全文获取类型
收费全文 | 343篇 |
免费 | 11篇 |
国内免费 | 1篇 |
专业分类
化学 | 238篇 |
晶体学 | 3篇 |
力学 | 2篇 |
数学 | 55篇 |
物理学 | 57篇 |
出版年
2023年 | 4篇 |
2021年 | 2篇 |
2020年 | 10篇 |
2019年 | 4篇 |
2018年 | 2篇 |
2016年 | 7篇 |
2015年 | 14篇 |
2014年 | 9篇 |
2013年 | 15篇 |
2012年 | 24篇 |
2011年 | 18篇 |
2010年 | 5篇 |
2009年 | 7篇 |
2008年 | 12篇 |
2007年 | 23篇 |
2006年 | 14篇 |
2005年 | 19篇 |
2004年 | 23篇 |
2003年 | 22篇 |
2002年 | 19篇 |
2001年 | 5篇 |
2000年 | 2篇 |
1999年 | 3篇 |
1998年 | 1篇 |
1997年 | 10篇 |
1996年 | 7篇 |
1995年 | 7篇 |
1994年 | 3篇 |
1993年 | 5篇 |
1992年 | 3篇 |
1991年 | 2篇 |
1990年 | 3篇 |
1989年 | 4篇 |
1988年 | 3篇 |
1987年 | 1篇 |
1986年 | 1篇 |
1985年 | 3篇 |
1984年 | 5篇 |
1983年 | 3篇 |
1982年 | 2篇 |
1981年 | 8篇 |
1980年 | 5篇 |
1979年 | 6篇 |
1978年 | 2篇 |
1977年 | 1篇 |
1974年 | 1篇 |
1973年 | 1篇 |
1970年 | 1篇 |
1969年 | 1篇 |
1968年 | 2篇 |
排序方式: 共有355条查询结果,搜索用时 15 毫秒
321.
K Morimoto S Fukanoki K Morisaka S H Hyon Y Ikada 《Chemical & pharmaceutical bulletin》1989,37(9):2491-2495
Preparations of beta-blockers, propranolol-HCl and atenolol, in poly(vinyl alcohol) (PVA) hydrogel were designed for the therapeutic treatment of hypertension by transrectal delivery. In vitro release characteristics and plasma drug concentration profiles after rectal administration in rats and dogs were examined. The PVA hydrogels containing beta-blockers were prepared by a low-temperature crystallization method. The release of beta-blockers from hydrogel preparations was consistent with Fickian diffusion (Higuchi model); the drug release versus the square root of release time profile gave a straight line over 60% of the total release process. The release of beta-blockers from hydrogel preparations increased at higher concentrations of PVA in the hydrogel preparations and was not affected by the pH of hydrogel preparations. Plasma concentrations of beta-blockers after rectal administration of hydrogels were higher than those after administration of suppositories (Witepsol H-15) in rats and dogs. The drug plasma concentrations increased at higher concentrations of PVA in hydrogel preparations. In the case of propranolol, which is a hepatic high-clearance drug, area under the blood concentration curve, 0-8 h after rectal administration of a hydrogel preparation (20% w/w PVA, pH 7.0) was 2.16 times and 5.26 times higher than those obtained with Witepsol H-15 suppository and oral administration, respectively. Rectal administration with PVA hydrogels is a favorable route for a hepatic high-clearance drug such as propranolol. 相似文献
322.
Onouchi H Miyagawa T Furuko A Maeda K Yashima E 《Journal of the American Chemical Society》2005,127(9):2960-2965
A poly(phenylacetylene) bearing a phosphonic acid monoethyl ester as the pendant forms a one-handed helical structure induced by an optically active amine, and this helicity can be "memorized"after the amine is replaced by achiral diamines. The helicity memory lasts for an extremely long time but spontaneously disappears after the achiral diamines are removed by a stronger acid, indicating the dynamic nature of the helicity memory. Here we report that such a dynamic memory could be "stored" after the pendant was converted to its methyl ester with diazomethane, resulting in the generation of a phosphorus stereogenic center with optical activity. The esterification enantioselectively proceeded through chirality transfer from the induced helical conformation or the helicity memory of the polyacetylene backbone. Although the enantioselectivity was low, the pendant chirality was significantly amplified in the polymer backbone at low temperatures, resulting in higher optical activity as an excess single-handed helix than that expected from the enantiomeric excess of the pendants. 相似文献
323.
Ishikawa M Maeda K Mitsutsuji Y Yashima E 《Journal of the American Chemical Society》2004,126(3):732-733
We have found an unprecedented memory of macromolecular helicity induced in an achiral sodium salt of poly(4-carboxyphenyl isocyanide) (poly-1-Na). Poly-1-Na folds into a one-handed helix through configurational isomerization around the C=N backbones by interactions with optically active amines in water. The helix remains when the optically active amines are completely removed, and further modifications of the side group to carboxy and esters can be possible without loss of the macromolecular helicity memory. 相似文献
324.
Katsuhiro Sumi Masaoki Furue Shun-Ichi Nozakura 《Journal of polymer science. Part A, Polymer chemistry》1985,23(12):3059-3067
Photochemical properties of Ru(bpy)2(poly-4-methyl-4′-vinyl-2,2′-bipyridine)Cl2 ( 2 ) were studied and compared with that of Ru(bpy)3Cl2. Continuous irradiation of a solution, which contains polymer 2 as a photosensitizer, methylviologen (MV2+) or 4,4′-bipyridinium-1,1′-bis(trimethylenesulfonate) (SPV) as an electron acceptor and triethanolamine (TEOA) as a sacrificial donor, resulted in the formation of viologen radical ion (MV+ or SPV?). The rate of formation of MV+ or SPV? for the polymer 2 system was smaller than that for the Ru(bpy)3 Cl2 systems. The reason for this fact was kinetically analyzed by quenching experiments of excited Ru(II) complexes by MV2+ or SPV, the photosensitized reactions of the TEOA–Ru(II) complex–MV2+ or -SPV systems, and the dye laser photolysis of the Ru(II) complex–MV2+ or -SPV systems. 相似文献
325.
Kimura H Tanigawa T Morisaka H Ikegami T Hosoya K Ishizuka N Minakuchi H Nakanishi K Ueda M Cabrera K Tanaka N 《Journal of separation science》2004,27(10-11):897-904
Separation of peptides by fast and simple two-dimensional (2D)-HPLC was studied using a monolithic silica column as a second-dimension (2nd-D) column. Every fraction from the first column, 5 cm long (2.1 mm ID) packed with polymer-based cation exchange beads, was subjected to separation in the 2nd-D using an octadecylsilylated (C18) monolithic sillica column (4.6 mm ID, 2.5 cm). A capillary-type monolithic silica C18column (0.1 mm ID, 10 cm) was also employed as a 2nd-D column with split flow/injection. Effluentof the first dimension (1st-D) was directly loaded into an injector loop of 2nd-D HPLC. UV and MS detection were successfully carried out at high linear velocity of mobile phase at 2nd-D using flow splitting for the 4.6 mm ID 2nd-D column, or with directconnection of the capillary column to the MS interface. Two-minute fractionation inthe 1st-D, 118-second loading, and 2-second injection by the 2nd-D injector, allowed one minute for gradient separation in the 2nd-D, resulting in a maximum peak capacity of about 700 within 40 min. The use of a capillary column in solvent consumption and better MS detectability compared to a larger-sized column. This kind of fast and simple 2D-HPLC utilizing monolithic silica columns will be useful for the separation of complex mixtures in a short time. 相似文献
326.
Nishimura T Tsuchiya K Ohsawa S Maeda K Yashima E Nakamura Y Nishimura J 《Journal of the American Chemical Society》2004,126(37):11711-11717
Three chiral N-methylfulleropyrrolidine bisadducts were prepared, isolated, and completely resolved into each enantiomer using a chiral HPLC column, which were then converted to the corresponding optically active, cationic C(60)-bisadducts to investigate if they could act as a macromolecular helicity inducer in a poly(phenylacetylene) bearing an anionic monoethyl phosphonate pendant (poly-1) in aqueous solution. Upon complexation with the chiral C(60)-bisadducts, only the trans-3 bisadduct exhibited the characteristic induced circular dichroism (ICD) in the UV-visible region of the polymer backbone in dimethyl sulfoxide-water mixtures due to the predominantly one-handed helix formation of poly-1, while the trans-2 and cis-3 bisadducts induced almost no apparent CD in the same region. These results indicate that the helicity induction on poly-1 is highly sensitive to the structure and geometry of the cationic C(60)-bisadducts with a different distance between the separated charges. 相似文献
327.
Katsuhiro Yamamoto Youhei Miwa Hiroyuki Tanaka Masato Sakaguchi Shigetaka Shimada 《Journal of polymer science. Part A, Polymer chemistry》2002,40(20):3350-3359
Nickel‐mediated atom transfer radical polymerization (ATRP) and iron‐mediated reverse ATRP were applied to the living radical graft polymerization of methyl methacrylate onto solid high‐density polyethylene (HDPE) films modified with 2,2,2‐tribromoethanol and benzophenone, respectively. The number‐average molecular weight (Mn) of the free poly(methyl methacrylate) (PMMA) produced simultaneously during grafting grew with the monomer conversion. The weight‐average molecular weight/number‐average molecular weight ratio (Mw/Mn) was small (<1.4), indicating a controlled polymerization. The grafting ratio showed a linear relation with Mn of the free PMMA for both reaction systems. With the same characteristics assumed for both free and graft PMMA, the grafting was controlled, and the increase in grafting ratio was ascribed to the growing chain length of the graft PMMA. In fact, Mn and Mw/Mn of the grafted PMMA chains cleaved from the polyethylene substrate were only slightly larger than those of the free PMMA chains, and this was confirmed in the system of nickel‐mediated ATRP. An appropriate period of UV preirradiation controlled the amount of initiation groups introduced to the HDPE film modified with benzophenone. The grafting ratio increased linearly with the preirradiation time. The graft polymerizations for both reaction systems proceeded in a controlled fashion. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 3350–3359, 2002 相似文献
328.
Optically active, cis-transoid poly(phenylacetylene) derivatives bearing a poly(gamma-benzyl-L-glutamate) [poly(PBGAm)] or poly(L-glutamic acid) [poly(PGAm)] chain as the pendant were prepared by polymerisation of the corresponding macromonomer with a rhodium catalyst followed by hydrolysis of the pendant ester groups. Their conformational changes in solution, induced by a helix-coil transition of the pendant polypeptides, were investigated using circular dichroism (CD) and absorption spectroscopies. A series of macromonomers with a different peptide chain lengths was synthesised by the polymerisation of the N-carboxyanhydride of gamma-benzyl-L-glutamate with a phenylacetylene bearing an alanine residue as the initiator. The obtained macromonomers (PBGAm) were further polymerised with a rhodium catalyst in N,N-dimethylformamide (DMF) to yield novel poly(phenylacetylene)s [poly(PBGAm)] with a poly(gamma-benzyl-L-glutamate) pendant. The poly(PBGAm) exhibited an induced circular dichroism (ICD) in the UV/Vis region of the polymer backbone in dimethyl sulfoxide (DMSO), probably due to the prevailing one-handed helix formation. The Cotton effect signs of a DMSO solution of the poly(PBGAm) were inverted and accompanied by a visible colour change in the presence of an increasing amount of chloroform or DMF containing lithium chloride. The results suggest that poly(PBGAm) may undergo a conformational change such as a helix-helix transition with a different helical pitch responding to a change in the alpha-helix content of the poly(gamma-benzyl-L-glutamate) pendant. Moreover, a water-soluble poly(PGAm) also showed a similar, but dramatic change in its helical conformation with a visible colour change stimulated by a helix-coil transition of the pendant poly(L-glutamic acid) chains by changing the pH in water. 相似文献
329.
Katsuhiro Mizoguchi 《先进技术聚合物》1995,6(1):15-24
This paper describes reviews about the characterization of optical and electronic (opto-electronic) organic materials including polymers, and their applications for advanced key devices used for computers and communications technologies. On the basis of the author's recent investigations, discussions are made on organic electroluminescent thin film materials for emissive display devices, polymer-dispersed liquid crystal materials for passive display devices, organic photo-conductive materials for electrophotographic printer devices, and highly electroconductive polymers for solid tantalum capacitors. Finally, technical issues and development prospects for the opto-electronic organic materials in the 21st century are suggested. 相似文献
330.
Hagiwara H Kobayashi K Miya S Hoshi T Suzuki T Ando M Okamoto T Kobayashi M Yamamoto I Ohtsubo S Kato M Uda H 《The Journal of organic chemistry》2002,67(17):5969-5976
The phytotoxins solanapyrones D (1) and E (2) have been synthesized from the decalone prepared by the domino Michael reaction of the kinetic enolate of optically pure acetylcyclohexene with methyl crotonate. The decalone was transformed into a solanapyrone core by equilibration into thermodynamically stable trans-decalone (11), dehydroxylation, and dehydration. Condensation of a methyl acetoacetate equivalent followed by cyclization installed a pyrone moiety. Introduction of a formyl or hydroxymethyl unit into the pyrone ring via Pummerer related reactions furnished solanapyrones D (1) and E (2). 相似文献