全文获取类型
收费全文 | 197篇 |
免费 | 7篇 |
专业分类
化学 | 148篇 |
晶体学 | 3篇 |
力学 | 2篇 |
数学 | 3篇 |
物理学 | 48篇 |
出版年
2024年 | 1篇 |
2023年 | 2篇 |
2021年 | 1篇 |
2020年 | 1篇 |
2018年 | 4篇 |
2016年 | 3篇 |
2015年 | 6篇 |
2014年 | 4篇 |
2013年 | 11篇 |
2012年 | 10篇 |
2011年 | 17篇 |
2010年 | 8篇 |
2009年 | 5篇 |
2008年 | 8篇 |
2007年 | 15篇 |
2006年 | 9篇 |
2005年 | 10篇 |
2004年 | 9篇 |
2003年 | 8篇 |
2002年 | 5篇 |
2001年 | 2篇 |
2000年 | 5篇 |
1999年 | 5篇 |
1998年 | 5篇 |
1997年 | 4篇 |
1996年 | 1篇 |
1994年 | 1篇 |
1993年 | 4篇 |
1992年 | 5篇 |
1991年 | 3篇 |
1990年 | 1篇 |
1989年 | 1篇 |
1988年 | 2篇 |
1987年 | 3篇 |
1984年 | 2篇 |
1983年 | 4篇 |
1982年 | 3篇 |
1981年 | 3篇 |
1980年 | 1篇 |
1979年 | 4篇 |
1978年 | 1篇 |
1977年 | 1篇 |
1976年 | 2篇 |
1975年 | 1篇 |
1974年 | 1篇 |
1971年 | 2篇 |
排序方式: 共有204条查询结果,搜索用时 500 毫秒
1.
2.
Itoh T Shichi T Yui T Takahashi H Inui Y Takagi K 《The journal of physical chemistry. B》2005,109(8):3199-3206
The present study is an investigation of a reversible thermal color change induced in lamella hybrids of poly(diacetylenecarboxylates) incorporated in layered double hydroxide (LDH) nanosheets. These poly-[m,n]/LDH hybrids prepared by the photo- or gamma-ray-induced polymerization of diacetylenecarboxylates, i.e., CH(3)(CH(2))(m)()(-)(1)CC-CC(CH(2))(n)()(-)(1)CO(2)(-) (mono-[m,n]), and intercalated in LDH lamella sheets, were observed to develop colors ranging from yellow to blue. The change in color was found to depend greatly on the alkyl carbon numbers of the mono-[m,n] (m,n = 10,11; 5,11; 10,5; 16,1) values. Moreover, the conformational alignment of the mono-[m,n] within the LDH was observed to be a crucial factor in color development, which was greatly affected by the intercalation degrees and extent of poly(ene-yne) linkage elongation of the polymers. For the poly-[m,n]/LDH hybrids investigated, a reversible color change was found to occur repeatedly and remarkably for the poly-[10,11]/LDH hybrid. This color change occurred at temperatures between ca. 20 and 80 degrees C back and forth from purple red to bright orange, in stark contrast to the irreversible color change for poly-[10,11] without LDH. Moreover, DSC and Raman spectroscopic studies of the LDH hybrids showed that the thermochromic temperature corresponded to the phase transition temperature of 80 degrees C. XRD analysis also indicated that the poly-[m,n]/LDH hybrid could retain its lamella structure during such thermochromic color changes, enabling conformational recovery in the polymer chains by a cooling down of the hybrids to temperatures lower than the transition temperature, while the nonhybrid poly-[10,11] powders exhibited an irreversible color change at 60 degrees C, above which the polymer powder turned amorphous. 相似文献
3.
The reaction of zirconium n-propoxide in glycol at 300°C yielded microcrystalline tetragonal zirconia (ZrO2). The crystallite size of the product depended on the carbon number of the glycol and increased in the following order (carbon
number of glycol): 2<6<4, which suggested that the heterolytic cleavage of O-C bond of gylcoxide formed by transesterification
is the prime factor for the formation of the product. In toluene, zirconium isopropoxide also gave tetragonal zirconia at
300°C, and zirconium tert-butoxide decomposed at 200°C yielding amorphous zirconia, while zirconium n-propoxide was stable at 300°C. These results suggest that the reaction in toluene depends on the structure of the alkyl group
of the alkoxides. Thus-obtained tetragonal zirconias maintained large surface areas (90–160 m2/g) even after calcination at 500°C. 相似文献
4.
Tatsuo SuzukiMasaharu Inui Seijiro HosokawaSusumu Kobayashi 《Tetrahedron letters》2003,44(18):3713-3716
Ketene N,O-acetals were prepared stereoselectively and submitted to a Lewis acid-mediated 1,3-rearrangement to afford C-alkylated products. The reactions proceeded in a stereoselective manner to construct a chiral quaternary carbon in high selectivity. The stereochemistry of the quaternary center was found to be opposite to that obtained by an anionic direct dienolate alkylation. 相似文献
5.
Determination of cadmium in river water by sequential metal vapour elution analysis (column temperature; > 1500 K) with argon and hydrogen carrier gas and with atomic absorption spectrometric detection is described. The column is made of a molybdenum capillary tube (i.d. 1.22 mm) and the temperature is 1760 K. The cadmium vapor was separated from those of calcium, iron and sodium. The calibration graph was linear up to 15 μ/ml. Relative standard deviations of 0.8–4.3% were obtained in the range 1 to 15 μ/ml. Cadmium in spiked samples (river water) was determined. The results were in good agreement with the amount spiked. 相似文献
6.
Rieko Furuyama Junji Saito Sei-ichi Ishii Makoto Mitani Shigekazu Matsui Yasushi Tohi Haruyuki Makio Naoto Matsukawa Hidetsugu Tanaka Terunori Fujita 《Journal of molecular catalysis. A, Chemical》2003,200(1-2):31-42
This contribution reports ethylene and propylene polymerization behavior of a series of Ti complexes bearing a pair of phenoxy–imine chelate ligands. The bis(phenoxy–imine)Ti complexes in conjunction with methylalumoxane (MAO) can be active catalysts for the polymerization of ethylene. Unexpectedly, this C2 symmetric catalyst produces syndiotactic polypropylene. 13C NMR spectroscopy has revealed that the syndiotacticity arises from a chain-end control mechanism. Substitutions on the phenoxy–imine ligands have substantial effects on both ethylene and propylene polymerization behavior of the complexes. In particular, the steric bulk of the substituent ortho to the phenoxy–oxygen is fundamental to obtaining high activity and high molecular weight for ethylene polymerization and high syndioselectivity for the chain-end controlled propylene polymerization. The highest ethylene polymerization activity, 3240 kg/mol-cat h, exhibited by a complex having a t-butyl group ortho to the phenoxy–oxygen, represents one of the highest reported to date for Ti-based non-metallocene catalysts. Additionally, the polypropylene produced exhibits a Tm, 140 °C, and syndioselectivity, rrrr 83.7% (achieved by a complex bearing a trimethylsilyl group ortho to the phenoxy–oxygen) that are among the highest for polypropylenes produced via a chain-end control mechanism. Hence, the bis(phenoxy–imine)Ti complexes are rare examples of non-metallocene catalysts that are useful for the polymerization of not only ethylene but also propylene. 相似文献
7.
Hirose H Sano H Mizutani G Eguchi M Ooya T Yui N 《Langmuir : the ACS journal of surfaces and colloids》2004,20(7):2852-2854
The effect of the mobility of ligands (maltose groups) in the polyrotaxanes (pRXs) on the structure of the surrounding water molecules was investigated. Raman spectra of collective OH stretching vibration of water molecules in aqueous solutions of maltose-pRX conjugates with different alpha-cyclodextrin (alpha-CD) threading on a poly(ethylene glycol) (PEG) chain was measured. The mobility of maltose groups was estimated by measuring the relaxation time T2 of the C1 protons in maltose groups bound on alpha-CD by NMR experiment. A positive correlation between the Raman intensity of the collective band and the relaxation time T2 was obtained. This result indicates that the degree of order of the water clusters is higher as the mobility of maltose groups increases in these conjugate solutions. It is suggested that rapid motion of maltose groups in the pRX conjugate can contribute to preserving ordered structure of the bulk water clusters. 相似文献
8.
Tsuneyuki Sato Shukei Inui Hitoshi Tanaka Tadatoshi Ota Mikiharu Kamachi Kohji Tanaka 《Journal of polymer science. Part A, Polymer chemistry》1987,25(2):637-652
The polymerization of di-n-butyl itaconate (DBI) intiated with AIBN was kinetically investigated in benezene. The polymerization rate (Rp) was expressed by: Rp = k[AIBN]0.5[DBI]1.7. The polymerization showed a considerably low overall activation energy of 15.3 kcal/mol. The initiator efficiency of AIBN in this system decreased with increasing DBI concentration, ranging from 0.34 to 0.55°C, which is ascribable to viscosity effect due to the monomer. From an ESR study, the polymerization system was found to involve two kinds of persistent radicals, namely, primary propagating ( III ) and propagating ( I ) radicals. The relative concentration of III to I increased with decreasing monomer concentration. Azo-nitrile initiators such as AVN and ACN similarly produced two persistent radicals, while MAIB, DBPO, and PBO yielded only propagating radical I as persistent. The MAIB-initiated polymerization of DBI was also performed in benzene. Similar kinetic features were observed, that is, a higher dependence of Rp on the DBI concentration and a low overall activation energy (14.4 kcal/mol). The following rate equation was obtained at 50°C:Rp = k[MAIB]0.5[DBI]1.6. The initiator efficiency of MAIB decreased with increasing DBI concentration, ranging from 0.32 to 0.53 at 50°C. The concentration of propagating radical I was determined by ESR at 50 and 61°C, from which kp and kt were estimated. The kp value increased with increasing monomer concentration, while the kt one decreased with the DBI concentration. These values are much lower compared with those of MMA. 相似文献
9.
10.