全文获取类型
收费全文 | 197篇 |
免费 | 11篇 |
专业分类
化学 | 150篇 |
力学 | 1篇 |
数学 | 42篇 |
物理学 | 15篇 |
出版年
2022年 | 1篇 |
2021年 | 1篇 |
2020年 | 1篇 |
2019年 | 7篇 |
2018年 | 1篇 |
2017年 | 6篇 |
2016年 | 4篇 |
2015年 | 9篇 |
2014年 | 4篇 |
2013年 | 8篇 |
2012年 | 9篇 |
2011年 | 10篇 |
2010年 | 10篇 |
2009年 | 7篇 |
2008年 | 13篇 |
2007年 | 17篇 |
2006年 | 15篇 |
2005年 | 17篇 |
2004年 | 11篇 |
2003年 | 7篇 |
2002年 | 1篇 |
2001年 | 5篇 |
1999年 | 3篇 |
1998年 | 3篇 |
1997年 | 1篇 |
1996年 | 2篇 |
1995年 | 1篇 |
1994年 | 5篇 |
1993年 | 2篇 |
1992年 | 1篇 |
1990年 | 2篇 |
1989年 | 1篇 |
1988年 | 2篇 |
1986年 | 1篇 |
1985年 | 2篇 |
1984年 | 1篇 |
1983年 | 1篇 |
1982年 | 1篇 |
1980年 | 3篇 |
1978年 | 1篇 |
1977年 | 1篇 |
1976年 | 1篇 |
1975年 | 2篇 |
1974年 | 1篇 |
1970年 | 1篇 |
1964年 | 1篇 |
1955年 | 1篇 |
1948年 | 3篇 |
排序方式: 共有208条查询结果,搜索用时 15 毫秒
151.
Heikki O. Hämäläinen Iiro S. Honkala Markku K. Kaikkonen Simon N. Litsyn 《Designs, Codes and Cryptography》1993,3(3):251-275
We study codes that are multiple coverings of the Hamming space
and discuss lower and upper bounds onK(n, r, ), the minimum cardinality of a binary code of lengthn such that the Hamming spheres of radiusr centered at the codewords cover
at least times. We also study the similar problem of multiple coverings containing repeated words. A table of bounds forn16,r4, 4 is given. 相似文献
152.
Pia Vuorela Eeva-Liisa Rahko Raimo Hiltunen Heikki Vuorela 《Journal of chromatography. A》1994,670(1-2):191-198
The retention behaviour of fifteen closely related coumarins in normal-phase overpressured layer chromatography (OPLC) was studied with the aim of comparing the retentions with those in normal-phase thin-layer chromatography (TLC) and high-performance liquid chromatography (HPLC) when optimization of the mobile phase was carried out according to the PRISMA system. The mobile phase optimization was carried out on TLC plates in unsaturated chambers. The resulting mobile phases were transposed to off-line, non-equilibrated OPLC and further to HPLC. The retention in TLC was measured at 37 selectivity points and in OPLC and HPLC at 13 points. Capacity factors (k′) and separation factors () were calculated in order to study the retention behaviour in the different systems. Two- and three-dimensional evaluations of k′ against selectivity points showed similar retention behaviours for the coumarins in TLC, OPLC and HPLC. The values for TLC, OPLC and HPLC showed similar patterns in the three-dimensional evaluations. The retention behaviour at different solvent strengths was also examined. According to quadratic regression, k′ showed a dependence on the change in solvent strength. OPLC, which can be considered as a “planar column” technique, and TLC are closely related methods, whereas HPLC shows a different behaviour in the elution process with regard to solvent strength. 相似文献
153.
Tuononen HM Suontamo R Valkonen J Laitinen RS Chivers T 《The journal of physical chemistry. A》2005,109(28):6309-6317
The electronic structures and molecular properties of S2N2 as well as the currently unknown chalcogen nitrides Se2N2 and SeSN2 have been studied using various ab initio and density functional methods. All molecules share a qualitatively similar electronic structure and can be primarily described as 2pi-electron aromatics having minor singlet diradical character of 6-8% that can be attributed solely to the nitrogen atoms. This diradical character is manifested in the prediction of their molecular properties, in which coupled cluster and multiconfigurational approaches, as well as density functional methods, show the best performance. The conventional ab initio methods RHF and MP2 completely fail to describe these systems. Predictions for the vibrational frequencies, IR intensities, Raman activities, and 14N, 15N, and 77Se chemical shifts, as well as singlet excitation energies of Se2N2 and SeSN2, have been made. The computed high-level spectroscopic data will be of considerable value in future efforts aimed at the preparation of the conducting polymers (SeN)x and (SeNSN)x. 相似文献
154.
Heikki Suomalainen und Evi Arhimo 《Fresenius' Journal of Analytical Chemistry》1948,128(2-3):206-210
Zusammenfassung Die Identität des aus Äpfelsäure — wahrscheinlich auch aus Asparaginsäure und Tyrosin — durch bromierende Permanganatoxydation entstehenden 2,4-Dinitrophenylhydrazinderivats mit sowohl aus Glyoxal als auch aus Dibromacetaldehyd hergestelltem Glyoxal-2,4-dinitrophenylosazon wurde festgestellt. Bei der Reaktion fungiert Dibromacetaldehyd als Zwischenprodukt.Auf Grund dieser Reaktion ist die Mikrobestimmungsmethode der Äpfelsäure vonPucher, Vickery undWakeman bearbeitet worden, die von A. A.Arhimo auch auf Asparaginsäure angewendet worden ist. 相似文献
155.
Shan J Chen J Nuopponen M Tenhu H 《Langmuir : the ACS journal of surfaces and colloids》2004,20(11):4671-4676
The thermally induced phase transition of the poly(N-isopropylacrylamide) (PNIPAM) brush covalently bound to the surface of the gold nanoparticles was studied using high-sensitivity microcalorimetry. Two types of PNIPAM monolayer protected clusters (MPCs) of gold nanoparticles were employed, denoted as the cumyl- and the cpa-PNIPAM MPCs, bearing either a phenylpropyl end group or a carboxyl end group on each PNIPAM chain, respectively. The PNIPAM chains of both MPCs exhibit two separate transition endotherms; i.e., the first transition with a sharp and narrow endothermic peak occurs at lower temperature, while the second one with a broader peak occurs at higher temperature. With increase of the MPC concentration, the transition temperature corresponding to the first peak only slightly changes but the second transition temperature strongly shifts to lower temperature. The calorimetric enthalpy change in the first transition is much smaller than that in the second transition. The ratio of the calorimetric enthalpy change to the van't Hoff enthalpy change indicates that in the first transition PNIPAM segments show much higher cooperativity than in the second one. The investigation of pH dependence of two-phase transitions further indicates the PNIPAM brush reveals two separate transitions even with a change in interchain/interparticle association. The observations are tentatively rationalized by assuming that the PNIPAM brush can be subdivided into two zones, the inner zone and the outer zone. In the inner zone, the PNIPAM segments are close to the gold surface, densely packed, less hydrated, and undergo the first transition. In the outer zone, on the other hand, the PNIPAM segments are looser and more hydrated, adopt a restricted random coil conformation, and show a phase transition, which is dependent on both concentration of MPC and the chemical nature of the end groups of the PNIPAM chains. Aggregation of the particles, which may also affect the phase transition, is briefly discussed. 相似文献
156.
Galant C Kjøniksen AL Knudsen KD Helgesen G Lund R Laukkanen A Tenhu H Nyström B 《Langmuir : the ACS journal of surfaces and colloids》2005,21(17):8010-8018
Aqueous mixtures of the anionic sodium dodecyl sulfate (SDS) surfactant and thermo-responsive poly(N-vinylcaprolactam) chains grafted with omega-methoxy poly(ethylene oxide) undecyl alpha-methacrylate (PVCL-g-C11EO42) have been characterized using turbidimetry and small-angle neutron scattering (SANS). Turbidity measurements show that the addition of SDS to a dilute aqueous copolymer solution (1.0 wt %) induces an increase of the cloud point (CP) value and a decrease of the turbidity at high temperatures. In parallel, SANS results show a decrease of both the average distance between chains and the global size of the objects in solution at high temperatures as the SDS concentration is increased. Combination of these findings reveals that the presence of SDS in the PVCL-g-C11EO42 solutions (1.0 wt %) promotes the formation of smaller aggregates and, consequently, leads to a more homogeneous distribution of the chains in solution upon heating of the mixtures. Moreover, the SANS data results show that the internal structure of the formed aggregates becomes more swollen as the SDS concentration increases. On the other hand, the addition of moderate amounts of SDS (up to 4 mm) to a semidilute copolymer solution (5.0 wt %) gives rise to a more pronounced aggregation as the temperature rises; turbidity and SANS studies reveal in this case a decrease of the CP value and an increase of the scattered intensity at low q. The overall picture that emerges from this study is that the degree of aggregation can be accurately tuned by varying parameters such as the temperature, level of surfactant addition, and polymer concentration. 相似文献
157.
Yohannes G Shan J Jussila M Nuopponen M Tenhu H Riekkola ML 《Journal of separation science》2005,28(5):435-442
Asymmetrical flow field-flow fractionation (AsFIFFF) was used to determine the hydrodynamic particle sizes, molar masses, and phase transition behaviour of various poly(N-isopropylacrylamide) (PNIPAM) samples synthesised by reversible addition--fragmentation chain transfer (RAFT) and conventional free radical polymerisation processes. The results were compared with corresponding data obtained by dynamic light scattering (DLS) and size exclusion chromatography (SEC). Agreement between the three methods was good except at higher molar masses, where the molar mass averages obtained by SEC were much lower than those obtained by AsFIFFF and light scattering. The aggregation of the polymers, which are thermally sensitive, was studied by DLS and AsFIFFF at various temperatures. In deionised water there was an abrupt change in the particle size due to phase separation at approximately equal to 32-35 degrees C. The critical temperatures determined by AsFIFFF were 3-5 degrees C higher than those obtained by DLS. 相似文献
158.
The C(12b)-C(1)-C(2)-C(3) stereochemical relationship in several racemic indolo[2,3-a]quinolizine derivatives has been determined by the application of conformational considerations to the 13C NMR spectral analysis. The proper shift assignment was confirmed by recording the spectra of selectively deuterated derivatives. The C(12b)-C(1)-C(2)-C(3) stereochemical relationship in indolo[2,3-a]quinolizines obtained by acid-induced cyclizadon of partially hydrogenated 3,5-dimethoxycarbonyl-1-[2-(3-indolyl)ethyl]pyridine derivatives is discussed. 相似文献
159.
Vladimir O. Aseyev Jyrki Juhanoja Heikki Tenhu Stanislav I. Klenin 《Journal of Polymer Science.Polymer Physics》1999,37(23):3337-3343
A high molar mass polycation poly(methacryloylethyl trimethylammonium methylsulphate), PMETMMS, dissolved in mixtures of water and acetone, was studied using light scattering during the reversible coil-to-globule transition. When the mass fraction of acetone in the solvent mixture, γ, is higher than 0.80, PMETMMS adopts a globular state but does not aggregate. The collapse of PMETMMS can also be induced by the dilution of the polymer solution, if 0.70 ≤ γ < 0.80, and the solvent composition is kept constant. The results obtained by light scattering have been confirmed using a transmission electron microscope with which the collapse of PMETMMS has been observed. At high polymer concentration and 0.70 ≤ γ < 0.80, a transient network is formed: coils strongly interact with each other via dipole–dipole interactions in a thermodynamically poor solvent. At low concentration regime when 0.70 ≤ γ < 0.80, or in solutions with the mass fraction of acetone higher than 0.80, all the PMETMMS molecules are collapsed. In the intermediate region, the collapse of PMETMMS is gradual and coils, globules, as well as fragments of the network coexist in the solution. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 3337–3343, 1999 相似文献
160.