全文获取类型
收费全文 | 1423篇 |
免费 | 146篇 |
国内免费 | 122篇 |
专业分类
化学 | 869篇 |
晶体学 | 19篇 |
力学 | 127篇 |
综合类 | 24篇 |
数学 | 221篇 |
物理学 | 431篇 |
出版年
2024年 | 3篇 |
2023年 | 18篇 |
2022年 | 45篇 |
2021年 | 59篇 |
2020年 | 63篇 |
2019年 | 43篇 |
2018年 | 38篇 |
2017年 | 57篇 |
2016年 | 57篇 |
2015年 | 57篇 |
2014年 | 79篇 |
2013年 | 111篇 |
2012年 | 72篇 |
2011年 | 79篇 |
2010年 | 60篇 |
2009年 | 79篇 |
2008年 | 103篇 |
2007年 | 88篇 |
2006年 | 74篇 |
2005年 | 61篇 |
2004年 | 60篇 |
2003年 | 55篇 |
2002年 | 32篇 |
2001年 | 39篇 |
2000年 | 35篇 |
1999年 | 25篇 |
1998年 | 25篇 |
1997年 | 35篇 |
1996年 | 21篇 |
1995年 | 17篇 |
1994年 | 13篇 |
1993年 | 13篇 |
1992年 | 7篇 |
1991年 | 8篇 |
1990年 | 8篇 |
1989年 | 5篇 |
1988年 | 8篇 |
1987年 | 2篇 |
1986年 | 3篇 |
1985年 | 4篇 |
1984年 | 4篇 |
1982年 | 11篇 |
1981年 | 4篇 |
1980年 | 2篇 |
1979年 | 2篇 |
1978年 | 2篇 |
1977年 | 1篇 |
1976年 | 2篇 |
1974年 | 1篇 |
1972年 | 1篇 |
排序方式: 共有1691条查询结果,搜索用时 15 毫秒
41.
Schmidt Sherry L. Myers Michele D. Kelley Stephen S. McMillan James D. Padukone Nandan 《Applied biochemistry and biotechnology》1997,(1):469-482
The use of membrane processes for the recovery of fermentation products has been gaining increased acceptance in recent years.
Pervaporation has been studied in the past as a process for simultaneous fermentation and recovery of volatile products such
as ethanol and butanol. However, membrane fouling and low permeate fluxes have imposed limitations on the effectiveness of
the process. In this study, we characterize the performance of a substituted polyacetylene membrane, poly[(l-trimethylsilyl)-l-propyne]
(PTMSP), in the recovery of ethanol from aqueous mixtures and fermentation broths. Pervaporation using PTMSP membranes shows
a distinct advantage over conventional poly(dimethyl siloxane) (PDMS) membranes in ethanol removal. The flux with PTMSP is
about threefold higher and the concentration factor is about twofold higher than the corresponding performance achieved with
PDMS under similar conditions. The performance of PTMSP with fermentation broths shows a reduction in both flux and concentration
factor relative to ethanol-water mixtures. However, the PTMSP membranes indicate initial promise of increased fouling resistance
in operation with cell-containing fermentation broths. 相似文献
42.
Liquid and solid cyclic peroxides derived from aliphatic ketones are explosive materials so their enthalpies of vaporization
and other thermodynamic or condensed-phase properties cannot be measured directly. In this work the enthalpies of vaporization
of peroxides at 298.15 K were estimated simply from gas chromatographic retention times measured at different temperatures.
The technique correlates changes in the retention times of compounds whose enthalpies of vaporization are known (called the
reference series), with those of the compounds of interest. If t
R′ is the adjusted retention time (retention time of each compound minus the retention time of unretained diethyl ether, used
as solvent) a plot of ln t
R′ against 1/T for each compound (reference compounds and cyclic peroxides) results in a straight line (r
2 > 0.99 for all compounds). The enthalpy of transfer from solution to the vapor state (Δsolg
H
m) can be obtained by multiplying the slope by the gas constant (R). A second plot correlates the enthalpies of transfer from
solution to the vapor state (Δsolg
H
m), as measured by gas–liquid chromatography (GLC), with enthalpies of vaporization of reference materials (Δvap
H
m at 298.15 K) available in the literature. C9–C15 fatty acid methyl esters and hydrocarbons were used as reference compounds. The enthalpies of vaporization of the cyclic
organic peroxides were calculated from the equation of the line obtained in this second correlation, the slope of which was
Δvap
H
m (at 298.15 K)/Δg
sol
H
m. The experiments were performed under isothermal conditions with a DB-5 capillary column, flame-ionization detection (FID),
and nitrogen as carrier gas. The column temperature was varied over a range of at least 30–70 K between 403 and 473 K, with
chromatograms being acquired at 10 K intervals. Enthalpies of vaporization of cyclic organic peroxides are not available in
the literature, and the values given in this paper, obtained by gas chromatography, are the first to be reported. 相似文献
43.
T.D. Klots P. Devlin W.B. Collier 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》1997,53(14):2445-2456
Infrared and Raman measurements for benzimidazole are presented and discussed, including its argon-matrix infrared spectrum. To assist in the assignment, benzimidazole's harmonic force fields for the 321G* and 631G* levels were scaled by scaled factors derived by fitting the respective computed force fields of other indene derivatives to previously reported experimental vibrational frequencies. Comparison to the best set of experimental wavenumbers, usually taken from the matrix, shows mean 321G* and 631G* deviations of 7.0 and 5.8 cm−1 for the planar modes, and 14.0 and 6.8 cm−1 for the nonplanar modes, respectively, with much of the error residing in imino-hydrogen group modes. Standard entropies are derived with the matrix wavenumbers and the methods of statistical mechanics. An attempt to determine standard entropies by calorimetric methods was unsuccessful. The triple-point temperature Ttp and enthalpy of fusion Δ1crHm only are reported. 相似文献
44.
The heats of combustion of trans-9,10-bis-hydroxymethyl-9,10-dihydrophenanthrene, trans-5-hydroxymethyl-5,6-dihydro-7H-dibenzo[a,c]cyclohepten-6-ol, 5-hydroxymethyl-5,6-dihydro-7H-di-benzo[a,c]cycloheptene, 6-hydroxymethyl-5,6-dihydro-7H-dibenzo[a,c]cycloheptene, 5H-dibenzo-[a,d]cyclohepten-5-ol and 5H-10,11-dihydrodibenzo[a,d]cyclohepten-5-ol were measured by means of a Gallenkamp adiabatic bomb calorimeter. Uncertainties in the determination of the heats of combustion ranged between 0.2 and 0.3%. The enthalpies of formation and atomization for the six compounds were derived. The experimental values of the heats of atomization were compared with those calculated using the Allen–Skinner bond energy scheme. Conclusions about energetic contributions which stabilize the structure of the investigated compounds were drawn. 相似文献
45.
The enthalpies of transfer of 2-methyl-2-propanol (TBA) from water to mixtures of water with methanol, ethanol and 1,4-dioxane
have been measured. The data are considered in terms of recently developed theory, and it is found that the enthalpies of
transfer can be reproduced quantitatively over most of the composition range in each solvent system. The parameters recovered
from the analyses indicate that the net effect of TBA on the solvent structure is a breaking of solvent-solvent bonds and
that TBA is preferentially hydrated in the aqueous alcohol systems, but randomly solvated in the water+1,4-dioxane system.
It is also found that the model parameters for TBA solvation in the alcohol systems are independent of the alcohol. 相似文献
46.
K.B. Helean S.V. Ushakov A. Navrotsky J. Lian J.M. Farmer 《Journal of solid state chemistry》2004,177(6):1858-1866
High-temperature oxide melt solution calorimetry and Rietveld refinements of powder X-ray diffraction data were used to investigate the structure (Fd3m; Z=8) and energetics of a series of RE2Ti2O7 (RE=Sm-Lu) compounds with the pyrochlore structure as well as La2Ti2O7 with a layered perovskite-type structure. All of the RE-titanates were found to be stable in enthalpy with respect to their oxides. In the pyrochlore series, Lu2Ti2O7 was least stable in enthalpy (ΔHf-ox at 298 K=−56.0±4.0 kJ/mol); the most stable materials were Gd-, Eu-, and Sm2Ti2O7 with ΔHf-ox at 298 K=−113.4±2.7, −106.1±4.2, −115.4±4.2 kJ/mol, respectively. In general, as the radius ratio of the A- to B-site cations, RA/RB, decreases, the pyrochlore structure becomes less stable. The trend of ionic radius of the RE3+ cation vs. ΔHf-ox at 298 K is non-linear and approximately parallels the increasing “resistance” to ion-beam-induced amorphization as RA/RB decreases. 相似文献
47.
Diantha R. Kelman Lisa F. Szczepura Karen I. Goldberg Werner Kaminsky Anne K. Hermetet Lily J. Ackerman John K. Swearingen Douglas X. West 《Journal of Molecular Structure》2002,610(1-3):143-150
N-2-(4-picolyl)-N′-2-chlorophenylthiourea, 4PicTu2Cl, monoclinic, P21/c, a=10.068(5), b=11.715(2),
β=96.88(4)°,
and Z=4; N-2-(6-picolyl)-N′-2-chlorophenylthiourea, 6PicTu2Cl, triclinic, P-1, a=7.4250(8), b=7.5690(16), c=12.664(3) Å, =105.706(17), β=103.181(13), γ=90.063(13)°, V=665.6(2) Å3 and Z=2 and N-2-(6-picolyl)-N′-2-bromophenylthiourea, 6PicTu2Br, triclinic, P-1, a=7.512(4), b=7.535(6), c=12.575(4) Å, a=103.14(3), β=105.67(3), γ=90.28(4)°, V=665.7(2) Å3 and Z=2. The intramolecular hydrogen bonding between N′H and the pyridine nitrogen and intermolecular hydrogen bonding involving the thione sulfur and the NH hydrogen, as well as the planarity of the molecules, are affected by the position of the methyl substituent on the pyridine ring. The enthalpies of fusion and melting points of these thioureas are also affected. 1H NMR studies in CDCl3 show the NH′ hydrogen resonance considerably downfield from other resonances in their spectra. 相似文献
48.
Alessandro Lezzi Sandra Cobianco Arnaldo Roggero 《Journal of polymer science. Part A, Polymer chemistry》1994,32(10):1877-1883
A series of chelating resins, derived from a macroreticular styrene-divinylbenzene (2%) copolymer beads grafted with various poly(ethylene glycols) HO? (? CH2? CH2? O? )n? H(n = 0, 4, 9, 13) and containing thiol groups as chelating functions, have been synthesized in a three-step reaction sequence. The structure of the functionalized resins was confirmed by IR spectrophotometry, elemental analysis, and differential scanning calorimetry. The complexation behavior of these thiol resins was investigated towards Hg(II), Cu(II), and Pb(II) ions in aqueous solution by a batch equilibration technique. The influence of pH on adsorption capacity was also examined. The adsorption values for metal ions' intake followed the order Hg(II) > Cu(II) > Pb(II). The affinity of these polymers towards Hg(II) ions was so high that the total mercury level in the liquid decreased from 20 ppm to below 10 ppb after 2 h of treatment. Polymers can be regenerated by washing with a solution of hydrochloric acid (6N) and 10% by weight of an aqueous solution of thiourea. © 1994 John Wiley & Sons, Inc. 相似文献
49.
Andrey G. Kazakov Taisya Y. Ekatova Julia S. Babenya Sergey S. Belyshev Vadim V. Khankin Alexander A. Kuznetsov Sergey E. Vinokurov Boris F. Myasoedov 《Molecules (Basel, Switzerland)》2022,27(10)
A new method of production of one of the most widely used isotopes in nuclear medicine, 177Lu, with high chemical purity was developed; this method includes irradiation of the HfO2 target with bremsstrahlung photons. The irradiated target was dissolved in HF and then diluted and placed onto a column filled with LN resin. Quantitative sorption of 177Lu could be observed during this process. The column later was rinsed with the mixture of 0.1 M HF and 1 M HNO3 and then 2 M HNO3 to remove impurities. Quantitative desorption of 177Lu was achieved by using 6 M HNO3. The developed method of 177Lu production ensures high purification of this isotope from macroquantities of hafnium and zirconium and radioactive impurities of carrier-free yttrium. The content of 177mLu in 177Lu in photonuclear production was determined. Due to high chemical and radionuclide purity, 177Lu obtained by the developed method can be used in nuclear medicine. 相似文献
50.
结合静态固相微萃取与液液萃取方法,采用目标物的同分异构体作一对一的回收率指示物以确保水中目标物定量的准确性,建立了气相色谱-质谱测定6种多溴联苯在聚二甲基硅氧烷和水相间的分配系数(Kf)的方法.本研究选用7μm厚度的固相微萃取头,将所测logKf与logKow(正辛醇-水分配系数)作图,通过比较其相关性来判断固相微萃取头涂层的萃取机理,得到了良好的线性关系(r=0.975 7),表明吸收是聚二甲基硅氧烷涂层与上述6种多溴联苯发生作用的主要机理.然而,该结论对于其它强憎水性有机污染物(VHOCs)是否具有普遍性,仍有待于进一步研究加以证明. 相似文献