2022年 | 58篇 |
2021年 | 89篇 |
2020年 | 69篇 |
2019年 | 65篇 |
2018年 | 34篇 |
2017年 | 40篇 |
2016年 | 97篇 |
2015年 | 101篇 |
2014年 | 110篇 |
2013年 | 184篇 |
2012年 | 219篇 |
2011年 | 245篇 |
2010年 | 154篇 |
2009年 | 138篇 |
2008年 | 254篇 |
2007年 | 244篇 |
2006年 | 223篇 |
2005年 | 191篇 |
2004年 | 140篇 |
2003年 | 132篇 |
2002年 | 111篇 |
2001年 | 43篇 |
2000年 | 66篇 |
1999年 | 43篇 |
1998年 | 42篇 |
1997年 | 42篇 |
1996年 | 42篇 |
1995年 | 53篇 |
1994年 | 40篇 |
1993年 | 39篇 |
1992年 | 31篇 |
1991年 | 31篇 |
1990年 | 32篇 |
1988年 | 36篇 |
1987年 | 29篇 |
1986年 | 33篇 |
1985年 | 42篇 |
1984年 | 32篇 |
1982年 | 20篇 |
1981年 | 38篇 |
1980年 | 29篇 |
1979年 | 23篇 |
1978年 | 38篇 |
1977年 | 24篇 |
1976年 | 28篇 |
1975年 | 22篇 |
1974年 | 28篇 |
1973年 | 27篇 |
1970年 | 20篇 |
排序方式: 共有4129条查询结果,搜索用时 250 毫秒
91.
The separation, characterization, and determination of mixtures of alkyl ether sulfates (AES) and fatty acids (C10-C16) in background electrolytes (BGEs) containing acetonitrile (ACN)-water mixtures is addressed. Due to inhibition of the ionization of the carboxylate groups, the migration time and the resolution between the fatty acids decreased when the water content of the BGE was reduced, but efficiency and resolution between the AES oligomers improved. The migration times increased and resolution improved by substituting 5% ACN by an equivalent amount of dioxane. A complete separation of the two surfactant classes, up to the AES oligomers with 8 ethylene oxide units (EOs) with respect to C10, with excellent resolution between the AES oligomers, while preserving a satisfactory resolution between the fatty acids, was achieved with a BGE containing 5 mM trimethoxybenzoic acid, 7 mM dipentylamine, 85% ACN, 5% dioxane, and 10% water. The two surfactant classes were increasingly resolved by further reducing the water content of the BGE. Thus, C2 (acetate) was resolved from the AES oligomers up to 7 EOs using 90% ACN and 5% dioxane, but the resolution between the heavier fatty acids was poor with this BGE. Identification of the AES oligomers was eased by the excellent regularity of the successive migration times; thus, within each AES subclass or series of oligomers with the same number of carbon atoms in the alkyl chain, the migration times decreased following a mild curve as the number of EOs increased. The way how the data obtained by indirect photometry (corrected peak areas that are proportional to the molar concentrations) should be managed to avoid systematic error when the calibration curve is constructed using an AES standard with an oligomer distribution different from that of the samples is discussed and equations are given. Decyl sulfate was successfully used as internal standard. The detection limits (S/N = 3) were of ca. 2 microM for individual AES oligomers. 相似文献
92.
Some laws in physics describe the change of a flux and are represented by parabolic equations of the form (*) \documentclass{article}\pagestyle{empty}\begin{document}$$\frac{{\partial u}}{{\partial t}}=\frac{\partial}{{\partial x_j }}(\eta \frac{{\partial u}}{{ax_j}}-vju),$$\end{document} j≤m, where η and vj are functions of both space and time. We show under quite general assumptions that the solutions of equation (*) with homogeneous Dirichlet boundary conditions and initial condition u(x, 0) = uo(x) satisfy The decay rate d > 0 only depends on bounds for η, v and G § Rm the spatial domain, while the constant c depends additionally on which norm is considered. For the solutions of equation (*) with homogeneous Neumann boundary conditions and initial condition u0(x) ≥ 0 we derive bounds d1u1 ≤ u(x, t) ≤ d2u2, Where di, i = 1, 2, depend on bounds for η, v and G, and the ui are bounds on the initial condition u0. 相似文献
93.
Silvia Stumpf Gudrun Goretzki Kerstin Gloe Karsten Gloe Wilhelm Seichte Edwin Weber Jan W. Bats 《Journal of inclusion phenomena and macrocyclic chemistry》2003,45(3-4):225-233
The di- and tetra-allyl ethers of tert-butylcalix[4]arene 1 and 2 have been prepared by alkylation of tert-butylcalix[4]arene with allyl bromide and K2CO3 using different reaction times. Solution 1H NMR measurement of the di-allyl ether 1 and X-ray crystal structures of the complexes of 1 with chloroform (1a) or methanol (1b) indicate the cone conformation of 1 in which intramolecular hydrogen bonding can be maximized. The crystalline state conformers 1a and 1b are distorted in different grades depending on the solvent. While methanol is incorporated in the macrocycle, chloroform molecules do not occupy the cage. The solution 1H NMR spectra of tetra-allyl ether 2 show the co-existence of the cone and partial cone conformation. The partial cone conformer of 2 was investigated by X-ray crystallography. In this compound hydrogen bonding is not existent. The conformer distribution is likely affected by steric and template effects. 相似文献
94.
Hans-Detlev Gilsing Jürgen Angerer Dietrich Prescher 《Monatshefte für Chemie / Chemical Monthly》2002,133(8):1147-1155
Summary. The synthesis of two oxidized metabolites of bis-(2-ethylhexyl)-phthalate is described. The target structures were obtained
by esterification of the appropriate alcohol carrying a protected hydroxy group with phthalic anhydride, followed by deprotection
and further oxidation.
Received February 26, 2002. Accepted March 6, 2002 相似文献
95.
H. H. Deubler K. Lekkas P. Sperr K. Dietrich 《Zeitschrift für Physik A Hadrons and Nuclei》1978,284(2):237-244
The process of instantaneous fission in deep inelastic collisions is investigated in a classical model. Kinetic energies and angular distributions of the fragments are calculated for the proposed reaction Pb+U atE cm inc =750 MeV; an experimental setup for the separation of the fragments originating from instantaneous fission from the fragments of thermal fission is explained. We also discuss fusion following instantaneous fission as a mechanism for the production of superheavy elements and arrive at rather promising estimates. 相似文献
96.
Dimethyl carbonate (DMC) was investigated as a mild, harmless and odorless reagent for pyrolytic methylation of fatty acids. Soybean oil was selected as test material for its high content of (poly)unsaturated fatty acids. Pyrolyses were performed at 500, 700 and 900 degrees C by means of a heated platinum filament pyrolyser on-line and off-line to the GC-MS apparatus. Methyl esters of palmitic, linoleic, oleic and stearic acid were formed as prominent products from off-line pyrolysis of soybean oil in the presence of DMC and zeolite 13X. Fatty acid methyl esters (FAMEs) were not observed at important levels in the absence of zeolite, while on-line Py-GC-MS experiments resulted principally in the formation of free fatty acids and hydrocarbons. The FAME profiles obtained from the DMC/zeolite off-line pyrolysis were compared to those resulting from tetramethylammonium hydroxide (TMAH) thermochemolysis and BF3-methanol procedure. The observed differences between pyrolysis and methanolysis methods were principally attributed to the thermal degradation of unsaturated fatty acids. The effectiveness of the DMC/zeolite pyrolytic methylation was further demonstrated by the analysis of tripalmitine and soybean seeds. 相似文献
97.
Lupane Pentacyclic Triterpenes Isolated from Stems and Branches of Maytenus imbricata (Celastraceae)
Silvia Ribeiro deSouzaeSilva GraciaDivina deFtimaSilva LucaCludio deAlmeidaBarbosa LucienirPains Duarte SidneyAugustoVieira Filho 《Helvetica chimica acta》2005,88(5):1102-1109
Four lupane pentacyclic triterpenes were isolated from the hexane extract of stems and branches of Maytenus imbricata Mart. ex Reissek : 3‐oxolup‐20(30)‐en‐29‐al ( 1 ), 30‐hydroxylup‐20(29)‐en‐3‐one ( 2 ), (11α)‐11‐hydroxylup‐20(29)‐en‐3‐one ( 3 ), and (3β)‐lup‐20(30)‐ene‐3,29‐diol ( 4 ). The structural identification of 1 – 4 was achieved by 1H‐ and 13C‐NMR techniques, including 2D experiments (HSQC, HMBC, and NOESY). 相似文献
98.
Modeling and simulation of free radical polymerization of styrene under semibatch reactor conditions
The first part of this approach is concerned with the elaboration of a radical polymerization model of styrenne, based on
a kinetic diagram that includes chemical and thermal initiation, propagation, termination by recombination and chain transfer
to the monomer. Furthermore, volume contraction during polymerization is considered, as well as the gel and glass effects.
The mathematical formalism that describes the model in terms of moments is explored in detail. The model was then used to
predict the changes in monomer conversion and molecular weight after intermediate addition of initiator and monomer. The results
of this operation are dependent on the conditions of the reaction mass, quantity, and moment of substance addition. Therefore,
the simulations were performed at different times with respect to the gel effect; before, during and after this phenomenon,
and also with respect to different temperatures and initiators. Increasing the initiator concentration before the gel effect
leads to an earlier appearance of the phenomenon and to a decrease in molecular weight. The ratio
reveals a polydispersity index smaller for the intermediate addition of initiator. No significant changes take place during
or after the gel effect. If along with the initiator, unreacted monomver (used to dissolve the initiator) enters the reactor,
a small dip in conversion is observed. The general conclusion of this paper reveals the intermediate addition of initiator
as a method to control polymer properties and to prevent the “dead-end” polymerization of styrene. 相似文献
99.
The large number of known stable compounds in which phosphorus has a low coordination number makes it clear that such compounds can no longer be regarded as “exotic” in main group chemistry. While the rich chemistry of P? C multiply bonded systems makes clear their affinity to their organic congeners, iminophosphanes in particular are also of increasing importance. The linkage of a phosphinidine fragment with an imine fragment via a multiple bond gives rise to a class of compounds with an unusually wide range of structural types. This in turn leads to a broad spectrum of chemical behavior which makes iminophosphanes extremely useful synthetic building blocks in organoelement chemistry. 相似文献
100.
FLUORESCENCE QUANTUM YIELDS OF 124-kDa PHYTOCHROME FROM OAT UPON EXCITATION WITHIN DIFFERENT ABSORPTION BANDS 总被引:1,自引:0,他引:1
Claudio G. Colombano Silvia E. Braslavsky Alfred R. Holzwarth Kurt Schaffner 《Photochemistry and photobiology》1990,52(1):19-22
Abstract— A fluorescence quantum yield (emission at650–850 nm) of π= (2.3 ± 0.3)10−3 was measured for the red-absorbing form (Pr) of 124-kDa phytochrome from etiolated oat seedlings ( Avena sativa ) upon excitation in the Soret band at Λexc = 380 nm. The small difference between this value and the previously determined quantum yield with Λexc = 640 nm, π= (3.5 ± 0.4)10−3 is attributed to a blue-absorbing emitter responsible for the "anomalous" or "blue" emission of the chromoprotein in the region from ca. 400 to 550 nm. The absorption of Pr at 380 nm is consequently somewhat lower than that measured directly from the spectrum. Processes from upper excited states of the Pr phytochromobilin-derived chromophore other than rapid relaxation to the emitting state are not important. A quantum yield of Φ ' 1.2 times 10−3 is estimated for the blue fluorescence. The proportion of the blue emitters relative to Pr appears to be relatively high. 相似文献