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101.
Using controlled radical polymerization to confirm the lower critical solution temperature of an N‐(alkoxyalkyl) acrylamide polymer in aqueous solution 下载免费PDF全文
Xeniya Savelyeva Lucia Li Milan Marić 《Journal of polymer science. Part A, Polymer chemistry》2015,53(1):59-67
N‐(3‐Methoxypropyl) acrylamide (MPAM) was polymerized by controlled radical polymerization (CRP) methods such as nitroxide‐mediated polymerization (NMP) and reversible addition–fragmentation chain‐transfer polymerization (RAFT). CRP was expected to yield well‐defined polymers with sharp lower critical solution temperature (LCST) transitions. NMP with the BlocBuilder (2‐([tert‐butyl[1‐(diethoxyphosphoryl)‐2,2‐dimethylpropyl]amino]oxy)‐2‐methylpropanoic acid) and SG1 ([tert‐butyl[1‐(diethoxyphosphoryl)‐2,2‐dimethylpropyl]amino] oxidanyl) initiating system revealed low yields and lack of control (high dispersity, ? ~ 1.5–1.6, and inhibition of chain growth). However, RAFT was far more effective, with linear number average molecular weight, , versus conversion, X, plots, low ? ~ 1.2–1.4 and the ability to form block copolymers using N,N‐diethylacrylamide (DEAAM) as the second monomer. Poly(MPAM) (with = 13.7–25.3 kg mol?1) thermoresponsive behavior in aqueous media revealed cloud point temperatures (CPT)s between 73 and 92 °C depending on solution concentration (ranging from 1 to 3 wt %). The and the molecular weight distribution were the key factors determining the CPT and the sharpness of the response, respectively. Poly(MPAM)‐b‐poly(DEAAM) block copolymer ( = 22.3 kg mol?1, ? = 1.41, molar composition FDEAAM = 0.38) revealed dual LCSTs with both segments revealing distinctive CPTs (at 75 and 37 °C for poly(MPAM) and poly(DEAAM) blocks, respectively) by both UV–Vis and dynamic light scattering. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 59–67 相似文献
102.
Benoît Lessard Milan Marić 《Journal of polymer science. Part A, Polymer chemistry》2009,47(10):2574-2588
Methyl methacrylate/styrene (MMA/S), ethyl methacrylate/styrene (EMA/S) and butyl methacrylate/styrene (BMA/S) feeds (>90 mol % methacrylate) were copolymerized in 50 wt % p‐xylene at 90 °C with 10 mol % of additional SG1‐free nitroxide mediator relative to unimolecular initiator (BlocBuilder®) to yield methacrylate rich copolymers with polydispersities w/ n = 1.23–1.46. kpK values (kp = propagation rate constant, K = equilibrium constant) for MMA/S copolymerizations were comparable with previous literature, whereas EMA/S and BMA/S copolymerizations were characterized by slightly higher kpK's. Chain extensions with styrene at 110 °C initiated by the methacrylate‐rich macroinitiators (number average molecular weight n = 12.9–33.5 kg mol?1) resulted in slightly broader molecular weight distributions with w/ n = 1.24–1.86 and were often bimodal. Chain extensions with glycidyl methacrylate/styrene/methacrylate (GMA/S/XMA where XMA = MMA, EMA or BMA) mixtures at 90 °C using the same macroinitiators resulted frequently in bimodal molecular weight distributions with many inactive macroinitiators and higher w/ n = 2.01–2.48. P(XMA/S) macroinitiators ( n = 4.9–8.9 kg mol?1), polymerized to low conversion and purified to remove “dead” chains, initiated chain extensions with GMA/MMA/S and GMA/EMA/S giving products with w/ n ~ 1.5 and much fewer unreacted macroinitiators (<5%), whereas the GMA/BMA/S chain extension was characterized by slightly more unreacted macroinitiators (~20%). © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 2574–2588, 2009 相似文献
103.
Haruhiko Fuwa Prof. Dr. Asami Saito Shinya Naito Keiichi Konoki Prof. Dr. Mari Yotsu‐Yamashita Prof. Dr. Makoto Sasaki Prof. Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2009,15(46):12807-12818
The stereocontrolled total synthesis of the originally proposed ( 1 ) and correct ( 2 ) structures of (+)‐neopeltolide, a novel marine macrolide natural product with highly potent antiproliferative activity against several cancer cell lines as well as potent antifungal activity, has been achieved by exploiting a newly developed Suzuki–Miyaura coupling/ring‐closing metathesis strategy. Alkylborate 44 , which was generated in situ from iodide 34 , was coupled with enol phosphate 8 by a Suzuki–Miyaura coupling. Ring‐closing metathesis of the derived diene 45 followed by stereoselective hydrogenation afforded tetrahydropyran 47 as a single stereoisomer in high overall yield from 34 . Our convergent strategy enabled us to construct the 14‐membered macrolactone core structure of 2 in a rapid and efficient manner. Total synthesis and biological evaluation of synthetic intermediates and designed synthetic analogues, performed to establish the structure–activity relationships of 2 , led to the discovery of a structurally simple yet potent cytotoxic analogue, 9‐demethylneopeltolide ( 54 ). 相似文献
104.
Ken Hosoya Tomoko Mori Mari Sakamoto Takuya Kubo Kunimitsu Kaya 《Chromatographia》2009,70(5-6):699-704
We report the chromatographic properties of a new type of epoxy polymer-based monolithic capillary column, the Tetrad-C column. The column was prepared by a completely new method—reaction of a tetra-functional epoxy monomer, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane (trade name Tetrad-C), with a diamine, 4-[(4-aminocyclohexyl)methyl)cyclohexane (BACM). This polymer monolith has no aromatic functional groups reducing chromatographic performance. The columns were carefully observed by scanning electron microscopy and evaluated chromatographically by use of a μ-HPLC system. It was found that morphological control of the epoxy polymer-based monolith was possible simply by changing the polymerization conditions, i.e., the polymerization temperature and/or the relative amounts of porogenic solvent and BACM. Another advantage was that volumetric shrinkage of the tetra-functional epoxy-based monolith during the polymerization reaction was much less than for the tri-functional epoxy-based monolithic (TEPIC) column reported in our previous paper. A Tetrad-C column 200 mm long afforded up to 10,000 plates for alkylbenzenes in reversed-phase-mode. This column can also work in HILIC mode, although the hydrophobicity of the column was greater than that of the TEPIC column. Heat treatment (160 °C for 2 h; to eliminate residual, unreacted, functional groups) had a negligible effect on column performance, indicating the columns were thermally stable. 相似文献
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108.
Beverina L Crippa M Landenna M Ruffo R Salice P Silvestri F Versari S Villa A Ciaffoni L Collini E Ferrante C Bradamante S Mari CM Bozio R Pagani GA 《Journal of the American Chemical Society》2008,130(6):1894-1902
Singlet oxygen sensitization by organic molecules is a topic of major interest in the development of both efficient photodynamic therapy (PDT) and aerobic oxidations under complete green chemistry conditions. We report on the design, synthesis, biology, and complete spectroscopic characterization (vis-NIR linear and two-photon absorption spectroscopy, singlet oxygen generation efficiencies for both one- and two-photon excitation, electrochemistry, intrinsic dark toxicity, cellular uptake, and subcellular localization) of three classes of innovative singlet oxygen sensitizers pertaining to the family of symmetric squaraine derivatives originating from pi-excessive heterocycles. The main advantage of pi-extended squaraine photosensitizers over the large number of other known photosensitizers is their exceedingly strong two-photon absorption enabling, together with sizable singlet oxygen sensitization capabilities, for their use at the clinical application relevant wavelength of 806 nm. We finally show encouraging results about the dark toxicity and cellular uptake capabilities of water-soluble squaraine photosensitizers, opening the way for clinical small animal PDT trials. 相似文献
109.
Frederick Trinh Tan Milan Mari? James A. Nicell 《Polymer Degradation and Stability》2008,93(8):1479-1485
The aerobic biological degradation of the synthetic aliphatic-aromatic co-polyester Ecoflex™ (BASF) by 29 strains of enzyme-producing soil bacteria, fungi and yeasts was investigated at moderate environmental conditions. Previous studies had shown that these materials could be degraded but these studies were done under thermophilic conditions. In this paper, a screening procedure was developed to assess the biodegradability of the co-polyester at ambient environmental conditions and to investigate the mechanism of biodegradation. Results showed that the aliphatic-aromatic co-polyester could be degraded by a number of different microorganisms. However, after 21 days exposure to even the most promising cultures of pure microorganisms, only partial degradation of the Ecoflex™ was accomplished and only a few samples showed visible signs of degradation as loosely defined by the mechanical weakening of the films. Weight loss was not as obvious as the visual degradation and suggested broader types of microbial attack. The bacteria studied preferentially degraded the bonds between aliphatic components of the copolymer and the rate of biodegradation of oligomers was appreciably faster than that for the polymer chains. Using GC-MS techniques, degradation intermediates were identified to be the monomers of the co-polyester. Gel permeation chromatography results suggested exo-enzyme type degradation, where the microbes hydrolysed the ester bonds at the termini of the polymeric chains preferentially. 相似文献
110.
K. Nakanishi T. Masukawa T. Nadai K. Yoshii S. Okada K. Miyajima 《Journal of inclusion phenomena and macrocyclic chemistry》1996,25(1-3):181-184
Triacetyl--cyclodextrin (TA--CyD), a hydrophobic cyclodextrin derivative, that is insoluble in water, was used to form a complex with flufenamic acid (FA). FA-TA--CyD complex formation was demonstrated by differential scanning calorimetry and powder X-ray diffractometry. The release rate of FA from the FA-TA--CyD complexes in phosphate buffer pH 6.8 was significantly retarded compared to that of FA from the FA and glucose mixture. When the FA-TA--CyD complexes were administered directly into the intraduodenal lumen, the plasma concentration of FA remained at a plateau level (10-18 g/ml) for 6–8 h. An increased mean residence time of FA following FA-TA--CyD complexes administration was observed. These results indicate that TA--CyD may serve as a hydrophobic carrier in prolonged-release preparations of FA. 相似文献