全文获取类型
收费全文 | 308篇 |
免费 | 15篇 |
国内免费 | 2篇 |
专业分类
化学 | 288篇 |
晶体学 | 1篇 |
数学 | 4篇 |
物理学 | 32篇 |
出版年
2023年 | 1篇 |
2022年 | 3篇 |
2021年 | 1篇 |
2020年 | 6篇 |
2019年 | 10篇 |
2018年 | 1篇 |
2017年 | 3篇 |
2016年 | 7篇 |
2015年 | 7篇 |
2014年 | 13篇 |
2013年 | 21篇 |
2012年 | 27篇 |
2011年 | 22篇 |
2010年 | 11篇 |
2009年 | 10篇 |
2008年 | 25篇 |
2007年 | 24篇 |
2006年 | 27篇 |
2005年 | 24篇 |
2004年 | 18篇 |
2003年 | 15篇 |
2002年 | 10篇 |
2001年 | 2篇 |
2000年 | 5篇 |
1999年 | 6篇 |
1998年 | 3篇 |
1997年 | 3篇 |
1995年 | 1篇 |
1994年 | 1篇 |
1993年 | 2篇 |
1991年 | 3篇 |
1984年 | 1篇 |
1982年 | 2篇 |
1981年 | 2篇 |
1977年 | 1篇 |
1976年 | 1篇 |
1975年 | 1篇 |
1973年 | 1篇 |
1972年 | 3篇 |
1971年 | 1篇 |
排序方式: 共有325条查询结果,搜索用时 827 毫秒
91.
A novel synthetic dopamine receptor bearing bidentate binding sites were prepared by covalent imprinting using a disulfide linkage which is cleaved and oxidized to a non-covalent sulfoxide recognition group. The used templates have dopamine-like structures connected to an allyl moiety via a disulfide and to a 4-vinylphenyl group via a cyclic boronic diester. After the polymerization, the ester bonds were hydrolyzed and the disulfide bond was reduced to remove the template moiety from the polymer matrix, followed by the oxidation to transform the thiol residues into sulfonic acid (post imprinted process). The imprinted polymer adsorbed dopamine selectively in aqueous solution with the two-point interaction, i.e. the formation of cyclic boronic diester and electrostatic interaction with the sulfonic acid residue. 相似文献
92.
Ryosuke Sakai Takafumi Yonekawa Issei Otsuka Ryohei Kakuchi Toshifumi Satoh Toyoji Kakuchi 《Journal of polymer science. Part A, Polymer chemistry》2010,48(5):1197-1206
Diacetylene monomers with respective lengths of the oxyethylene chains were cyclopolymerized with a rhodium catalyst to produce novel poly(phenylacetylene)s bearing a different cavity size of the chiral crown ether in the repeating units ( 2a – c ). In the circular dichroism spectra of the resulting polymers, characteristic Cotton effects were observed in the range from 350 to 500 nm corresponding to the absorption of the conjugated polymer backbone, indicating that the polymers possessed a helical structure with an excess single screw sense induced by the covalently bonded binaphthyl units. The host–guest complexation of 2a – c with achiral guests produced a chiroptical change based on the fluctuation in the main chain conformation. The behavior of the complexation‐induced chiroptical change was essentially dictated by the cavity size of the binaphthocrown ether units. Additionally, a chirality‐responsive helicity change was observed in the case of the complexation of 2a – c with chiral guests, which also depended on the crown ether size. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 1197–1206, 2010 相似文献
93.
Kassai H Satomi Y Fukada Y Takao T 《Rapid communications in mass spectrometry : RCM》2005,19(2):269-274
Protein isoprenylation, an important post-translational modification with a lipid, involves the selective attachment of two types of isoprenoids, farnesyl (C15) and geranylgeranyl (C20). The isoprenoid is linked via a thioether bond to the C-terminal cysteine residue of a variety of cellular proteins, including the heterotrimeric G protein gamma-subunits. One member of the G protein family, transducin (Talpha/Tbetagamma), plays a central role in visual transduction, and the structure-function relationship has been extensively studied with purified proteins, predominantly with bovine transducin that was shown to be farnesylated at the C-terminal cysteine residue of the gamma-subunit (Tgamma). We report here the structure of the C-terminal modification of mouse Tgamma, which has not yet been elucidated owing to the low amount of protein that can be isolated from the mouse retina. Electrospray ionization mass spectrometry (ESI-MS) of the high-performance liquid chromatography (HPLC)-purified Tgamma was in good agreement with the calculated mass of the farnesylated and methylated form of mouse Tgamma (Pro1-Cys70). A 'top-down' analysis of intact Tgamma using an ESI hybrid quadrupole time-of-flight (TOF) tandem mass spectrometer provided isoprenyl-specific ions that were observed to produce ions separated by 204 Da from the conventional (unmodified) precursor ion or the C-terminal sequence ions. Such characteristic fragmentation on an isoprenoid observed in top-down analysis could be useful in general for determining the type of isoprenylation as well as probing the site of modification in the protein sequence. 相似文献
94.
Synthetic polymers which can adsorb bisphenol A (BPA) and related compounds were prepared by a covalent molecular imprinting technique. BPA dimethacrylate, used as template molecule, was polymerized with a crosslinker, triethylene glycol dimethacrylate (TEGDMA) or trimethylol propane trimethacrylate (TRIM). After the polymerization treatment with dilute NaOH was used to cleave BPA from the polymers. For high recovery of BPA with low polymer matrix degradation, the hydrolysis conditions were determined to be treatment with 1.0 mol L–1 NaOH for 48 h. The binding sites generated by the hydrolysis were evaluated by determination of the retentivity of BPA, BPA analogues, and other endocrine disruptors. The polymers strongly adsorbed compounds with two hydroxyl groups at the 4,4-positions. Generally the TEGDMA-based polymers had stronger affinity than the TRIM-based polymers, although the TRIM-based polymer adsorbed steroidal hormones with two hydroxyl groups, for example 17-estradiol and 17-estradiol, more strongly than the TEGDMA-based polymer, meaning that the crosslinkers affected the properties of the binding sites and, depending upon the target molecules, suitable crosslinkers should be chosen in this system. 相似文献
95.
Mylene M UyShinji Ohta Mihoko YanaiEmi Ohta Toshifumi HirataSusumu Ikegami 《Tetrahedron》2003,59(6):731-736
Three new spirocyclic sesquiterpenes designated exiguamide (1), exicarbamate (2) and exigurin (3), together with (−)-10-epi-axisonitrile-3 (4), have been isolated from the marine sponge Geodia exigua. All four compounds possess the spiro[4.5]decene skeleton and their structures were determined on the basis of spectroscopic data. The structure of 1 was confirmed by X-ray crystallographic analysis and the absolute configuration was determined by applying the modified Mosher's method on its amine derivative. Exiguamide (1) inhibited cell fate specification during sea urchin embryogenesis at a minimum inhibitory concentration of 0.4 μM. 相似文献
96.
We report the synthesis of various thiophene/phenylene co‐oligomers with a total number of thiophene and benzene (phenylene) rings of 6 to 8. These compounds include a phenyl‐capped sexithiophene, a thienyl‐capped quaterphenylene, as well as block and alternating co‐oligomers. The synthesis is based on either the Suzuki coupling reaction or the direct dimerization coupling. The latter method produces symmetric molecules with an even total ring number. These reaction schemes enabled us to obtain the target compounds in high quality. Although the resulting materials are difficult to dissolve in organic solvents and therefore difficult to identify by usual 1H nmr spectroscopy, they have successfully been identified through Fourier‐transform ir spectroscopy. The specific group frequencies of ring‐stretching and out‐of‐plane deformation modes are characteristic of the substitution pattern of the individual thiophene and benzene rings. 相似文献
97.
Tomoko Imai Kohei Hayakawa Toshifumi Satoh Harumi Kaga Toyoji Kakuchi 《Journal of polymer science. Part A, Polymer chemistry》2002,40(20):3443-3448
Enantiomer‐selective polymerization of (RS)‐(phenoxymethyl)thiirane (RS‐ 1 ) was carried out with ZnEt2/L ‐α‐amino acid as an initiator system, and the effect of the initiator system on the enantiomer selectivity was examined with various amino acids. All polymerizations heterogeneously proceeded, and every initiating system was effective in producing optically active polymers. For the polymerization of RS‐ 1 with diethylzinc (ZnEt2)/L ‐leucine (1/1), the conversion was 43.7% in 12 days, and the number‐average molecular weight of the polymer was 18,000. The enantiomer selectivity was maximum when the molar ratio of the two components in the ZnEt2/L ‐α‐amino acid system was 1:1. When the ZnEt2/L ‐leucine (1/1) system was used in the polymerization, the best result was obtained with an enantiomer‐selectivity value of 5.36. During the polymerization, the S enantiomer was preferentially consumed, and the isotactic‐rich polymer was enriched in the S configurational units produced. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 3443–3448, 2002 相似文献
98.
Polylactide (PLA)-grafted dextran (Dex-graft-PLA) of various contents of sugar units was synthesized by anionic polymerization of L-lactide (L-LA) using the alkoxide of partially trimethylsilylated dextran (TMSDex) and subsequently removing the trimethylsilyl (TMS) groups. The copolymer showed different solubility from L-LA homopolymer with increasing the content of sugar units. We prepared bovine serum albumin (BSA)-loaded microspheres (MS)s according to a water-in-oil-in-water emulsion-solvent evaporation/extraction method using methylene chloride/DMSO as an organic cosolvent. MSs prepared from Dex-graft-PLA [MS(Dex-graft-PLA)s] exhibited higher loading efficiency of BSA than MSs prepared from PLLA [MS(PLLA)s]. The in vitro release rate of BSA from MS(Dex-graft-PLA) was faster than that from MS(PLLA). BSA released from MS(Dex-graft-PLA) maintained the secondary structure of native BSA to a great extent, compared with BSA released from MS(PLLA). 相似文献
99.
Toshifumi Takeuchi Yuji Minato Masayoshi Takase Hideyuki Shinmori 《Tetrahedron letters》2005,46(52):9025-9027
Molecular recognition materials bearing halogen bonding-based binding sites were synthesized by a non-covalent imprinting technique using a 2,3,5,6-tetrafluoro-4-iodostyrene (TFIS) as the functional monomer. The binding sites were generated by co-polymerizing TFIS, styrene and divinylbenzene in the presence of the template molecule (4-dimethylaminopyridine—DMAP). The imprinted polymer preferentially adsorbed aminopyridine derivatives, suggesting that halogen bonding may play a role in the selective recognition of analytes by the synthesized synthetic receptor. 相似文献
100.
Mamoru Yasui Toshifumi Shiroya Keiji Fujimoto Haruma Kawaguchi 《Colloids and surfaces. B, Biointerfaces》1997,8(6):267-319
Poly(N-isopropylacrylamide)s (PNIPAMs) carboxylated at one chain end or both ends were prepared by polymerization using 4,4-azobis(N,N,-cyanopentanoic acid) (V-501) as an initiator and β-mercaptopropionic acid (MPA) as a chain transfer reagent. One end group of PNIPAM carboxylated at both ends was conjugated with latex particles, and another with trypsin using carbodiimide. Differential scanning calorimetry (DSC) revealed that PNIPAM on the particles exhibited a drastic phase transition, and that the transition temperature was largely elevated when the enzyme was immobilized at the chain end. Therefore, PNIPAM on the particles showed two phase transitions because of the coexistence of the enzyme-conjugated and non-conjugated PNIPAMs. The activity of trypsin immobilized on the particles with the PNIPAM spacer showed significant temperature dependence. The apparent relative activity increased above the transition temperature of non enzyme-conjugated PNIPAM on the particles. One of the reasons for this is that the diffusion of the substrate changed discontinuously around the transition temperature. Therefore, the temperature dependence of the enzymatic activity was significantly affected by the molecular size of the substrates. The enzymatic activity was also influenced by the surface density of trypsin and PNIPAM on the particle, and the molecular weight of the PNIPAM spacer. 相似文献