全文获取类型
收费全文 | 3125篇 |
免费 | 94篇 |
国内免费 | 10篇 |
专业分类
化学 | 1997篇 |
晶体学 | 27篇 |
力学 | 76篇 |
数学 | 325篇 |
物理学 | 804篇 |
出版年
2023年 | 28篇 |
2022年 | 66篇 |
2021年 | 60篇 |
2020年 | 66篇 |
2019年 | 81篇 |
2018年 | 81篇 |
2017年 | 72篇 |
2016年 | 126篇 |
2015年 | 75篇 |
2014年 | 118篇 |
2013年 | 240篇 |
2012年 | 182篇 |
2011年 | 206篇 |
2010年 | 137篇 |
2009年 | 140篇 |
2008年 | 208篇 |
2007年 | 177篇 |
2006年 | 145篇 |
2005年 | 125篇 |
2004年 | 90篇 |
2003年 | 71篇 |
2002年 | 63篇 |
2001年 | 38篇 |
2000年 | 37篇 |
1999年 | 15篇 |
1998年 | 20篇 |
1997年 | 15篇 |
1996年 | 25篇 |
1995年 | 32篇 |
1994年 | 30篇 |
1993年 | 35篇 |
1992年 | 30篇 |
1991年 | 34篇 |
1990年 | 26篇 |
1989年 | 27篇 |
1988年 | 18篇 |
1987年 | 32篇 |
1986年 | 22篇 |
1985年 | 24篇 |
1984年 | 17篇 |
1983年 | 20篇 |
1982年 | 18篇 |
1981年 | 21篇 |
1980年 | 18篇 |
1979年 | 23篇 |
1978年 | 11篇 |
1976年 | 9篇 |
1975年 | 7篇 |
1974年 | 9篇 |
1965年 | 7篇 |
排序方式: 共有3229条查询结果,搜索用时 250 毫秒
81.
Sarkar J Sharma A Shenoy V 《Langmuir : the ACS journal of surfaces and colloids》2005,21(4):1457-1469
We study the phenomenon of debonding in a thin soft elastic film sandwiched between two rigid plates as one of the plates is brought into intimate contact and then pulled away from contact proximity by application of a normal force. Nonlinear simulations based on minimization of total energy (composed of stabilizing elastic strain energy and destabilizing adhesive interaction energy) are employed to address the problems of contact hysteresis, cavitation, crack morphology, variation of contact area, snap-off distance, pull-off force, work done, and energy loss. Below a critical distance (d(c)) upon approach, simulations show the formation of columnar structures and nonrandom, regularly arranged nanocavities at the soft interface at a length scale of approximately 3h (h being the thickness of the film). The persistence of such instability upon withdrawal (distance >d(c)) indicates a contact hysteresis, which is caused by an energy barrier that separates the metastable states of the patterned configuration and the global minimum state of the flat film. The energy and the pull-off force are found to be nonequilibrium and nonunique properties depending on the initial contact, defects, noise, etc. Three broad pathways of debonding leading to adhesive failure of the interface, depending on the stiffness of the film, step size of withdrawal, and the imposed noise, are identified: a catastrophic column collapse mode, a peeling mode involving a continuous decrease in the contact area, and a column splitting mode. The first two modes are caused by a very high stress concentration near the cavity edges. These metastable patterned configurations engender pull-off forces that are orders of magnitude smaller than that required to separate two flat surfaces from contact. 相似文献
82.
Molecular geometries of two structural forms of 2'-deoxyguanosine (keto-N9R and keto-N7R, R = the sugar moiety) considering both the C2'-endo and C3'-endo conformations of the sugar ring and those of the complexes of these species with two water molecules each were optimized employing the ab initio RHF procedure. A mixed basis set consisting of the 6-311+G* basis set for the nitrogen atom of the amino group and the 4-31G basis set for all the other atoms was used. The RHF calculations were followed by correlation correction of the total energy at the MP2 level. Both the structural forms of 2'-deoxyguanosine were solvated using the polarized continuum model (PCM) of the self-consistent reaction field (SCRF) theory and the corresponding RHF optimized geometries at the RHF and MP2 levels. Geometry optimization was also performed in aqueous media using the Onsager model at the RHF level using the above-mentioned mixed basis set, and subsequently, using the reoptimized geometries, single-point MP2 calculations were performed. It is found that both the keto-N9R and keto-N7R forms of 2'-deoxyguanosine as well as their complexes with two water molecules each would occur, particularly at the water-air interface. Though the normal Watson-Crick-type base pairing would not be possible with the keto-N7R form of 2'-deoxyguanosine(G*), two other (G*-C and G*-T) base pairing schemes may occur with this form of the nucleoside, which may cause mutation. The present calculated geometry of the keto-N9R form of the anti-conformation of 2'-deoxyguanosine including the dihedral angle chi(CN) agree satisfactorily with the available crystallographic results. The present results also agree satisfactorily with those obtained by other authors earlier for the keto-N9R form of 2'-deoxyguanosine using B3LYP and MP2 methods employing the 6-31G* basis set. Using transition state calculations, it is shown that tautomerism of guanine and other similar molecules where the tautomers would coexist would be facilitated by the occurrence of the H(+) and OH(-) fragments of water molecules. Further, this coexistence of the two tautomers appears to make the C8 carbon atom located between the N7 and N9 nitrogen atoms susceptible to attack by the OH(-) group. Thus, an explanation is obtained for the efficient formation of the reaction product 8-hydroxy-2'-deoxyguanosine, which serves as a biomarker for oxidative damage to DNA in biological systems. 相似文献
83.
Spectrophotometric Determination of Rhenium(IV) with Thiocyanate,TX-100 and N,N′-Diphenylbenzamidine
A spectrophotometric method to determine rhenium(IV) at trace level is based on the extraction of Re(IV)-SCN? complex in sulphuric acid media with N,N′-diphenylbenzamidine(DPBA) in presence of a non-ionic surfactant triton X-100 (TX-100) in chloroform. The complex shows maximum absorbance at 435 nm with amolar absorptivity value of 4.24 × 104 L mol?1 cm?1 at an acidity range 3.5-6.5 M H2SO4. The method followed Beer's Law for the system Re(IV)-SCN?(TX-100)-DPBA upto 4.0 μg Re(IV) mL?1. The detection limit of the method is 5 ppb. None of the tested foreign ions, except molybdenum(VI), interfere with the determination of rhenium. The interference due to molybdenum could effectively be removed by prior precipitation with oxine. The effect of various analytical parameters on the extraction of the metal are discussed. 相似文献
84.
Summary The title reaction has been followed spectrophotometrically at 325 nm (max of [Mn(CN)6]3–) under pseudo-first order conditions with cyanide in a large excess at pH=10.0, I=0.1M (NaClO4) and 25°C. The reaction follows first-order kinetics in [MnEDTA(OH)]2– and exhibits variable-order dependence in [CN–] one at high cyanide concentration, and two at low cyanide concentration. The product of above reaction has been identified as [Mn(CN)6]3–.The kinetics of the reverse reaction,i.e., the reaction of [Mn(CN)6]3- with EDTA4– have also been followed spectrophotometrically. This reactions is first-order with respect to both [Mn(CN)
6
3–
] and [EDTA4–] and exhibits an inverse first-order dependence on [CN–]. A six-step mechanism has been proposed in which the penultimate step is rate-determining. The activation parameters have been obtained and support the postulated mechanism. 相似文献
85.
Anuradha Mishra Malvika Bajpai Sunita Pal Monika Agrawal Sushant Pandey 《Colloid and polymer science》2006,285(2):161-168
The application of Tamarindus
indica seed mucilage (Tam), a food grade polysaccharide, and its acrylamide grafted copolymer as flocculants was assessed for the first time for removal of various types of dyes from model textile wastewater containing azo, basic, and reactive dyes. Acrylamide grafted T. indica mucilage (Tam-g-PAM) was obtained by ceric ion initiated polymerization technique. A series of contact time experiments were conducted to assess the system variables such as concentrations of mucilage and dyes and pH. These flocculants reduce the dye concentration by flocculation and settling. The grafted copolymer, Tam-g-PAM showed better results for dye removal. The optimal flocculant concentration, which was required to effect flocculation, was independent of dye concentration within the range examined. Both the flocculants performed better for removal of azo dyes than for reactive and basic dyes. 相似文献
86.
Summary The kinetics of the silver(I)-catalysed oxidation of malonic acid by peroxodiphosphate (pdp) was studied in acetate buffers. The rate law as represented by-d[pdp]/dt = {(k
1
K
inf2
sup-1
[H+]2 + k
2[H+] + k
3
K
3)/ ([H+]2/K
2 + [H+] + K
3)}[pdp][Ag(I)] conforms to the proposed mechanism. The rate is independent of malonic acid concentrations. Acetate ions do not affect the rate; however, the rate decreases as the ionic strength increases. A probable portrait of reaction events is suggested. A comparative analysis of the reactivity pattern of malonic acid towards peroxodiphosphate and peroxodisulphate in presence of silver(I) has been made. 相似文献
87.
11 and 12 molar reactions of dioxouranium(VI) acetate dihydrate with the monobasic bidentateSchiff bases,o-HOC6H4CH=NR oro-HOC10H6CH=NR (R=C2H5,n-C3H7,n-C4H9 or C6H5) and bibasic tridentateSchiff bases,o-HOC6H4CH=NR(OH) oro-HOC10H6CH=NR(OH) (R=–CH2CH(CH3)- or —CH2CH2CH2–) have been studied and derivates of the type UO2(OAc)2(SBH), UO2(OAc)2(SBH)2, UO2(OAc)2(SBH
2) and UO2(OAc)2(SBH
2)2 (whereSBH andSBH
2 represent monobasic bidentate and bibasic tridentateSchiff base molecules respectively) have been isolated. These have been characterized by elemental analysis, conductance measurements and IR spectral studies.
UO2 2+-Komplexe von Schiff-Basen. VII. Uranylacetat-Komplexe mit monobasischen zweizähnigen und bibasischen dreizähnigen Schiff-Basen
Zusammenfassung Es wurden in 1:1- und 1:2-molaren Reaktionen von UO2(OAc)2·2H2O mitSchiff-Basen (L) Komplexe des Typs UO2(OAc)2 L bzw. UO2(OAc)2 L 2 isoliert. Die Komplexe wurden mittels Elementaranalyse, Leitfähigkeitsmessungen und IR-Spektren untersucht.相似文献
88.
M. K. Mishra 《Colloid and polymer science》1982,260(5):508-510
In an attempt to modify fibrous protein, methyl methacrylate (MMA) has been graft copolymerized onto Mulberry silk in an aqueous medium by using peroxydiphosphate — fructose redox system. Graft copolymerizations were carried out at 45, 50, and 55 °C for a period from 1 to 6 hr. Percentage grafting was found to be dependent upon reaction temperature, time, concentration of monomer, acid, peroxydiphosphate and fructose. The rate of grafting (R
p
) and the induction period (I
p
of MMA was determined as a function of total initial monomer concentration. 相似文献
89.
K. C. Mishra B. N. Dev S. M. Mohapatra W. M. Gibson T. P. Das 《Hyperfine Interactions》1983,16(1-4):997-1000
The electronic energy levels and wave functions of fluorine and chlorine atoms adsorbed at the <111> surface of silicon are obtained by the Hartree-Fock procedure applied to clusters simulating the surface structure. Minimising the total energy with respect to the positions of the halogen atoms, the Si-Cl distance in the adsorbed system was found to be in good agreement with that from a recent SEXAFS measurement, there being no corresponding data presently available for fluorine on silicon surface. The calculated19 f * nuclear quadrupole coupling constants using the electronic wave functions for SiH3F and the larger cluster Si4H9F, simulating the surface, differed substantially in contrast to the situation for the Si-F distance, indicating that the quadrupole coupling is a more sensitive indicator of the adequacy of the cluster chosen to represent the surface system. Experimental results for the coupling constants are awaited for comparison with theory. 相似文献
90.
Bruce S. Dien Nick Nagle Kevin B. Hicks Vijay Singh Robert A. Moreau Melvin P. Tucker Nancy N. Nichols David B. Johnston Michael A. Cotta Quang Nguyen Rodney J. Bothast 《Applied biochemistry and biotechnology》2004,115(1-3):937-949
Approximately 9% of the 9.7 billion bushels of corn harvested in the United States was used for fuel ethanol production in 2002, half of which was prepared for fermentation by dry grinding. The University of Illinois has developed a modified dry grind process that allows recovery of the fiber fractions prior to fermentation. We report here on conversion of this fiber (Quick Fiber [QF]) to ethanol. QF was analyzed and found to contain 32%wt glucans and 65%wt total carbohydrates. QF was pretreated with dilute acid and converted into ethanol using either ethanologenic Escherichia coli strain FBR5 or Saccharomyces cerevisiae. For the bacterial fermentation the liquid fraction was fermented, and for the yeast fermentation both liquid and solids were fermented. For the bacterial fermentation, the final ethanol concentration was 30 g/L, a yield of 0.44 g ethanol/g of sugar(s) initially present in the hydrolysate, which is 85% of the theoretical yield. The ethanol yield with yeast was 0.096 gal/bu of processed corn assuming a QF yield of 3.04 lb/bu. The residuals from the fermentations were also evaluated as a source of corn fiber oil, which has value as a nutraceutical. Corn fiber oil yields were 8.28%wt for solids recovered following prtetreatment. 相似文献