全文获取类型
收费全文 | 436篇 |
免费 | 26篇 |
国内免费 | 21篇 |
专业分类
化学 | 337篇 |
晶体学 | 11篇 |
力学 | 5篇 |
综合类 | 1篇 |
数学 | 41篇 |
物理学 | 88篇 |
出版年
2023年 | 5篇 |
2022年 | 5篇 |
2021年 | 12篇 |
2020年 | 9篇 |
2019年 | 4篇 |
2018年 | 4篇 |
2017年 | 7篇 |
2016年 | 16篇 |
2015年 | 10篇 |
2014年 | 12篇 |
2013年 | 24篇 |
2012年 | 24篇 |
2011年 | 24篇 |
2010年 | 20篇 |
2009年 | 15篇 |
2008年 | 22篇 |
2007年 | 23篇 |
2006年 | 31篇 |
2005年 | 17篇 |
2004年 | 7篇 |
2003年 | 10篇 |
2002年 | 13篇 |
2001年 | 9篇 |
2000年 | 8篇 |
1999年 | 5篇 |
1998年 | 5篇 |
1997年 | 3篇 |
1996年 | 3篇 |
1995年 | 12篇 |
1994年 | 9篇 |
1993年 | 8篇 |
1992年 | 8篇 |
1990年 | 3篇 |
1989年 | 6篇 |
1988年 | 3篇 |
1985年 | 3篇 |
1984年 | 8篇 |
1982年 | 10篇 |
1981年 | 6篇 |
1980年 | 8篇 |
1978年 | 3篇 |
1975年 | 4篇 |
1974年 | 3篇 |
1973年 | 3篇 |
1969年 | 4篇 |
1967年 | 3篇 |
1963年 | 2篇 |
1956年 | 2篇 |
1935年 | 2篇 |
1930年 | 2篇 |
排序方式: 共有483条查询结果,搜索用时 31 毫秒
11.
Robert J. Maxwell Alan R. Lightfield Alida A. M. Stolker 《Journal of separation science》1995,18(4):231-234
An in-line collector assembly designed for use in supercritical fluid extraction (SFE) vessels is described. This assembly enables solutes extracted by supercritical fluids (SF) to be retained in-line on standard solid phase extraction (SPE) columns. The assembly consists of a standard 1 mL or 3 mL SPE column fitted into a specially fabricated Teflon© sleeve. The SPE column-Teflon sleeve assembly is inserted into the SFE vessel followed by the sample matrix. This unit forms a leak-tight seal with the vessel's end-cap up to pressures of 680 bar. The choice of sorbents used in the in-line SPE columns is dependent upon the properties of the solute in the supercritical state. After SFE is completed, the SPE column is removed and the solutes are recovered in 1–2 mL of the eluting solvent. No further clean-up is normally required prior to chromatographic analysis of the analyte. A comparison was made of recoveries by in-line and off-line (after SF decompression) techniques for the SFE of three anabolic steroids in fortified chicken liver. The HPLC chromatograms of the steroids from the off-line SPE columns were too complex for quantitation, because of coeluting artifacts, whereas chromatograms obtained from in-line SPE columns were free from UV-absorbing interferences and were easily quantified. 相似文献
12.
S. S. Berman K. W. M. Siu P. S. Maxwell D. Beauchemin V. P. Clancy 《Fresenius' Journal of Analytical Chemistry》1989,333(6):641-644
Summary The methylmercury concentrations in three existing marine biological certified reference materials — TORT-1, DORM-1 and DOLT-1 — are determined by gas chromatography with electron capture detection, cold vapour atomic absorption spectrometry and inductively coupled plasma mass spectrometry after selective isolation of methylmercury. Two such procedures were used. These and the three analytical techniques are evaluated and compared. The certified methylmercury concentrations are: TORT-1, 0.128 ± 0.014; DORM-1, 0.731±0.060; and DOLT-1, 0.080 ± 0.011 g Hg/g dry weight.
Meeresbioligische Referenzmaterialien für Methylquecksilber: Analytische Methoden der Zertifizierung相似文献
13.
We obtain sharp bounds on some basic functionals defined on the sets of all analytic functions having the representations \(f\left( z \right) \equiv \int\limits_{ - 1}^1 {\frac{{d\mu \left( t \right)}}{{z - t}}} \) and \(\varphi \left( z \right) \equiv \int\limits_{ - 1}^1 {\frac{{z\mu \left( t \right)}}{{1 - tz}}} \) ; respectively. Here μ is a probability measure. 相似文献
14.
Step-scan FTIR time-resolved spectroscopy (S2FTIR TRS) in acetonitrile-d3 has been used to probe the acceptor ligand in metal-to-ligand charge transfer (MLCT) excited states of amide-substituted polypyridyl complexes of RuII and in analogues appended to polystyrene. On the basis of ground-to-excited state shifts in v(C = O) of -31 cm-1 for the amide group in [RuII(bpy)2(bpyCONHEt')]2+ (bpyCONHEt' = 4'-methyl-2,2'-bipyridine-4-carboxamide-Et'; Et' = -CH2CH2BzCH2CH3) (1) and in the derivatized polystyrene abbreviated [PS-[CH2-CH2NHCObpy-RuII(bpy)2]20]40+ (3), the excited-state dipole is directed toward the amide-containing pyridyl group in the polymer side chain. Smaller shifts in v(C = O) of -17 cm-1 in [RuII(4,4'-(CONEt2)2bpy)2-(bpyCONHEt')]2+ (2) and in the derivatized polystyrene abbreviated [PS-[CH2CH2NHCObpy-RuII(4,4'-(CONEt2)2bpy)2]20]40+ (4) indicate that the excited-state dipole is directed toward one of the diamide bpy ligands. The nearly identical results for 1 and 3 and for 2 and 4 show that the molecular and electronic structures of the monomer excited states are largely retained in the polymer samples. These conclusions about dipole orientation in the polymers are potentially of importance in understanding intrastrand energy transfer dynamics. The excited-state dipole in 3 is oriented in the direction of the covalent link to the polymer backbone, and toward nearest neighbors. In 4, it is oriented away from the backbone. 相似文献
15.
Connecting two facially-protected porphyrins was expected to lead to an equal mixture of laterally-bridged doubly-protected bis-porphyrins; one in which the two porphyrin units were protected on the same face (syn) and one with the two prophyrin units protected on opposite faces (anti). Addition of a co-factor (bidentate ligand) was expected to lead predominantly to the syn-bis-porphyrin by a templated self-replication process. This concept was explored using Baldwin's capped porphyrin. Bis(capped porphyrins) were synthesised in several steps starting from zinc(II) capped porphyrin 2. Nitration of 2 followed by reduction and photo-oxidation yields a mixture of zinc(II) porphyrindiones 7 and 8 that can separated by HPLC. The condensation of 2 molar eq. of zinc(II) porphyrin-7,8-dione 8 with 1,2,4,5-benzenetetramine leads to the formation of a 1:1 mixture of syn- and anti-dizinc(II) bis(7,8-capped porphyrins), 11 and 12, respectively, that have almost identical spectroscopic properties. These two geometric isomers were distinguished by significant differences in their molecular recognition properties. Likewise the syn- and anti-dizinc(II) bis(2,3-capped porphyrins), 9 and 10, respectively, are synthesised from the related zinc(II) capped porphyrin-2,3-dione 7, and were also identified using molecular recognition studies. The molecular recognition properties of these bis(capped porphyrins) were utilised in studies of self-replicating porphyrin systems. The results show that tetraazaanthraceno-bis-porphyrins 9-12 can catalyse their own formation but self-replication was not observed. These results highlight the potential that these interesting hosts have as templates in supramolecular chemistry, synthesis and catalysis. 相似文献
16.
S. L. Maxwell III 《Journal of Radioanalytical and Nuclear Chemistry》2006,270(3):651-655
Summary The measurement of radium isotopes in natural waters is important for oceanographic studies and for public health reasons.
Radium-226 (T1/2 = 1620 y) is one of the most toxic of the long-lived alpha-emitters present in the environment due to its long life and its
tendency to concentrate in bones, which increases the internal radiation dose of individuals. The analysis of 226Ra and 228Ra in natural waters can be tedious and time-consuming. Different sample preparation methods are often required to prepare
226Ra and 228Ra for separate analyses. A rapid method has been developed at the Savannah River Environmental Laboratory that effectively
separates both 226Ra and 228Ra (via 228Ac) for assay. This method uses MnO2 Resin from Eichrom Technologies (Darien, IL, USA) to preconcentrate 226Ra and 228Ra rapidly from water samples, along with 133Ba tracer. DGA Resinò (Eichrom) and Ln-Resinò (Eichrom) are employed in tandem to prepare 226Ra for assay by alpha-spectrometry and to determine 228Ra via the measurement of 228Ac by gas proportional counting. After preconcentration, the manganese dioxide is dissolved from the resin and passed through
stacked Ln-Resin-DGA Resin cartridges that remove uranium and thorium interferences and retain 228Ac on DGA Resin. The eluate that passed through this column is evaporated, redissolved in a lower acidity and passed through
Ln-Resin again to further remove interferences before performing a barium sulfate microprecipitation. The 228Ac is stripped from the resin, collected using cerium fluoride microprecipitation and counted by gas proportional counting.
By using vacuum box cartridge technology with rapid flow rates, sample preparation time is minimized. 相似文献
17.
Lilian F. J. Noël Ian A. Maxwell Willy J. M. Van Well Anton L. German 《Journal of polymer science. Part A, Polymer chemistry》1994,32(11):2161-2168
Recently a model has been developed capable of predicting absolute monomer concentrations and their ratios in the polymer, aqueous, and monomer droplet phases as a function of conversion in batch emulsion copolymerizations without using any adjustable parameters. In this article the sensitivity of model predictions of composition drift toward deviations of 10% in all model parameters (maximum swellabilities of monomer in the polymer phase, water solubilities, reactivity ratios, and monomer and polymer densities) was estimated using the monomer combination methyl methacrylate-styrene as an example. From the sensitivity analysis it can be concluded that the reactivity ratios are the most important parameters affecting composition drift. The effects of deviations in maximum swellabilities and monomer and polymer densities on composition drift can be neglected, while the water solubility is important only in those cases where the amount of monomer in the aqueous phase cannot be neglected as compared with the total monomer amount. © 1994 John Wiley & Sons, Inc. 相似文献
18.
Colloidal gold nanocrystals have been used to develop a new class of nanobiosensors that is able to recognize and detect specific DNA sequences and single-base mutations in a homogeneous format. At the core of this biosensor is a 2.5-nm gold nanoparticle that functions as both a nano-scaffold and a nano-quencher (efficient energy acceptor). Attached to this core are oligonucleotide molecules labeled with a thiol group at one end and a fluorophore at the other. This hybrid bio/inorganic construct is found to spontaneously assemble into a constrained arch-like conformation on the particle surface. Binding of target molecules results in a conformational change, which restores the fluorescence of the quenched fluorophore. Unlike conventional molecular beacons with a stem-and-loop structure, the nanoparticle probes do not require a stem, and their background fluorescence increases little with temperature. In comparison with the organic quencher Dabcyl (4,4'-dimethylaminophenyl azo benzoic acid), metal nanoparticles have unique structural and optical properties for new applications in biosensing and molecular engineering. 相似文献
19.
D Lathrop D Franke R Maxwell T Tepe R Flesher Z Zhang H Eckert 《Solid state nuclear magnetic resonance》1992,1(2):73-83
The ability of the 90 degrees-t1-180 degrees pulse sequence to produce accurate dipole-dipole coupling information in solids is investigated. To this end, the experimental 31P spin echo decays are measured for eighteen crystalline phosphides and phosphorus chalcogenides and compared with simulations, based on the known internuclear distances in these compounds. The experimental results are generally found accurate in compounds where the dominant contribution to the dipole-dipole coupling arises from nuclei in structurally inequivalent sites with large chemical shift anisotropies. For this situation, the quantum mechanical "flip-flop" term in the dipolar Hamiltonian is suppressed and the dipole-dipole coupling is entirely heteronuclear in character. All of those compounds that do not obey this condition show accelerated spin echo decays due to a fractional contribution of the flip-flop term and possibly incomplete refocusing of chemical shift terms on the time scale of the experiment. The results confirm on an empirical basis that the spin echo NMR technique can provide accurate dipole-dipole coupling information (and thus distance distributions) in disordered solids and glasses. 相似文献
20.
Maxwell A. Cairns Keith R. Dixon Martin A.R. Smith 《Journal of organometallic chemistry》1977,135(1):C33-C34
Syntheses of cis-[PtCl(CH2COCH3)(PEt3)2], cis-[PtCl(CH2NO2) (PEt3)2], and trans-[Pt(CCPh)2 (PEt3)2] are described. The procedure involves reaction of cis-[PtCl2(PEt3)2] with Ag2O and acidic CH bonds to precipitate AgC1 and generate a PtC bond. The method may represent a new general route to platinum—carbon bonds. 相似文献