全文获取类型
收费全文 | 6352篇 |
免费 | 80篇 |
国内免费 | 9篇 |
专业分类
化学 | 3774篇 |
晶体学 | 72篇 |
力学 | 138篇 |
数学 | 745篇 |
物理学 | 1712篇 |
出版年
2016年 | 64篇 |
2015年 | 63篇 |
2014年 | 65篇 |
2013年 | 241篇 |
2012年 | 160篇 |
2011年 | 182篇 |
2010年 | 118篇 |
2009年 | 128篇 |
2008年 | 191篇 |
2007年 | 212篇 |
2006年 | 209篇 |
2005年 | 229篇 |
2004年 | 182篇 |
2003年 | 170篇 |
2002年 | 147篇 |
2001年 | 84篇 |
2000年 | 71篇 |
1999年 | 95篇 |
1998年 | 54篇 |
1997年 | 89篇 |
1996年 | 119篇 |
1995年 | 111篇 |
1994年 | 72篇 |
1993年 | 70篇 |
1992年 | 67篇 |
1991年 | 72篇 |
1990年 | 78篇 |
1989年 | 67篇 |
1988年 | 78篇 |
1987年 | 87篇 |
1986年 | 60篇 |
1985年 | 83篇 |
1984年 | 81篇 |
1983年 | 72篇 |
1982年 | 85篇 |
1981年 | 71篇 |
1980年 | 90篇 |
1979年 | 71篇 |
1978年 | 88篇 |
1977年 | 81篇 |
1976年 | 73篇 |
1975年 | 78篇 |
1974年 | 55篇 |
1973年 | 50篇 |
1972年 | 40篇 |
1968年 | 43篇 |
1967年 | 41篇 |
1955年 | 59篇 |
1934年 | 43篇 |
1928年 | 38篇 |
排序方式: 共有6441条查询结果,搜索用时 546 毫秒
171.
McMillan SA Haubein NC Snurr RQ Broadbelt LJ 《Journal of chemical information and computer sciences》2003,43(6):1820-1828
Moderate to large size molecules in solution have complex energy surfaces due to intramolecular (conformational) and intermolecular (many-body) interactions. The first principles Monte Carlo (FPMC) method, previously shown to effectively locate minimum-energy structures for systems with only many-body complexity, has been extended to address conformational flexibility by adding three new Monte Carlo move types. The primary advantage of the FPMC method is the ability to efficiently locate minimum energy structures of molecules with conformational flexibility in the presence of explicit solvent molecules using highly accurate quantum chemical calculations. The additions to FPMC were validated by studying conformers of glycerol, glyceraldehyde, and a large humic acid monomer unit. The structure of glyceraldehyde in the presence of one and two water molecules was also explored to demonstrate the power of FPMC to study systems with both conformational and many-body degrees of freedom. 相似文献
172.
A method for flow-through liquid scintillation counting in reversed-phase liquid chromatography (RP-LC) based on the continuous extraction of aqueous column eluates with a water-immiscible liquid scintillator is evaluated in terms of sensitivity, reproducibility and extra-column band broadening. 3H- and 14C-labelled phenylthiohydantoinamino acid derivatives of widely different polarity serve as model compounds. For extractable derivatives, counting efficiencies of over 30 and 80% can be obtained for 3H and 14C, respectively. The reproducibility and extra-column band broadening depend on the mixing ratio of scintillator and LC eluent; relative standard deviations (peak areas) of less than 3% can be obtained. The sensitivity of flow-through counting can be increased at least 150-fold by storing the segmented scintillator/eluate stream in a capillary storage loop. After the separation is complete, the stream is re-introduced into the radioactivity detector at reduced flow-rates to increase the mean residence time, i.e., the counting time, in the detector. 相似文献
173.
Summary A technique is presented for the extraction of free and conjugated drugs and related compounds out of small quantities of urine. The method is designed in such a way that many samples can be tested for a great number of substances at the same time. Furthermore, we tried to achieve a high quality analysis using when ever possible chemicals with relatively low toxicity to men and environment. Therefore we avoided e.g., halogenated hydrocarbons. The detection of the substances is only performed by thin-layer chromatography (TLC) using well known reagents, like ninhydrin, Dragendorff, iodoplatinate and ferric chloride solutions. If necessary, the extracts can also be used with other Chromatographic techniques, particularly with GC/MS, if a substance has to be clearly identified. Approximately 500 authentical urines have been analyzed in a 1 year period using the method described. We found about 75 different substances. These results are presented in a table. 相似文献
174.
John J. Lenhart Linda A. Figueroa Bruce D. Honeyman David Kaneko 《Colloids and surfaces. A, Physicochemical and engineering aspects》1997,120(1-3):243-254
This paper reports the development of a treatment system, using animal chitin as a passive biosorbent, for removing U(VI) from aqueous waste streams. An integral part of this system is a model that provides for the optimization of the treatment system through simulation of U(VI) removal efficiency based on the characteristics of the influent waste stream. The model accounts for changing solution matrix conditions through the coupling of surface complexation and mass transfer models. Complexation of U(VI) by chitin surface sites was modeled using FITEQL. Application of FITEQL in the “forward” mode provided the sorbed and aqueous phase concentrations needed for the mass transfer model. The mass transfer model was derived for both batch and continuously stirred tank reactor (CSTR) configurations using Fick's Law, reactor mass balances and rate law expressions. The coupled model was successfully validated using CSTR data at pH 6.5 and rate constants determined from batch sorption experiments. The CSTR configuration yields a steady-state, eighty percent U(VI) removal for 1 μM influent U(VI) with a solution-phase pH of 6.5 and 3.9 g l−1 chitin. 相似文献
175.
Zusammenfassung Durch Einwirkung von SOCl2 auf 4-Hydroxycumarin bzw. 4-Hydroxycarbostyril sind Bis-(4-hydroxycumarinyl-[3])-sulfid (I) und Bis-(4-hydroxycarbostyril-[3])-sulfid (II) leicht zugänglich. Diese Sulfide können zu Dicumarino- bzw. Dicarbostyrilo-(1,4)-oxathiinen (III bzw. IV) cyclisiert werden.
Herrn KollegenH. Bretschneider, Innsbruck, mit den besten Wünschen zum 60. Geburtstag.
Aus der DissertationTh. Kappe, Universität Graz 1961, S. 78–83. 相似文献
Bis-(4-hydroxycoumarinyl-[3])-sulfide (I) and bis-(4-hydroxycarbostyril-[3])-sulfide (II) have been prepared by the reaction between SOCl2 and 4-hydroxycoumarin and 4-hydroxycarbostyril. Cyclisation of these sulfides yielded dicoumarino- (III) and dicarbostyrilo-oxathiin-(1.4) (IV).
Herrn KollegenH. Bretschneider, Innsbruck, mit den besten Wünschen zum 60. Geburtstag.
Aus der DissertationTh. Kappe, Universität Graz 1961, S. 78–83. 相似文献
176.
Coulomb excitation of the first excited 2+-state was measured usingα-particles to determine reduced transition probabilities,B(E2; 0 gs + →2 1 + ), in nuclei with a closed shell of 82 neutrons. TheB(E2; 0 gs + →2 1 + -values are 10.2 single-particle units (spu) for138Ba, 13.5 spu for140Ce, 11.9 spu for142Nd and 11.6 spu for144Sm. The uncertainty ranges from 1.3 % to 2.3 %. 相似文献
177.
G. Dlubek J. Stejny Th. Lüpke D. Bamford K. Petters Ch. Hübner M. A. Alam M. J. Hill 《Journal of Polymer Science.Polymer Physics》2002,40(1):65-81
High‐quality positron lifetime measurements (70 million total counts) are reported for polyethylenes (PEs) of different crystallinities (Xc = 3–82%). The specific volumes of the crystalline and amorphous phases (Vc and Va, respectively) were estimated from density and wide‐angle X‐ray scattering (WAXS) experiments. Some samples (those with low values of Xc) were branched PEs, and those with high values of Xc were linear PEs for which Xc was varied with changes in the crystallization temperature. Both Vc and Va increase with decreasing Xc in the range 0% ≤ Xc ≤ 56% (the branched PEs) but are constant for Xc ≥ 56% (the linear PEs). The lifetime spectra were analyzed with the MELT and LIFSPECFIT routines. Artifacts that can appear in the spectrum analysis were checked via an analysis of computer‐generated spectra. Four lifetime components appeared in all of the PEs; the two long‐lived ones are attributed to pick‐off annihilation of ortho‐positronium (o‐Ps) in crystalline regions (τ3) and in holes of the amorphous phase (τ4). With increasing Xc, τ3 decreases from about 1.2 to 1 ns, τ4 decreases from 3.0 to 2.5 ns, and the intensity I4 decreases from 29 to 0%. An increase in I3 from 6 to 12% was observed. A comparison with simulations shows that the true I3 value approaches 0 for Xc → 0%. The decrease in I4 is weaker than the increase in Xc; this leads to the conclusion that the apparent specific o‐Ps yield in the amorphous phase I4Xc increases with Xc. Possible reasons for this surprising results are discussed. The fractional free hole volume [h = (Va ? Vocc)/Va, where Vocc is the crystalline occupied volume] was estimated from density and WAXS results. Between Xc = 0 and 56%, h decreases from 0.151 to 0.090, but it does not change further above Xc = 56%. The mean size (v) of the local free volumes (holes) estimated from τ4 decreases from 200 to 150 Å3. The number density of holes (Nh) calculated from these values (Nh = h/v) also decreases from 0.8 to 0.6 nm?3 in the range 0% ≤ Xc ≤ 56%. The values of Va, Vc, h, and Nh increase with an increasing degree of branching but do not vary for linear PEs. The possible influence of a crystalline–amorphous interfacial phase (three‐phase model) on the observed lifetime parameters is also discussed. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 40: 65–81, 2002 相似文献
178.
179.
Nelson A Belitsky JM Vidal S Joiner CS Baum LG Stoddart JF 《Journal of the American Chemical Society》2004,126(38):11914-11922
A self-assembled pseudopolyrotaxane consisting of lactoside-displaying cyclodextrin (CD) "beads" threaded onto a linear polyviologen "string" was investigated for its ability to inhibit galectin-1-mediated T-cell agglutination. The CDs of the pseudopolyrotaxane are able to spin around the axis of the polymer chain as well as to move back and forth along its backbone to alter the presentation of its ligand. This supramolecular superstructure incorporates all the advantages of polymeric structures, such as the ability to span large distances, along with a distinctively dynamic presentation of its lactoside ligands to afford a neoglycoconjugate that can adjust to the relative stereochemistries of the lectin's binding sites. The pseudopolyrotaxane exhibited a valency-corrected 10-fold enhancement over native lactose in the agglutination assay, which was greater than the enhancements observed for lactoside-bearing trivalent glycoclusters and a lactoside-bearing chitosan polymer tested using the same assay. The experimental results indicate that supramolecular architectures, such as the pseudopolyrotaxane, provide tools for investigating protein-carbohydrate interactions. 相似文献
180.
J.W. Hofstraat M. Engelsma R.J. Van De Nesse C. Gooijer N.H. Velthorst U.A.Th. Brinkman 《Analytica chimica acta》1986
The coupling of liquid chromatography (l.c.) on narrow-bore columns to thin-layer chromatography (t.l.c.) is described. The effluent from a l.c. column can be deposited on a t.l.c. plate after a normal-phase or reversed-phase separation without serious loss of chromatographic information. Both silica and alkyl-modified silica plates can be used for storage. The interface is a fused silica capillary which connects the column outlet to the spray jet assembly of a Linomat applicator for t.l.c. The stored chromatogram can serve as starting point for a new separation, but also allows the use of detection principles which are normally not compatible with l.c. The chromatography of some polynuclear aromatic hydrocarbons is used to illustrate the possibilities of the combinations. 相似文献