全文获取类型
收费全文 | 797篇 |
免费 | 20篇 |
国内免费 | 3篇 |
专业分类
化学 | 632篇 |
晶体学 | 10篇 |
力学 | 8篇 |
数学 | 39篇 |
物理学 | 131篇 |
出版年
2023年 | 6篇 |
2022年 | 2篇 |
2021年 | 6篇 |
2020年 | 9篇 |
2019年 | 10篇 |
2018年 | 6篇 |
2017年 | 4篇 |
2016年 | 16篇 |
2015年 | 15篇 |
2014年 | 17篇 |
2013年 | 40篇 |
2012年 | 30篇 |
2011年 | 65篇 |
2010年 | 26篇 |
2009年 | 27篇 |
2008年 | 51篇 |
2007年 | 45篇 |
2006年 | 60篇 |
2005年 | 47篇 |
2004年 | 48篇 |
2003年 | 47篇 |
2002年 | 42篇 |
2001年 | 15篇 |
2000年 | 12篇 |
1999年 | 14篇 |
1998年 | 9篇 |
1997年 | 8篇 |
1996年 | 7篇 |
1995年 | 9篇 |
1994年 | 5篇 |
1993年 | 6篇 |
1992年 | 8篇 |
1991年 | 6篇 |
1990年 | 8篇 |
1989年 | 7篇 |
1988年 | 8篇 |
1987年 | 6篇 |
1986年 | 4篇 |
1985年 | 8篇 |
1984年 | 5篇 |
1983年 | 2篇 |
1982年 | 3篇 |
1981年 | 11篇 |
1980年 | 6篇 |
1979年 | 9篇 |
1978年 | 8篇 |
1977年 | 12篇 |
1975年 | 1篇 |
1974年 | 1篇 |
1968年 | 2篇 |
排序方式: 共有820条查询结果,搜索用时 15 毫秒
11.
Ritthiruangdej P Kasemsumran S Suwonsichon T Haruthaithanasan V Thanapase W Ozaki Y 《The Analyst》2005,130(10):1439-1445
Near-infrared (NIR) transflectance spectra in the region of 1100-2500 nm were measured for 100 Thai fish sauces. Quantitative analyses of total nitrogen (TN) content, pH, refractive index, density and brix in the Thai fish sauces and their qualitative analyses were carried out by multivariate analyses with the aid of wavelength interval selection method named searching combination moving window partial least squares (SCMWPLS). The optimized informative region for TN selected by SCMWPLS was the region of 2264-2428 nm. A PLS calibration model, which used this region, yielded the lowest root mean square error of prediction (RMSEP) of 0.100% w/v for the PLS factor of 5. This prediction result is significantly better than those obtained by using the whole spectral region or informative regions selected by moving window partial least squares regression (MWPLSR). As for pH, density, refractive index and brix, the 1698-1722, and 2222-2258 nm regions, the 1358-1438 nm region, the 1774-1846, and 2078-2114 nm regions, and the 1322-1442, and 2000-2076 nm regions were selected by SCMWPLS as the optimized regions. The best prediction results were always obtained by use of the optimized regions selected by SCMWPLS. The lowest RMSEP for pH, density, refractive index and brix were 0.170, 0.007 g cm(-3), 0.0079 and 0.435 degrees Brix, respectively. Qualitative models were developed by using four supervised pattern recognitions, linear discriminant analysis (LDA), factor analysis-linear discriminant analysis (FA-LDA), soft independent modeling of class analog (SIMCA), and K neareat neighbors (KNN) for the optimized combination of informative regions of the NIR spectra of fish sauces to classify fish sauces into three groups based on TN. All the developed models can potentially classify the fish sauces with the correct classification rate of more than 82%, and the KNN classified model has the highest correct classification rate (95%). The present study has demonstrated that NIR spectroscopy combined with SCMWPLS is powerful for both the quantitative and qualitative analyses of Thai fish sauces. 相似文献
12.
The dispersive component
s
d
of the surface free energy of glass fibers and its interaction energy with alkanes, benzene, 1-nitropropane, ethyleneglycol, glycerol, formamide, and water were quantitatively determined by the tensiometric method within two liquids. The values of nondispersive interaction energy I
SL
p
were found to be a linear function of the square root of the nondispersive component of the surface free energy of liquids. This suggests that the nondispersive interaction energy may be represented by the geometric mean of the nondispersive component of the surface free energy of a solid and a liquid. The slope gave the nondispersive component
s
p
of the surface free energy. The
s
p
values are 33 and 14 mJ/m2 for the untreated and aminosilane-treated fibers, respectively, suggesting that organophilic character has developed on the surface after aminosilane treatment. The
s
p
value was almost similar after the treatment, probably because of the polar characteristics of amino groups. 相似文献
13.
Oderaotoshi Y Cheng W Fujitomi S Kasano Y Minakata S Komatsu M 《Organic letters》2003,5(26):5043-5046
High diastereo- and enantioselectivities were obtained for the asymmetric 1,3-dipolar cycloaddition of azomethine ylides generated from N-alkylideneglycine esters with dipolarophiles using chiral phosphine-copper complexes as catalysts. Whereas the cycloaddition of azomethine ylides catalyzed by metal salts generally afforded endo-adducts as the predominant product, the present method is the first example of an exo-selective cycloaddition. [reaction: see text] 相似文献
14.
15.
Yukihiro Shintani Keiji Hirako Masanori Motokawa Yoshihiko Takano Masahiro Furuno Hiroyoshi Minakuchi Mitsuyoshi Ueda 《Analytical sciences》2004,20(12):1721-1723
An interconnecting technique, the "PDMS connection method", for quartz microchips in a high-pressure system is presented. The connection between quartz microchips is an essential technology for modular microfluidic devices, such as microchip-HPLC. PDMS was applied to the seal material, being spread on the seal side of the chips, and set into the metal housing. The characteristics of the PDMS connection method concerning pressure resistance and the extension of the peak were examined. The experimental results showed a good seal at 5 MPa, which seem to be sufficient for realizing microchip-HPLC utilizing a monolithic silica capillary column as a separation medium. The influence of the extra column effect on chromatographic separation was almost the same as in the case using a commercial union fitting. In addition, the PDMS connection enabled the detachability of chip-based modules with user-friendliness. Our experimental findings suggest that the novel PDMS connection method can possibly be applied as a generic technology in high-pressure microTAS. 相似文献
16.
Hiromori Tsutsumi Ken Okanishi Mikiji Miyata Kiichi Takemoto 《Journal of polymer science. Part A, Polymer chemistry》1990,28(6):1527-1538
Inclusion polymerization of 1-chlorobutadiene was studied using 3α,12α-dihydroxy-5β-cholan-24-oic acid (deoxycholic acid, DCA) as host molecules. It was found that the poly(1-chlorobutadiene) had almost 100% of head to tail, trans-1,4-structure on the basis of 13C-NMR and IR spectroscopies. This was the first example of preparing the highly regulated poly(1-chlorobutadiene) by using the inclusion polymerization technique. The polymers obtained were optically active and the maximum value of specific rotation was [α]D-41.9°. Both the rate constants and the value of activation energy of the elementary reactions of inclusion polymerization of 1-chlorobutadiene were determined by graphical evaluation. The activation energy of propagation and termination was 11.7 and 11.1 kcal/mol, respectively. 相似文献
17.
Okada Y Yokozawa M Akiba M Oishi K O-kawa K Akeboshi T Kawamura Y Inokuma S Nakamura Y Nishimura J 《Organic & biomolecular chemistry》2003,1(14):2506-2511
A variety of aromatic compounds with both activating and deactivating substituents were brominated with sodium monobromoisocyanurate (SMBI) 1, diethyl ether, diethyl ether-methanesulfonic acid, trifluoroacetic acid, or sulfuric acid were employed as solvents. Thus nitrobenzene was conveniently brominated in sulfuric acid, benzene was readily monobrominated in diethyl ether-methanesulfonic acid, and phenol was selectively brominated at the ortho position under mild conditions in refluxing diethyl ether. With substituents that are easily protonated, trifluoroacetic acid may be employed as solvent in the reaction with 1, in contrast NBS was ineffective in trifluoroacetic acid. This renders 1 a superior reagent relative to NBS. In addition to aromatics, alkenes, ketones and esters were also brominated with 1. Diethyl malonate was brominated with 1 and then subjected to a Bingel reaction with NaH to afford the desired methanofullerene in reasonable yield. 相似文献
18.
Vibrational spectra reveal that ice VII′ transforms to low-density amorphous ice (LDA) at low temperature on release of pressure to ambient pressure and low temperature. The measurements were obtained using in situ Raman spectroscopy of samples of ice VII′ as a function of pressure at 135 K. The observation of this direct decompression-induced VII′-LDA transition complements the previously observed pressure-induced reversible transition between LDA and high-density amorphous ice (HDA) at 120–140 K and the temperature-induced amorphization of metastable ice VII and ice VIII at 0.1 MPa. 相似文献
19.
The mechanism of charge-induced high spin is studied in pi-conjugated molecules by means of a model-Hamiltonian approach. Intersite Coulomb interactions are taken into account in a pi-conjugated moiety, which is coupled with two localized spins through exchange interactions. We clarify spin alignment in neutral and oxidized states by exact numerical calculations including all the correlation effects. In thianthrene-based molecules, one-electron oxidation induces strong ferromagnetic correlation between the localized spins irrespective of the spin alignment in the neutral state. The localized spins are coupled to the delocalized hole spin ferromagnetically, leading to a high-spin state in the oxidized molecule. Our calculations on structural dependence and effective exchange interaction are consistent with the recent experiment of thianthrene bis(nitronyl nitroxide). By comparing the thianthrene-based molecule with the anthracene-based one, we clarify the role of superexchange interactions via the sulfur atoms. 相似文献
20.
A new compound of sodium nonatitanate, Na2Ti9O19, has been prepared by the hydrothermal reactions of titanium dioxide gel with sodium hydroxide aqueous solution. The crystal has a C-centered monoclinic lattice with the unit-cell dimensions a = 12.2, b = 3.78, c = 15.3Å, and β = 98.0°. It is expected that the structure consists of a framework different from those in tri-, hexa-, hepta-, and octatianates. 相似文献