全文获取类型
收费全文 | 1165篇 |
免费 | 46篇 |
国内免费 | 9篇 |
专业分类
化学 | 829篇 |
晶体学 | 16篇 |
力学 | 35篇 |
数学 | 137篇 |
物理学 | 203篇 |
出版年
2023年 | 12篇 |
2022年 | 27篇 |
2021年 | 28篇 |
2020年 | 26篇 |
2019年 | 23篇 |
2018年 | 12篇 |
2017年 | 11篇 |
2016年 | 44篇 |
2015年 | 39篇 |
2014年 | 41篇 |
2013年 | 79篇 |
2012年 | 75篇 |
2011年 | 112篇 |
2010年 | 72篇 |
2009年 | 56篇 |
2008年 | 85篇 |
2007年 | 54篇 |
2006年 | 59篇 |
2005年 | 82篇 |
2004年 | 69篇 |
2003年 | 55篇 |
2002年 | 44篇 |
2001年 | 18篇 |
2000年 | 19篇 |
1999年 | 11篇 |
1998年 | 14篇 |
1997年 | 4篇 |
1996年 | 6篇 |
1995年 | 3篇 |
1994年 | 2篇 |
1993年 | 3篇 |
1992年 | 8篇 |
1991年 | 1篇 |
1990年 | 5篇 |
1989年 | 2篇 |
1988年 | 3篇 |
1987年 | 2篇 |
1985年 | 3篇 |
1984年 | 1篇 |
1981年 | 3篇 |
1972年 | 2篇 |
1971年 | 3篇 |
1970年 | 1篇 |
1955年 | 1篇 |
排序方式: 共有1220条查询结果,搜索用时 15 毫秒
21.
[reaction: see text] We have developed, on the basis of a chelation-strategy, an efficient copper-catalyzed aziridination protocol with the use of 5-methyl-2-pyridinesulfonamide and PhI(OAc)(2). The reaction proceeds smoothly under mild conditions to give aziridines in moderate to good yields in the absence of external ligands or bases. The coordination-assisted approach offers the additional benefits that efficient deprotection of the N-substituent and selective aziridine ring-opening are effectively achieved. 相似文献
22.
Second-order rate constants have been measured spectrophotometrically for the reactions of O-2,4-dinitrophenyl thionobenzoate (1) and 2,4-dinitrophenyl benzoate (2) with a series of substituted pyridines in 80 mol % H(2)O/20 mol % DMSO at 25.0 +/- 0.1 degrees C. The Br?nsted-type plots obtained are nonlinear with beta(1) = 0.26, beta(2) = 1.07, and pK(a) degrees = 7.5 for the reactions of 1 and beta(1) = 0.40, beta(2) = 0.90, and pK(a) degrees = 9.5 for the reactions of 2, suggesting that the pyridinolyses of 1 and 2 proceed through a zwiterionic tetrahedral intermediate T(+/-) with a change in the rate-determining step at pK(a) degrees = 7.5 and 9.5, respectively. The thiono ester 1 is more reactive than its oxygen analogue 2 except for the reaction with the strongest basic pyridine studied (pK(a) = 11.30). The k(1) value is larger for the reactions of 1 than for those of 2 in the low pK(a) region, but the difference in the k(1) value becomes negligible with increasing the basicity of pyridines. On the other hand, 1 exhibits slightly larger k(2)/k(-1) ratio than 2 in the low pK(a) region but the difference in the k(2)/k(-1) ratio becomes more significant with increasing the basicity of pyridines. Pyridines are more reactive than alicyclic secondary amines of similar basicity toward 2 in the pK(a) above ca. 7.2 but less reactive in the pK(a) below ca. 7.2. The k(1) value is slightly larger, but the k(2)/k(-1) ratio is much smaller for the reactions of 2 with pyridines than with isobasic secondary amines in the low pK(a) region, which is responsible for the fact that the weakly basic pyridines are less reactive than isobasic secondary amines. 相似文献
23.
Nak Bae Kim Young Suk Kim Joon Kon Kim Keung Shik Park 《Journal of Radioanalytical and Nuclear Chemistry》1988,125(2):403-417
A Peak Identification and Activity Determination (PIAD) computer program has been developed. A new concept of peak significance is introduced and a great change has been made to the currently used associated gamma lines technique in calculating the confidence index; confidence factor is also given to the gamma line of a nuclide that is not seen in the spectrum. The program is written in Fortran IV under the operating system of RSX-11M. 相似文献
24.
Attila R. Imre W. Alexander Van Hook Bong Ho Chang Young Chan Bae 《Monatshefte für Chemie / Chemical Monthly》2003,134(12):1529-1539
Summary. Upper critical solution temperatures (UCSTs) for liquid–liquid demixing in a set of mixtures of linear alkanes (pentane (N
1=5) to pentacontane (N
1=50)) with an oligostyrene (1241amu, N
2=12) are reported. We find strong correlation between the Hildebrand solubility parameters of the alkanes and the UCST. Correlations are developed which enable predictions concerning the miscibility of mixtures of compounds with longer chains. 相似文献
25.
26.
Kim SY Augustine S Eo YJ Bae BS Woo SI Kang JK 《The journal of physical chemistry. B》2005,109(19):9397-9403
We use a first-principles calculation and small-angle neutron scattering (SANS) to investigate the mechanism and the nanosize products of the sol-gel reaction with diphenylsilanediol (DPD) and 3-methacryloxypropyltrimethoxysilane (MEMO) precursors in synthesizing a hybrid waveguide material. It is predicted that switching between a DPD hydroxyl and a MEMO methoxy with a reaction rate of 6.8 x 10(-6) s(-1) at 300 K is the fastest process for the first reaction step, thus generating diphenylmethoxysilanol (DPM) and 3-methacryloxypropyldimethoxysilanol (MEDO) as products. However, we determine that this reaction pathway could be modified by the presence of the H2O released from a catalyst such as Ba(OH)2.H2O. Next, switching between the DPM hydroxyl and the MEDO methoxy is followed to generate diphenyldimethoxysilane (DPDM) and 3-methacryloxypropylmethoxysilanediol (MEMDO). However, condensation between a MEMDO hydroxyl and a DPDM methoxy is found to be most favorable for the third reaction step, which generates the DPDM-MEMDO dimer and CH3OH molecule as products. In a similar fashion, a DPDM methoxy of the DPDM-MEMDO dimer can condense with a MEMDO hydroxyl of the second DPDM-MEMDO dimer to increase the chain, but its reaction rate of 2.8 x 10(-11) s(-1) is predicted to be about 5 times smaller than that between a DPDM methoxy and a MEMDO hydroxyl. This implies that the reaction rate for the larger nanostructures becomes smaller. Additionally, our SANS measurements determine that the final products from our sol-gel reaction are on the nanometer scale, at sizes from 1.76 to 2.36 nm. 相似文献
27.
28.
The effect of phenyl substituents on the release rates of esterase-sensitive coumarin-based prodrugs
A coumarin-based prodrug system has been recently developed in our laboratory for the preparation of esterase-sensitive prodrugs of amines, peptides, and peptidomimetics. The drug release rates from this prodrug system were found to be dependent on the structural features of the drug moiety. In certain cases, the release can be undesirably slow for drugs that are secondary amines with relatively high pKa's. Aimed at finding ways to manipulate the release rates to suit the need of different drugs, we have examined the effect of the phenyl ring substitutions on the release kinetics of such prodrugs and found that appropriately positioned alkyl substituents on the phenyl ring could help to facilitate the release by as much as 16-fold. Therefore, introduction of alkyl substituents on the phenyl ring should allow us to manipulate the release rates and, therefore, time profiles for different drugs. 相似文献
29.
30.
BMS794833 inhibits macrophage efferocytosis by directly binding to MERTK and inhibiting its activity
Seung-Hyun Bae Jung-Hoon Kim Tae Hyun Park Kyeong Lee Byung Il Lee Hyonchol Jang 《Experimental & molecular medicine》2022,54(9):1450
Myeloid epithelial reproductive proto-oncogene tyrosine kinase (MERTK) plays an essential role in modulating cancer immune tolerance by regulating macrophage efferocytosis. Studies are underway to develop small-molecule chemicals that inhibit MERTK as cancer immunotherapeutic agents, but these efforts are in their early stages. This study identified BMS794833, whose primary targets are MET and VEGFR2, as a potent MERTK inhibitor and developed a real-time efferocytosis monitoring system. The X-ray cocrystal structure revealed that BMS794833 was in contact with the ATP-binding pocket and the allosteric back pocket, rendering MERTK inactive. Homogeneous time-resolved fluorescence kinetic and Western blotting analyses showed that BMS794833 competitively inhibited MERTK activity in vitro and inhibited the autophosphorylation of MERTK in macrophages. We developed a system to monitor MERTK-dependent efferocytosis in real time, and using this system, we confirmed that BMS794833 significantly inhibited the efferocytosis of differentiated macrophages. Finally, BMS794833 significantly inhibited efferocytosis in vivo in a mouse model. These data show that BMS794833 is a type II MERTK inhibitor that regulates macrophage efferocytosis. In addition, the real-time efferocytosis monitoring technology developed in this study has great potential for future applications.Subject terms: Biochemistry, Cell biology 相似文献