全文获取类型
收费全文 | 436篇 |
免费 | 12篇 |
国内免费 | 2篇 |
专业分类
化学 | 298篇 |
晶体学 | 8篇 |
力学 | 2篇 |
综合类 | 1篇 |
数学 | 27篇 |
物理学 | 114篇 |
出版年
2023年 | 3篇 |
2022年 | 3篇 |
2021年 | 10篇 |
2020年 | 12篇 |
2019年 | 11篇 |
2018年 | 6篇 |
2017年 | 7篇 |
2016年 | 4篇 |
2015年 | 10篇 |
2014年 | 8篇 |
2013年 | 27篇 |
2012年 | 17篇 |
2011年 | 18篇 |
2010年 | 15篇 |
2009年 | 16篇 |
2008年 | 18篇 |
2007年 | 36篇 |
2006年 | 36篇 |
2005年 | 33篇 |
2004年 | 12篇 |
2003年 | 16篇 |
2002年 | 15篇 |
2001年 | 11篇 |
2000年 | 7篇 |
1999年 | 7篇 |
1997年 | 4篇 |
1996年 | 5篇 |
1995年 | 5篇 |
1994年 | 5篇 |
1993年 | 5篇 |
1992年 | 6篇 |
1991年 | 2篇 |
1988年 | 2篇 |
1986年 | 5篇 |
1985年 | 8篇 |
1984年 | 5篇 |
1983年 | 2篇 |
1982年 | 7篇 |
1981年 | 6篇 |
1980年 | 4篇 |
1979年 | 4篇 |
1978年 | 1篇 |
1977年 | 5篇 |
1976年 | 2篇 |
1975年 | 1篇 |
1974年 | 1篇 |
1973年 | 2篇 |
1968年 | 1篇 |
1967年 | 1篇 |
1966年 | 1篇 |
排序方式: 共有450条查询结果,搜索用时 609 毫秒
1.
Toshiki Kono Toshikazo Sakaguchi Yanming Hu Masashi Shiotsuki Fumio Sanda Toshio Masuda 《Journal of polymer science. Part A, Polymer chemistry》2006,44(20):5943-5953
Phenylacetylene (PA) derivatives having two polar groups (ester, 2a – d ; amide, 4) or one cyclic polar group (imide, 5a – c ) were polymerized using (nbd)Rh+[(η6‐C6H5)B?(C6H5)3] catalyst to afford high molecular weight polymers (~1 × 106 – 4 × 106). The hydrolysis of ester‐containing poly(PA), poly( 2a) , provided poly(3,4‐dicarboxyPA) [poly ( 3 )], which could not be obtained directly by the polymerization of the corresponding monomer. The solubility properties of the present polymers were different from those of poly(PA) having no polar group; that is, poly( 2a )–poly( 2d ) dissolved in ethyl acetate and poly( 4 ) dissolved in N,N‐dimethylformamide, while poly(PA) was insoluble in such solvents. Ester‐group‐containing polymers [poly( 2a )–poly( 2d )] afforded free‐standing membranes by casting from THF solutions. The membrane of poly( 2a ) showed high carbon dioxide permselectivity against nitrogen (PCO2/PN2 = 62). © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 5943–5953, 2006 相似文献
2.
Ramesh P Okazaki T Taniguchi R Kimura J Sugai T Sato K Ozeki Y Shinohara H 《The journal of physical chemistry. B》2005,109(3):1141-1147
Double-wall carbon nanotubes (DWNTs) have been selectively synthesized over Fe/Co loaded mesoporous silica by catalytic chemical vapor deposition of alcohol. Several silica materials with desired pore diameter and morphology have been investigated for the DWNT growth. The diameter distribution and selectivity of the DWNT are found to depend on the reaction temperature, pore size, and thermal stability of the support material. A high-yield synthesis of DWNTs has been achieved at 900 degrees C over high-temperature stable mesoporous silica. The outer diameter of DWNTs is found to be in the range of 1.5-5.4 nm with a "d" spacing of 0.38 +/- 0.02 nm between inner and outer layers, which is much larger than those of multiwall carbon nanotubes. 相似文献
3.
The 1,4-elimination reaction of 1-amino-4-methoxy-(2Z)-alkenes is shown to proceed with high (1E,3E)-stereoselectivities to afford the corresponding 4-substituted-1-amino-1,3-dienes in good yield. The scope and stereochemical features of the synthetic method are described. 相似文献
4.
Angiotensin I‐converting enzyme (ACE) inhibitory peptide was isolated from the hen ovotransferrin hydrolysate using chymotryptic hydrolysis by two steps of reverse‐phase high‐performance liquid chromatography. The amino sequence of this novel peptide was identified as Lys‐Val‐Arg‐Glu‐Gly‐Thr‐Thr‐Tyr that inhibited ACE activity in vitro in a concentration‐dependent manner with an effective concentration (IC50) of 102.8 μM. Also, this inhibition was identified as noncompetitive using the Lineweaver‐Burk plot. Moreover, the antihypertensive action of this novel peptide was investigated by an intravenous injection into spontaneously hypertensive rats (SHR). A dose‐dependent reduction of systolic blood pressure by this peptide was observed after 40 min of treatment and it decreased the blood pressure markedly at the maximal dose (1 nmol/mL/kg). The maximal blood pressure lowering activity of this peptide was calculated as 163% of captopril (10 pmol/mL/kg) that was used as positive control. In conclusion, the obtained data suggests that Lys‐Val‐Arg‐Glu‐Gly‐Thr‐Thr‐Tyr has an ability to inhibit ACE activity and decrease the systolic blood pressure in hypertensive animals. 相似文献
5.
6.
The densities of aqueous solutions of the phosphonium halides, Bu
4-n
Ph
n
PX(n=0–4), some of which were synthesized from the phosphines, were measured at 15, 25 and 35°C. Partial molal volumes at infinite dilution,
, and B
v
coefficients for the apparent molal volumes were determined at each temperature. For the first four cations
varies little with n. For all salts B
v
are negative but become less negative with increasing n. The temperature dependence of B
v
is positive for butyl-rich salts (n<2) but negative for phenyl-rich salts (n>1). Also it appears that
is relatively large for phenyl-rich cations in comparison with that for butyl-rich cations. 相似文献
7.
Kiyokawa T Kanaori K Tajima K Kawaguchi M Mizuno T Oku J Tanaka T 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(14):3548-3554
The alpha-helical coiled coils have a representative amino acid sequence of (abcdefg)(n) heptad repeats. We previously reported that two peptides named IZ-2A and IZ-2W formed an (IZ-2A)(2)/IZ-2W heterotrimer with an Ala-Ala-Trp interaction in the hydrophobic core. In this paper, we describe the selective formation of AAB- and ABC-type heterotrimers. To increase the selectivity of the AAB-type heterotrimeric formation, Lys residues at the f position were mutated to either an Ala or a Gln residue to form IZ-2A(fA) or IZ-2W(fQ). Separately, both IZ-2A(fA) and IZ-2W(fQ) have a random structure at pH 7 and 20 degrees C. However, together IZ-2A(fA) and IZ-2W(fQ) form a 2:1 complex with a thermal transition midpoint (Tm) of 48 degrees C. This procedure was applied to prepare the ABC-type heterotrimer, in which two sets of Ala-Ala-Trp interactions were designed in the hydrophobic core. Interhelical interaction between the e and g positions and the alpha-helical propensity of the amino acid at the f position were also considered in the design. The resultant three peptides selectively formed the ABC-type heterotrimer with a Tm of 51 degrees C. Other peptide combinations had random coil properties. 相似文献
8.
Shuichi Naito Shigeru Aida Toshiki Kasahara Toshihiro Miyao 《Research on Chemical Intermediates》2006,32(3-4):279-290
In situ infrared spectroscopy was applied to elucidate the reaction mechanism of CO hydrogenation over Pd/CeO2. Instead of direct dissociation of CO, a new reaction pathway is proposed for methane formation, involving geminal dicarbonyl intermediates and (HCO)2(a) intermediates, which may be located on the surface of Pd covered with thin layers of reduced ceria (SMSI effect). Transformation of methane formation sites into methanol formation ones by the oxidation with water vapor formed during the CO?H2 reaction is proposed, which may be located on the Pd (111) planes adjacent to ceria support. 相似文献
9.
We synthesized Leu‐Arg‐Pro‐Val‐Ala‐Ala‐Glu, the peptide contained in lactoferrin (Lf), to identify the angiotensin converting enzyme (ACE) inhibition. In an attempt to know the structure‐activity relationship of this peptide, we replaced Pro (the third amino acid residues from N‐terminal) or Val (the fourth amino acid residues from N‐terminal) with Ala (neutral amino acid), Glu (acidic amino acid) or Lys (basic amino acid) to produce six peptides. From the in vitro ACE inhibition (IC50) of these synthesized peptides, the original peptide (Leu‐Arg‐Pro‐Val‐Ala‐Ala‐Glu) showed higher ACE inhibition than the replaced six peptides. Thus, replacement of Pro at the third amino acid residues or Val at the fourth position with Ala, Glu or Lys revealed the ACE inhibition to be lower than the original form of Leu‐Arg‐Pro‐Val‐Ala‐Ala‐Glu. Otherwise, we added one peptide at the C‐terminal of Leu‐Arg‐Pro‐Val‐Ala‐Ala‐Glu and found both products with an addition of Val (Leu‐Arg‐Pro‐Val‐Ala‐Ala‐Glu‐Val) or Ile (Leu‐Arg‐Pro‐Val‐Ala‐Ala‐Glu‐Ile) showing a lower ACE inhibition than the original one. The ACE inhibitions produced by both replaced peptides were without significance. Also, deletion of the last peptide at the C‐terminal (Leu‐Arg‐Pro‐Val‐Ala‐Ala) failed to produce a marked change of ACE inhibition as compared to the original one. These results suggest that Pro and Val are essential in the peptide for inhibition of ACE activity. 相似文献
10.
Sumio Kato Masataka Ogasawara Mikio Sugai Shinichi Nakata 《Catalysis Surveys from Asia》2004,8(1):27-34
Studies on the role of oxygen vacancy in structural change of nonstoichiometric perovskites and a property of oxygen-deficient perovskite-related K2NiF4 compounds are reviewed.The structural changes on which the authors focused are cation ordering and lattice distortion. The relationship between the distortion and oxygen vacancy was investigated by comparing the structures of Sr2(Sr1-xMx)TaO6-d (M = Ca2+ and Nd3+) solid solutions. It was found that distortion of a perovskite-type lattice decreased with an increasing amount of oxygen vacancies. In order to investigate the relationship between the cation ordering on octahedral sites and oxygen vacancy, structures of stoichiometric Sr2-xLaxCo1-yTa1+yO6 and oxygen-deficient Sr2-xLaxMg1-yTa1+yO6-d solid solutions were compared. The authors' work reveals that the cation ordering affects the amount of oxygen vacancies in addition to cation charge and size. 相似文献