全文获取类型
收费全文 | 683篇 |
免费 | 41篇 |
国内免费 | 3篇 |
专业分类
化学 | 574篇 |
晶体学 | 5篇 |
力学 | 4篇 |
数学 | 37篇 |
物理学 | 107篇 |
出版年
2024年 | 1篇 |
2023年 | 8篇 |
2022年 | 16篇 |
2021年 | 25篇 |
2020年 | 27篇 |
2019年 | 22篇 |
2018年 | 23篇 |
2017年 | 12篇 |
2016年 | 36篇 |
2015年 | 22篇 |
2014年 | 23篇 |
2013年 | 41篇 |
2012年 | 42篇 |
2011年 | 74篇 |
2010年 | 22篇 |
2009年 | 28篇 |
2008年 | 35篇 |
2007年 | 35篇 |
2006年 | 41篇 |
2005年 | 36篇 |
2004年 | 28篇 |
2003年 | 32篇 |
2002年 | 23篇 |
2001年 | 5篇 |
2000年 | 11篇 |
1999年 | 6篇 |
1998年 | 4篇 |
1997年 | 5篇 |
1996年 | 3篇 |
1995年 | 1篇 |
1994年 | 6篇 |
1993年 | 7篇 |
1992年 | 7篇 |
1991年 | 1篇 |
1990年 | 3篇 |
1989年 | 1篇 |
1988年 | 2篇 |
1987年 | 1篇 |
1985年 | 1篇 |
1984年 | 2篇 |
1982年 | 1篇 |
1981年 | 2篇 |
1978年 | 1篇 |
1975年 | 2篇 |
1974年 | 1篇 |
1973年 | 1篇 |
1969年 | 1篇 |
排序方式: 共有727条查询结果,搜索用时 31 毫秒
51.
S. Hayami T. Kawahara G. Juhász K. Kawamura K. Uehashi O. Sato Y. Maeda 《Journal of Radioanalytical and Nuclear Chemistry》2003,255(3):443-447
The magnetic properties of the spin-crossover compound, [Fe(qsal)2]NCSe·2DMSO (N-(8-quinolyl)-salicyladimine) (1), have been measured. We have discovered that the compound 1 exhibits a wide "thermal hysteresis loop" of 115 K (T1/2 = 324 K and T1/2 = 209 K) in the first cycle. Thermogravimetric analysis shows that solvent molecules of the compound 1 are removed at around 324 K. This means that the hysteresis loop observed for the first cycle is only an apparent one. Following the first loop, the compound 1 shows a spin-crossover in warming mode. The spin transition occurs at T1/2= 285 K and T1/2 = 209 K and the hysteresis width can be estimated to be 76 K, which is one of the largest values reported so far for spin-crossover compounds. It is thought that the cooperativity produced in the compound mainly arises from the intermolecular interactions between the quinoline and the phenyl rings. 相似文献
52.
53.
54.
Kazuki Fukushima Olivier Coulembier Julien M. Lecuyer Hamid A. Almegren Abdullah M. Alabdulrahman Fares D. Alsewailem Melanie A. Mcneil Philippe Dubois Robert M. Waymouth Hans W. Horn Julia E. Rice James L. Hedrick 《Journal of polymer science. Part A, Polymer chemistry》2011,49(5):1273-1281
We describe the organocatalytic depolymerization of poly(ethylene terephthalate) (PET), using a commercially available guanidine catalyst, 1,5,7‐triazabicyclo[4.4.0]dec‐5‐ene (TBD). Postconsumer PET beverage bottles were used and processed with 1.0 mol % (0.7 wt %) of TBD and excess amount of ethylene glycol (EG) at 190 °C for 3.5 hours under atmospheric pressure to give bis(2‐hydroxyethyl) terephthalate (BHET) in 78% isolated yield. The catalyst efficiency was comparable to other metal acetate/alkoxide catalysts that are commonly used for depolymerization of PET. The BHET content in the glycolysis product was subject to the reagent loading. This catalyst influenced the rate of the depolymerization as well as the effective process temperature. We also demonstrated the recycling of the catalyst and the excess EG for more than 5 cycles. Computational and experimental studies showed that both TBD and EG activate PET through hydrogen bond formation/activation to facilitate this reaction. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011 相似文献
55.
56.
Yasuaki Tokudome Kazuki Nakanishi Kazuyoshi Kanamori Koji Fujita Hirofumi Akamatsu Teiichi Hanada 《Journal of colloid and interface science》2009,338(2):506-513
Detailed nanostructures have been investigated for hierarchically porous alumina aerogels and xerogels prepared from ionic precursors via sol–gel reaction. Starting from AlCl3·6H2O and poly(ethylene oxide) (PEO) dissolved in a H2O/EtOH mixed solvent, monolithic wet gels were synthesized using propylene oxide (PO) as a gelation initiator. Hierarchically porous alumina xerogels and aerogels were obtained after evaporative drying and supercritical drying, respectively. Macroporous structures are formed as a result of phase separation, while interstices between the secondary particles in the micrometer-sized gel skeletons work as mesoporous structures. Alumina xerogels exhibit considerable shrinkage during the evaporative drying process, resulting in relatively small mesopores (from 5.4 to 6.2 nm) regardless of the starting composition. For shrinkage-free alumina aerogels, on the other hand, the median mesopore size changes from 13.9 to 33.1 nm depending on the starting composition; the increases in PEO content and H2O/EtOH volume ratio both contribute to producing smaller mesopores. Small-angle X-ray scattering (SAXS) analysis reveals that variation of median mesopore size can be ascribed to the change in agglomeration state of primary particles. As PEO content and H2O/EtOH ratio increase, secondary particles become small, which results in relatively small mesopores. The results indicate that the agglomeration state of alumina primary particles is influenced by the presence of weakly interacting phase separation inducers such as PEO. 相似文献
57.
A macrocyclic host molecule that comprised two different rotating modules, cerium(IV) bis(porphyrinate)s and ferrocenyl rotating units, exhibiting contraction/expansion motion was synthesized, which can be regarded as a prototype of artificial molecular spring driven by cooperative guest binding in 1:6 stoichiometry. 相似文献
58.
Kazuki Fukushima Yoshiharu Kimura 《Journal of polymer science. Part A, Polymer chemistry》2008,46(11):3714-3722
Simultaneous solid‐state polycondensation (SSP) of the powdery prepolymers of poly(L ‐lactic acid) (PLLA) and poly(D ‐lactic acid) (PDLA) can produce entire stereocomplexed poly(lactic acid)s (sc‐PLA) with high molecular weight and can be an alternative synthetic route to sc‐PLA. Ordinary melt polycondensations of L ‐ and D ‐lactic acids gave the PLLA and PDLA prepolymers having medium molecular weight which were pulverized for blending in 1:1 ratio. The resultant powder blends were then subjected to SSP at 130–160 °C for 30 h under a reduced pressure of 0.5 Torr. Some of the products thus obtained attained a molecular weight (Mw) as high as 200 kDa, consisting of stereoblock copolymer of PLLA and PDLA. A small amount of the stereocomplex should be formed in the boundaries of the partially melted PLLA and PDLA where the hetero‐chain connection is induced to generate the blocky components. The resultant SSP products showed predominant stereocomplexation after their melt‐processing in the presence of the stereoblock components in spite of containing a small amount of racemic sequences in the homo‐chiral PLLA and PDLA chains. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 3714–3722, 2008 相似文献
59.
Kazuki Kawabe 《Catalysis Surveys from Asia》2010,14(3-4):111-115
A new process for the production of mono-ethylene glycol (MEG; HOCH2CH2OH) was developed by Mitsubishi Chemical Corporation (MCC) to meet its growing demand in the world. While the MEG selectivity of conventional non-catalyzed process is around 89% under typical conditions, that of the new process exceeds 99%. The key of the high selectivity is the two-step synthesis via ethylene carbonate. The first step reaction is catalyzed by phosphonium salts and generates ethylene carbonate as an intermediate. This is followed by hydrolysis of ethylene carbonate in the second step. Several commercial plants of the new process have already been operated world-wide. 相似文献
60.
Kazuki Itoh 《Geometriae Dedicata》2014,168(1):177-196
We prove an analogue of the Cheeger–Gromoll splitting theorem for sub-Riemannian manifolds with the measure contraction property instead of the nonnegativity of the Ricci curvature. If such a sub-Riemannian manifold contains a straight line, then the manifold splits diffeomorphically, where the splitting is not necessarily isometric. We prove that such a sub-Riemannian manifold containing a straight line cannot split isometrically under some typical condition in sub-Riemannian geometry. Heisenberg groups are such examples. 相似文献