全文获取类型
收费全文 | 10083篇 |
免费 | 459篇 |
国内免费 | 20篇 |
专业分类
化学 | 7128篇 |
晶体学 | 91篇 |
力学 | 322篇 |
数学 | 1498篇 |
物理学 | 1523篇 |
出版年
2023年 | 59篇 |
2022年 | 69篇 |
2021年 | 158篇 |
2020年 | 184篇 |
2019年 | 178篇 |
2018年 | 212篇 |
2017年 | 166篇 |
2016年 | 370篇 |
2015年 | 314篇 |
2014年 | 321篇 |
2013年 | 690篇 |
2012年 | 726篇 |
2011年 | 804篇 |
2010年 | 430篇 |
2009年 | 389篇 |
2008年 | 698篇 |
2007年 | 718篇 |
2006年 | 647篇 |
2005年 | 587篇 |
2004年 | 435篇 |
2003年 | 401篇 |
2002年 | 352篇 |
2001年 | 138篇 |
2000年 | 117篇 |
1999年 | 104篇 |
1998年 | 70篇 |
1997年 | 61篇 |
1996年 | 107篇 |
1995年 | 71篇 |
1994年 | 59篇 |
1993年 | 65篇 |
1992年 | 57篇 |
1991年 | 41篇 |
1990年 | 30篇 |
1989年 | 39篇 |
1988年 | 21篇 |
1987年 | 35篇 |
1985年 | 63篇 |
1984年 | 45篇 |
1983年 | 23篇 |
1982年 | 56篇 |
1981年 | 44篇 |
1980年 | 52篇 |
1979年 | 44篇 |
1978年 | 37篇 |
1977年 | 36篇 |
1976年 | 50篇 |
1975年 | 39篇 |
1974年 | 29篇 |
1973年 | 30篇 |
排序方式: 共有10000条查询结果,搜索用时 234 毫秒
151.
Composite of polyacrylamide-bentonite (PAA-B) was prepared by direct polymerisation of PAA in a suspension of bentonite (B). Adsorption and thermodynamic features of phytic acid (Phy) adsorption onto B, PAA and PAA-B, and those of Fe3+, Zn2+, UO2
2+ adsorption onto PAA-B and its modification by Phy (PAA-B-Phy) have been investigated. The reusability, storagability, ion selectivity and recoverability of sorbed ions with 1 M HCl have also been considered.The chemical and physical structure of adsorbents has been characterised by means of FT-IR and XRD. All adsorption isotherms for Phy and the ions were L-type of the Giles classification except, the one which is S type for adsorption of Phy onto PAA. The maximum adsorption capacities for the ions adsorbed were in order of UO2
2+ > Fe3+ > Zn2+ for PAA-B and Zn2+ > Fe3+ > UO2
2+ for PAA-B-Phy. Langmuir equilibrium constants for the adsorption of ions onto PAA-B-Phy were significantly higher than those found for PAA-B; the magnitude of increase for UO2
2+ was about 100. The thermodynamic parameters indicated that adsorption reactions are spontaneous in terms of adsorption free enthalpy.The chemical structure of PAA-B-Phy was not changed at the end of the studies of reusability and storagability. The composite was selective for UO2
2+ of the ions of interest.The composite of PAA-B and its modification by Phy have been used for the first time in this investigation. It is proposed that the composites can be practically used in the investigations and applications of adsorption. 相似文献
152.
Travert A Nakamura H van Santen RA Cristol S Paul JF Payen E 《Journal of the American Chemical Society》2002,124(24):7084-7095
Hydrogen adsorption on Mo[bond]S, Co[bond]Mo[bond]S, and Ni[bond]Mo[bond]S (10 1 macro 0) surfaces has been modeled by means of periodic DFT calculations taking into account the gaseous surrounding of these catalysts in working conditions. On the stable Mo[bond]S surface, only six-fold coordinated Mo cations are present, whereas substitution by Co or Ni leads to the creation of stable coordinatively unsaturated sites. On the stable MoS(2) surface, hydrogen dissociation is always endothermic and presents a high activation barrier. On Co[bond]Mo[bond]S surfaces, the ability to dissociate H(2) depends on the nature of the metal atom and the sulfur coordination environment. As an adsorption center, Co strongly favors molecular hydrogen activation as compared to the Mo atoms. Co also increases the ability of its sulfur atom ligands to bind hydrogen. Investigation of surface acidity using ammonia as a probe molecule confirms the crucial role of sulfur basicity on hydrogen activation on these surfaces. As a result, Co[bond]Mo[bond]S surfaces present Co[bond]S sites for which the dissociation of hydrogen is exothermic and weakly activated. On Ni[bond]Mo[bond]S surfaces, Ni[bond]S pairs are not stable and do not provide for an efficient way for hydrogen activation. These theoretical results are in good agreement with recent experimental studies of H(2)[bond]D(2) exchange reactions. 相似文献
153.
Paolesse R Nardis S Venanzi M Mastroianni M Russo M Fronczek FR Vicente MG 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(5):1192-1197
5,10,15-Triphenylcorrole (1) reacts with the Vilsmeier reagent (POCl(3)/DMF) to give the corresponding 3-formyl derivative 3 as the major product. The regioselectivity of the reaction was proven by X-ray crystallography and only traces of the 2-formyl isomer were observed. A more polar product is also observed and this compound becomes the major product when an excess of DMF is used for the preparation of the Vilsmeier reagent, while the formation of the 3-formyl isomer is almost completely suppressed. X-ray crystallography allowed us to identify this compound as the fully substituted N-ethane bridged derivative 4, formed from the attack of the Vilsmeier reagent at the inner core of the macrocycle. This compound is unique among porphyrinoid macrocycles, and further confirms the peculiarity of corrole chemistry. 相似文献
154.
Ignés-Mullol J Claret J Albalat R Crusats J Reigada R Romero MT Sagués F 《Langmuir : the ACS journal of surfaces and colloids》2005,21(7):2948-2955
Preparation of Langmuir monolayers of a mixture of trans- and cis-isomers of an azobenzene derivative, 4-[4-[(4-octylphenyl)azo]phenoxy]butanoic acid, results in the segregation of birefringent trans-isomer domains embedded in an isotropic medium of cis-isomers. Brewster angle microscopy observations allow us to identify different textures inside the domains depending on surface pressure, temperature, and domain size. The evolution of the monolayer in the dark, from initial droplets formed after spreading to a stable stripe texture, is described. The dynamics of domain coalescence and some morphological transitions induced by temperature and surface pressure changes are also discussed. A simple theoretical model is included to supplement some of these experimental observations. 相似文献
155.
Summary A
tail-made polymer matrix is proposed to remove strontium ions from aqueous
solutions. The removal behavior of strontium ions on a crosslinked copolymer
containing methacrylic acid as functional groups was investigated as a function
of sorptive concentration, time, temperature and pH. It was observed that an
increase of these parameters enhanced the removal of Sr(II) ions from aqueous
solution. It is found that a maximum adsorption of Sr(II) ions can be obtained
on the crosslinked copolymer after 30 minutes and at pH 8. The increase of
Sr(II) ion concentration in the solution resulted in an increase in the amount
of Sr(II) ions adsorbed on the crosslinked copolymer containing methacrylic
acid as functional groups. However, after a maximum of Sr(II) concentration in
the solution, the percentage of adsorbed Sr(II) ions decreased. The adsorption
data are well represented by the Freundlich, Langmuir and Dubinin-Radushkevich
(D-R) isotherms. The adsorption capacity of the copolymer and the free energy
change were calculated by using the D-R isotherm. For the adsorption of Sr(II)
ions on the crosslinked copolymer the thermodynamic parameters (DH°,DS° andDG°) were
calculated.</p>
</p> 相似文献
156.
Mustafa Şenyel T. Raci Sertbakan Güneş Kürkçüoğ Ergün Kasap Ziya Kantarci 《Journal of inclusion phenomena and macrocyclic chemistry》2001,39(1-2):175-180
Three Hofmann-diaminododecane-type clathrates of the form M(1,12-diaminododecane) Ni(CN)4G (M = Co, Ni or Cd; G = benzene, naphthalene, anthracene, phenanthrene or biphenyl) have been prepared in powder form. The 1,12-diaminododecane molecules in the host lattice permit the inclusion of bulky guest molecules. The spectral features suggest that these compounds are similar in structure to the other Hofmann-diam-type clathrates. 相似文献
157.
Teresa Kowalska 《Monatshefte für Chemie / Chemical Monthly》1985,116(10):1129-1132
An explanation is given for the two possible ways of determination of the activity coefficients of solutes, when applying a new thermodynamic model of adsorption and partition chromatography, i. e. the binary solutions model. 相似文献
158.
Fernando J. S. Oliveira Francisca P. de França 《Applied biochemistry and biotechnology》2005,122(1-3):581-591
Hexane is a toxic volatile organic compound that is quite abundant in gas emissions from chemical industries and printing
press and painting centers, and it is necessary to treat these airstreams before they discharge into the atmosphere. This
article presents a treatment for hexane-contaminated air in steady-state conditions using an internal-loop airlift bioreactor
inoculated with a Pseudomonas aeruginosa strain. Bioprocesses were conducted at 20-mL/min, a load of 1.26 g/m3 of C6H14, and a temperature of 28°C. The results of hexane removal efficiencies were presented as a function of the inoculum size
(approx 0.07 and 0.2 g/L) and cell reuse. Bioprocess monitoring comprises quantification of the biomass, the surface tension
of the medium, and the hexane concentration in the fermentation medium as well as in the inlet and outlet airstreams. The
steady-state results suggest that the variation in inoculum size from 0.07 to 0.2 g/L promotes hexane abatement from the influent
from 65 to 85%, respectively. Total hydrocarbon removal from the waste gas was achieved during experiments conducted using
reused cells at an initial microbial concentration of 0.2 g/L. 相似文献
159.
I. M. Miranda Salvado F. M. A. Margaça J. Teixeira 《Journal of Sol-Gel Science and Technology》1994,2(1-3):289-294
Silica-titania gels, prepared in acidic conditions, with contents of TiO2 up to 6 mol%, have been studied by small angle neutron scattering (SANS) as wet gel with increasing aging times. In all samples, small primary particles have been found with a diameter of about 3 nm. At the gel point, cylindrical clusters, ca. 10 nm long, were observed as well. These grow with aging time, becoming branched. The cluster-cluster diffusion limited aggregation model is found to be consistent with the SANS results. The growth process is independent of the TiO2 content. It is mainly influenced by the ratio of the aging time to the gelation time. 相似文献
160.
Ben Salah M Vilminot S André G Richard-Plouet M Bourée-Vigneron F Mhiri T Kurmoo M 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(8):2048-2057
[Mn(3)(OH)(2)(SO(4))(2)(H(2)O)(2)] and its deuterated analogue were synthesized by a hydrothermal technique and characterized by differential thermal analysis, thermogravimetric analysis, and IR spectroscopy. Its nuclear structure, determined by single-crystal X-ray analysis and Rietveld analysis of neutron powder-diffraction data, consists of a 3D network of chains of edge-sharing Mn(1)O(6), running along the c axis, connected by the apices of Mn(2)O(6) and SO(4) units. It is isostructural to the nickel analogue. Determination of the magnetic structure and measurements of magnetization and heat capacity indicate the coexistence of both magnetic long-range ordering (LRO) and short-range ordering (SRO) below a Néel temperature of 26 K, while the SRO is retained at higher temperatures. The moments of the two independent Mn atoms lie in the bc plane, and that of Mn(1) rotates continuously by 54 degrees towards the c axis on decreasing the temperature from 25 to 1.4 K. While the SRO may be associated with frustration of the moments within a Mn(3) trimer, the LRO is achieved by antiparallel alignment of the four symmetry-related trimers within the magnetic unit cell. A spin-flop field, measured by dc and ac magnetization on a SQUID, is observed at 15 kOe. 相似文献