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61.
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
62.
Aya Yoshimura Akihiro Nomoto Mari Uchida Hiroki Kusano Tomokazu Saeki Akiya Ogawa 《Research on Chemical Intermediates》2017,43(6):3433-3443
The functionalization of polysilanes is an important subject in materials science because functionalized polysilanes are expected to exhibit potentially innovative properties. This research aims at the addition of a water-shedding property to polysilanes by introducing perfluoroalkyl groups into their skeleton. The photoinduced iodoperfluoroalkylation of various vinylsilanes takes place successfully upon irradiation with a xenon lamp: vinylmonosilanes undergo iodoperfluoroalkylation with perfluoroalkyl iodides (RfI) regioselectively, and the corresponding perfluoroalkylated silanes are obtained in moderate to high yields. Detailed optimization of the photoinduced iodoperfluoroalkylation has been investigated to apply this method to the functionalization of polysilanes. Polysilanes having vinyl groups can be synthesized by the reductive coupling of dichlorovinylsilanes with samarium diiodide (SmI2) and samarium metal (Sm) upon irradiation with visible light. The synthesized vinylpolysilanes and RfI (about 1.0 mM CHCl3 solution) are coated on a glass plate sequentially, and then the following photoirradiation with light of a wavelength over 300 nm successfully adds an excellent water-shedding property to the glass plate. 相似文献
63.
64.
Lone AM Bachovchin DA Westwood DB Speers AE Spicer TP Fernandez-Vega V Chase P Hodder PS Rosen H Cravatt BF Saghatelian A 《Journal of the American Chemical Society》2011,133(30):11665-11674
Peptidases play vital roles in physiology through the biosynthesis, degradation, and regulation of peptides. Prolyl endopeptidase-like (PREPL) is a newly described member of the prolyl peptidase family, with significant homology to mammalian prolyl endopeptidase and the bacterial peptidase oligopeptidase B. The biochemistry and biology of PREPL are of fundamental interest due to this enzyme's homology to the biomedically important prolyl peptidases and its localization in the central nervous system. Furthermore, genetic studies of patients suffering from hypotonia-cystinuria syndrome (HCS) have revealed a deletion of a portion of the genome that includes the PREPL gene. HCS symptoms thought to be caused by lack of PREPL include neuromuscular and mild cognitive deficits. A number of complementary approaches, ranging from biochemistry to genetics, will be required to understand the biochemical, cellular, physiological, and pathological mechanisms regulated by PREPL. We are particularly interested in investigating physiological substrates and pathways controlled by PREPL. Here, we use a fluorescence polarization activity-based protein profiling (fluopol-ABPP) assay to discover selective small-molecule inhibitors of PREPL. Fluopol-ABPP is a substrate-free approach that is ideally suited for studying serine hydrolases for which no substrates are known, such as PREPL. After screening over 300,000 compounds using fluopol-ABPP, we employed a number of secondary assays to confirm assay hits and characterize a group of 3-oxo-1-phenyl-2,3,5,6,7,8-hexahydroisoquinoline-4-carbonitrile and 1-alkyl-3-oxo-3,5,6,7-tetrahydro-2H-cyclopenta[c]pyridine-4-carbonitrile PREPL inhibitors that are able to block PREPL activity in cells. Moreover, when administered to mice, 1-isobutyl-3-oxo-3,5,6,7-tetrahydro-2H-cyclopenta[c]pyridine-4-carbonitrile distributes to the brain, indicating that it may be useful for in vivo studies. The application of fluopol-ABPP has led to the first reported PREPL inhibitors, and these inhibitors will be of great value in studying the biochemistry of PREPL and in eventually understanding the link between PREPL and HCS. 相似文献
65.
Uchiyama K Kondo M Yokochi R Takeuchi Y Yamamoto A Inoue Y 《Journal of separation science》2011,34(13):1525-1530
A simple, selective and rapid analytical method for determination of trimethoprim (TMP) in honey samples was developed and validated. This method is based on a SPE technique followed by HPLC with photodiode array detection. After dilution and filtration, aliquots of 500 μL honey samples were directly injected to an on-line SPE HPLC system. TMP was extracted on an RP SPE column, and separated on a hydrophilic interaction chromatography column during HPLC analysis. At the first detection step, the noise level of the photodiode array data was reduced with two-dimensional equalizer filtering, and then the smoothed data were subjected to derivative spectrum chromatography. On the second-derivative chromatogram at 254 nm, the limit of detection and the limit of quantification of TMP in a honey sample were 5 and 10 ng/g, respectively. The proposed method showed high accuracy (60-103%) with adequate sensitivity for TMP monitoring in honey samples. 相似文献
66.
A proficiency test including the screening analysis of antibiotics in beef using cryogenicly minced materials was organized by RIKILT in 2009. The test included blank beef samples and beef samples spiked with either flumequine or a combination of lincomycin and spectinomycin around the maximum residue limits [1]. The suitability of the materials was demonstrated with a homogeneity and a stability study. This study showed that cryogenically minced spiked muscle material is suited for proficiency tests aiming at the screening and the confirmatory analysis.Of the 26 participants, 23 carried out their in-house screening approach involving microbial, biochemical or instrumental methods, or a combination of these to cover the broad range of antibiotic groups. The false negative rate was 73% for microbial methods, 50% for biochemical and 22% for instrumental methods. These results indicate that substantial effort is needed to improve screening approaches and that more regular proficiency tests are needed to reveal the shortcomings in the currently applied screening methods. 相似文献
67.
Nakato T Yamada Y Nakamura M Takahashi A 《Journal of colloid and interface science》2011,354(1):38-44
We investigated photoinduced electron accumulation in a colloidal system of layered hexaniobate that is known as a photocatalytically active wide band-gap semiconductor, and attempted to control the photoresponse by introducing additives into the colloid. The inorganic nanosheets were obtained by exfoliation of the layered oxide. UV-irradiation of the colloids led to electron accumulation in the nanosheets to generate reduced niobate species. Propylammonium ions introduced as the exfoliating reagent and present as the counter ions of niobate nanosheets were indicated as the electron donor that stabilized the electron-accumulating state. Yield and half-life of the reduced niobate species greatly increased by adding an appropriate amount of photochemically inert clay nanosheets, while they increased only a little by the addition of molecular electron donors such as EDTA and triethanolamine. Moreover, the molecular species diminished the enhancement effect of the clay nanosheets. The results suggested that the photochemical event was not explained by direct interactions between the semiconductor nanosheets and the additives at molecular level but governed by indirect interactions between the colloid components regulated by the colloid structure. 相似文献
68.
The collision complex formed from a vibrationally excited reactant undergoes redissociation to the reactant, intramolecular vibrational relaxation (randomization of vibrational energy), or chemical reaction to the products. If attractive interaction between the reactants is large, efficient vibrational relaxation in the complex prevents redissociation to the reactants with the initial vibrational energy, and the complex decomposes to the reactants with low vibrational energy or converts to the products. In this paper, we have studied the branching ratios between the intramolecular vibrational relaxation and chemical reaction of an adduct HO(v)-CO formed from OH(X(2)Π(i)) in different vibrational levels v = 0-4 and CO. OH(v = 0-4) generated in a gaseous mixture of O(3)/H(2)/CO/He irradiated at 266 nm was detected with laser-induced fluorescence (LIF) via the A(2)Σ(+)-X(2)Π(i) transition, and H atoms were probed by the two-photon excited LIF technique. From the kinetic analysis of the time-resolved LIF intensities of OH(v) and H, we have found that the intramolecular vibrational relaxation is mainly governed by a single quantum change, HO(v)-CO → HO(v-1)-CO, followed by redissociation to OH(v-1) and CO. With the vibrational quantum number v, chemical process from the adduct to H + CO(2) is accelerated, and vibrational relaxation is decelerated. The countertrend is elucidated by the competition between chemical reaction and vibrational relaxation in the adduct HOCO. 相似文献
69.
C. M. Mari 《Ionics》2003,9(5-6):365-369
Aim of the lecture is to present the operating principles of non-Nernstian electrochemical devices, the state of the art as
well as the weight of the electrode materials electrocatalytic properties in the design of planar sensors.
Paper presented at the 9th EuroConference on Ionics, Ixia, Rhodes, Greece, Sept. 15–21, 2002. 相似文献
70.
Laura L. Tomasevich Stephen M. Zitelli Chelsey R. Gillen Neal J. Baker Jason M. Conley Mari Lynne Starr Patrick J. Carroll 《Tetrahedron letters》2007,48(4):599-602
Condensation of ninhydrin with tryptamide or tryptamine followed by Lewis acid-induced rearrangement provided yohimbanones that were readily converted to β-carbolines via oxidative ring cleavage. The analogous condensation-rearrangement with 3,4-dimethoxyphenethylamine and ninhydrin afforded an oxyprotoberberine, which was further oxygenated at the 13a position. 相似文献