全文获取类型
收费全文 | 446篇 |
免费 | 26篇 |
国内免费 | 68篇 |
专业分类
化学 | 497篇 |
力学 | 1篇 |
综合类 | 3篇 |
数学 | 1篇 |
物理学 | 38篇 |
出版年
2021年 | 1篇 |
2020年 | 5篇 |
2019年 | 8篇 |
2018年 | 6篇 |
2017年 | 13篇 |
2016年 | 15篇 |
2015年 | 14篇 |
2014年 | 14篇 |
2013年 | 45篇 |
2012年 | 20篇 |
2011年 | 22篇 |
2010年 | 24篇 |
2009年 | 13篇 |
2008年 | 34篇 |
2007年 | 23篇 |
2006年 | 26篇 |
2005年 | 27篇 |
2004年 | 22篇 |
2003年 | 27篇 |
2002年 | 34篇 |
2001年 | 29篇 |
2000年 | 28篇 |
1999年 | 15篇 |
1998年 | 19篇 |
1997年 | 5篇 |
1996年 | 6篇 |
1995年 | 12篇 |
1994年 | 4篇 |
1993年 | 9篇 |
1992年 | 5篇 |
1991年 | 4篇 |
1990年 | 1篇 |
1989年 | 1篇 |
1984年 | 1篇 |
1983年 | 1篇 |
1981年 | 1篇 |
1980年 | 3篇 |
1978年 | 2篇 |
1977年 | 1篇 |
排序方式: 共有540条查询结果,搜索用时 15 毫秒
61.
A series of new N‐benzoyl‐N‐tert‐butyl‐N′‐(β‐triphenylgermyl)propionylhydrazines were synthesized by the condensation reaction of β‐triphenylgermyl propanoic acid with N‐benzoyl‐N‐tert‐butylhydrazines in good yields by using N,N′‐dicyclohexylcorbodiimide as dehydrating agent. These title compounds were evaluated for molting hormone mimicking activity. The results of bioassay showed that the compounds exhibit moderate larvicidal activity, and toxicity assays indicated that the title compounds can induce a premature, abnormal and lethal larval molt. We found that the title compounds possess potential anticancer activities in vitro. Copyright © 2002 John Wiley & Sons, Ltd. 相似文献
62.
Cristian Grigoras Virgil Percec 《Journal of polymer science. Part A, Polymer chemistry》2005,43(2):319-330
The metal‐catalyzed living radical polymerization of methyl methacrylate, n‐butyl acrylate, and styrene, initiated with p‐toluenesulfonyl bromide and phenoxybenzene‐4,4′‐disulfonyl bromide and catalyzed with CuBr/2,2′‐bipyridine (bpy) and various self‐regulated Cu‐based catalytic systems such as Cu2O/bpy, Cu2S/bpy, Cu2Se/bpy, and Cu2Te/bpy, is reported. Similarities and differences between the arenesulfonyl chloride and arenesulfonyl bromide initiators are discussed. The arenesulfonyl bromide initiators require reduced reaction times to produce polymers in high conversions under milder reaction conditions than the corresponding arenesulfonyl chloride initiators. At the same time, they exhibit 100% initiator efficiency and generate polymers with narrow molecular weight distributions and functional chain ends. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 319–330, 2005 相似文献
63.
Hélène Pellissier Author Vitae 《Tetrahedron》2007,63(16):3235-3285
64.
Andreas Muehlebach Franois Rime 《Journal of polymer science. Part A, Polymer chemistry》2003,41(21):3425-3439
Poly(n‐butyl acrylate) macromonomers with predetermined molecular weights (1300 < number‐average molecular weight < 23,000) and low polydispersity indices (<1.2) were synthesized from bromine‐terminated atom transfer radical polymerization polymers via end‐group substitution with acrylic acid and methacrylic acid. These macromonomers, having a high degree of end‐group functionalization (>90%), were radically homopolymerized to obtain comb polymers. A high macromonomer concentration, combined with a low radical flux, was needed to obtain a high conversion of the macromonomers and a reasonable degree of polymerization. By the traditional radical copolymerization of the hydrophobic macromonomers with the hydrophilic monomer N,N‐dimethylaminoethyl methacrylate (DMAEMA), amphiphilic comb copolymers were obtained. The conversions of the macromonomers and comonomer were almost quantitative under optimized reaction conditions. The molecular weights were high (number‐average molecular weight ≈70,000), and the molecular weight distribution was broad (polydispersity index ≈ 3.5). Kinetic measurements showed simultaneous decreases in the macromonomer and DMAEMA concentrations, indicating a relatively homogeneous composition of the comb copolymers over the whole molecular weight range. This was supported by preparative size exclusion chromatography. The copolymerization of poly(n‐butyl acrylate) macromonomers with other hydrophilic monomers such as acrylic acid or N,N‐dimethylacrylamide gave comb copolymers with multimodal molecular weight distributions in size exclusion chromatography and extremely high apparent molecular weights. Dynamic light scattering showed a heterogeneous composition consisting of small (6–9 nm) and large (23–143 nm) particles, probably micelles or other type of aggregates. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3425–3439, 2003 相似文献
65.
66.
Tadashi Narita Hiroshi Hamana Fumiaki Sekiya Yasuyuki Nojima 《Journal of polymer science. Part A, Polymer chemistry》2007,45(5):908-910
To report a new polymerization reaction phenomenon, this article examines the polymerization of butyl vinyl ether and N‐vinylcarbazole in the presence of 2‐benzoxypentafluoropropene [CF2?C(CF3)OCOC6H5 or BPFP]. The homopolymer of butyl vinyl ether was produced in the presence of a catalytic amount of BPFP in high yields. N‐Vinylcarbazole, which is a monomer well‐known for producing its homopolymer under cationic polymerization conditions, also yielded its homopolymer in the presence of BPFP. It was concluded that some cationic species would be yielded by the addition of BPFP. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 908–910, 2007. 相似文献
67.
Poly (methyl methacrylate/butyl acrylate) [P(MMA/BA)] copolymers (M η~2×105) with different mass percentages of PMMA (100/0, 90/10, 81/19, and 75/25), were synthesized by the method of solution polymerization. In addition to the normal α and ρ peak, a third τ peak is observed in thermally stimulated depolarization current (TSDC) spectra of the copolymers in the high temperature region. The α peak‐corresponds to the glass transition, the ρ peak originates from the detrapping of trapped carriers in the bulk amorphous structure related with flexible side groups, and the τ peak can be attributed to the charge detrapping related to the liquid–liquid transition of the copolymers. The three peaks all move to lower temperature with an increase of the BA component, indicating that the flexible side groups of butyl acrylate not only have an effect of plasticization on the glass transition and liquid–liquid transition, but also make the trap depth shallower and the detrapping process easier for the ρ and τ peaks. The experimental results confirm that TSDC analysis is very sensitive for investigating the liquid–liquid transition of polymers. The liquid–liquid transition temperature (T LL) of the copolymers follows a type of the Fox equation. Fitting the results gives a T LL of 102°C for polybutyl acrylate. 相似文献
68.
Chunxia Zhao Zhe Sun Bailing Liu Gang Peng 《Journal of Macromolecular Science: Physics》2013,52(10):1453-1464
Gemin-surfactant modified montmorillonite (G-MMT) was successfully prepared by an ion exchange reaction and characterized via Fourier-transform infrared spectroscopy (FTIR) and X-ray diffraction (XRD). The P(BA-VAc)/G-MMT emulsion was prepared via an in-situ polymerization method using potassium persulfate (K2S2O8, KPS) as an initiator. Ammonium polyphosphate (APP) was introduced for obtaining P(BA-VAc)/APP/G-MMT flame-retardant latex with a constant total content of 15 wt% of APP and G-MMT in P(BA-VAc). The flame retardancy and thermal behavior of the latex films were investigated by limiting oxygen index (LOI), vertical burning test (UL-94) and thermal gravimetric analysis (TG/DTA). Compared with the P(BA-VAc)/APP composite, the LOI value of P(BA-VAc)/APP/G-MMT containing 0.5 wt% G-MMT at the same total additive loading increased to 29.1 from 20.0 and its UL-94 increased from no rating to V-0. Thermal gravimetric (TG) data showed that the amount of residues increased significantly with the loading of G-MMT. In addition, the LOI values increased with the increase in char residues. The morphology and microstructure of the residues generated during LOI testing were investigated by scanning electron microscopy (SEM). The outer surfaces of P(BA-VAc)/APP/G-MMT charred layers were more continuous and compact than those of P(BA-VAc)/APP. 相似文献
69.
Sandrine Duluard Joseph Grondin Jean‐Luc Bruneel Guy Campet Marie‐Hlne Delville Jean‐Claude Lassgues 《Journal of Raman spectroscopy : JRS》2008,39(9):1189-1194
The Raman and Infrared (IR) spectra of poly(methyl methacrylate) (PMMA) membranes plasticized by ionic liquids of the (1 − x)[1‐butyl‐3‐methylimidazolium bis(trifluoromethanesulfonyl)imide (BMITFSI)],xLiTFSI type, where BMI+ is the 1‐butyl‐3‐methylimidazolium cation and TFSI− the bis(trifluoromethanesulfonyl)imide anion, are analyzed for a lithium bis(trifluoromethane sulfone)imide (LiTFSI) mole fraction x = 0.23 and PMMA contents from 0 to 50 wt%. The lithium is found to have an average coordination of about three CO groups and less than one TFSI− anion. It plays the role of a cross‐linker between the ester groups of PMMA and the nonvolatile ionic liquid. Addition of PMMA to the (1 − x)(BMITFSI),xLiTFSI ionic liquid lowers the conductivity but might improve the lithium transference number by transforming the [Li(TFSI)2]− anionic clusters present in the pure ionic liquid into a mixed coordination by ester groups and TFSI− anions. Copyright © 2008 John Wiley & Sons, Ltd. 相似文献
70.
Simultaneous measurement of methyl tert‐butyl ether and tert‐butyl alcohol in human serum by headspace solid‐phase microextraction gas chromatography–mass spectrometry 下载免费PDF全文
Rui Zhang Yong Mei Yanru Liu Hao Dai Hongfang Xia Xin Zhang Yukang Wu Yingying Gu Xiaowu Peng 《Biomedical chromatography : BMC》2015,29(10):1492-1498
The abundant production of methyl tert‐butyl ether (MTBE) and its widespread use have led to an increase in the potential for human exposure. This work described a simple, fast, sensitive, reliable and low‐cost method for the simultaneous measurement of MTBE and its metabolite, tert‐butyl alcohol (TBA) in human serum by headspace solid‐phase microextraction gas chromatography–mass spectrometry. Extraction conditions were optimized and 40 °C, 10 min, 250 rpm and 0.3 g NaCl for a 1 mL sample were the optimal conditions. This method showed good analytical performance in terms of sensitivity with limits of detection in serum (1 mL) of 0.03 µg/L for MTBE and 0.05 µg/L for TBA, accuracy (mean recovery values) from 75.8% to 85.8%, precision (relative standard deviations) <10% and sample stability (biodegradation) <10% after 28 days. A verification experiment proved the reproducibility and stability of this method as well. Finally the method was used to detect 212 specimens, and the internal dose levels for MTBE in human serum were presented in China. Copyright © 2015 John Wiley & Sons, Ltd. 相似文献