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121.
Gas—phase high resolution NMR is a potentially useful new tool for the study of rotational isomerism. The methods of measurement are explained, with the care necessary for sample preparations. The main areas of application at present are a) dynamic NMR study of conformational interconversion processes and b) conformational analysis for populations and energies through coupling constants. For the latter, our recent results on 1,2-disubstituted propanes such as 1,2-dichloropropane, 1,2-di(methoxy-d3)propane and 1-methoxy-2-propanol are discussed. 相似文献
122.
Benzyl chloromethyl ether reacts with carbonyl compounds in the presence of SmI2 to afford alcohols (I), which are subsequently subjected to hydrogenolysis to yield diols (II). 相似文献
123.
Tsuneo Okubo Hiroshi Kimura Hiromi Hase Keizo Yamaguchi Tatsuo Taniguchi Katsutoshi Nagai 《Colloid and polymer science》2004,282(3):250-255
Colloidal single crystals of cationic polymer spheres (198–250 nm in diameter) in deionized aqueous dispersions were formed for the first time. The spheres used were poly(styrene-co-methacryloyloxyphenyldimethylsulfonium) cations. These cations are unstable in deionized suspensions with mixed beds of cation-exchange and anion-exchange resins. This was clarified by reflection spectroscopy, pH, conductance and -potential measurements for 250 days after suspension preparation. Colloidal crystals formed over a period of 24 h for the deionized suspensions at sphere concentrations higher than 0.09 in volume fraction. The nearest-neighbor intersphere distances coincide satisfactorily with the calculated values using the diameter and the concentration of the spheres. Alloy crystals formed from binary mixtures of the cationic polymer spheres and the anionic silica spheres when the ratio of the volume fraction of cationic spheres against the sum of the both cationic and anionic spheres was smaller than 0.3. 相似文献
124.
Tsuneo Okubo Akira Tsuchida Hideki Yoshimi Kazumori Taguchi Shigeharu Kiriyama 《Colloid and polymer science》2002,280(3):228-233
Rotational relaxation times (τ) of anisotropic tungstic acid colloids (3.24 μm in major axis) in aqueous suspension are measured in microgravity (0G), normal gravity (1G) and at 2G. The measurements at 0G and 2G are achieved by parabolic and circular flights, respectively. The limiting slopes of the relaxation curves in the plots of
the transmitted light intensity against time are close to zero at 0G irrespective of the flow directions in the flow cell, whereas those at 1G and especially at 2G depend on the flow direction by the convection of the suspension and particle sedimentation. Experimental errors at the τ
values at 0G are small compared with those at 1G and 2G, which is ascribed to the lack of movement of impurities in the suspension such as quite small air bubbles, which cannot
be recognized with the naked eye, and the convection of the suspension in microgravity. More reliable rotational relaxation
times are obtained in microgravity; however, the relaxation times themselves are quite insensitive to gravity. Theτ values observed are larger than those calculated from the particle size, which indicates the important contribution of the
electrical double layers formed around the colloidal particles.
Received: 22 February 2001 Accepted: 13 June 2001 相似文献
125.
A new P-chiral phosphine ligand, (R,R)-2,3-bis(tert-butylmethylphosphino)quinoxaline, has been prepared by the reaction of enantiomerically pure tert-butylmethylphosphine-borane with 2,3-dichloroquinoxaline. This ligand, in contrast to most of the previously reported P-chiral ligands, is an air-stable solid and exhibits excellent enantioselectivities in both Rh-catalyzed asymmetric hydrogenations and Rh- or Pd-catalyzed carbon-carbon bond-forming reactions. 相似文献
126.
127.
Kenichiro Todoroki Yasuhiro Ishii Koji Toyoda Takashi Ikawa Jun Zhe Min Koichi Inoue Shuji Akai Toshimasa Toyo’oka 《Analytical and bioanalytical chemistry》2013,405(25):8121-8129
In this paper, we report a new type of chiral high-performance liquid chromatography (HPLC) column—a so-called dress-up chiral column—featuring a chiral stationary phase adsorbed reversibly in a commercial fluorous HPLC column through fluorous interactions. We synthesized perfluroalkylated proline derivatives as chiral stationary phase compounds and then adsorbed them reversibly in the fluorous HPLC column through the pumping of their solutions. By using this dress-up chiral column and fluorophobic elution of an aqueous copper(II) sulfate/MeOH mixture, we could enantioseparate seven racemic amino acids within 40 min. When we washed the dress-up chiral column with fluorophilic tetrahydrofuran or MeOH, the adsorbed chiral stationary phase compounds desorbed from the column, completely destroying its enantioseparation ability. The relative standard deviation of the retention times, the number of theoretical plates, and the resolution for each of four preparations of the dress-up columns were all less than or equal to 9.53 % in 20-times repeated analysis, and were all less than or equal to 18.7 % in four different preparations, respectively. 相似文献
128.
Crystal growth and morphology of colloidal crystals of silica spheres (81.2 nm in diameter) are observed directly on a video-tape camera. Crystal growth from the round-shaped, small single crystals to the angular-shaped ones is clear. It is observable that the single crystals are packed densely and separated from each other with the grain boundaries. The morphology of colloidal crystals is quite similar to that of typical crystals such as metals, proteins, and ice. 相似文献
129.
Satoshi Horino Tomoya Nishio Shinji Kawanishi Shinya Oki Koichi Nishihara Dr. Takashi Ikawa Dr. Kyohei Kanomata Karla Wagner Prof. Dr. Harald Gröger Prof. Dr. Shuji Akai 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(60):e202202437
Natural lipases typically recognize enantiomers of alcohols based on the size differences of substituents near the carbinol moiety and selectively react with the R enantiomers of secondary alcohols. Therefore, lipase-catalyzed dynamic kinetic resolution (DKR) of racemic secondary alcohols produces only R enantiomers. We report herein a method for obtaining S enantiomers by DKR of secondary 3-(trialkylsilyl)propargyl alcohols by using a well-known R-selective Pseudomonas fluorescens lipase in combination with a racemization catalyst VMPS4, in which the silyl group reverses the size relationship of substituents near the carbinol moiety. We have already reported R-selective DKR of the corresponding propargyl alcohols without substituents on the ethynyl terminal carbon, and the presence of an easily removable silyl group has enabled us to produce both enantiomers of propargyl alcohols in high chemical yields and with high enantiomeric excess. In addition, immobilization of the lipase on Celite was found to be important for achieving a high efficiency of the DKR. 相似文献
130.
Gas chromatography–electron ionization–mass spectrometry quantitation of valproic acid and gabapentin,using dried plasma spots,for therapeutic drug monitoring in in‐home medical care 下载免费PDF全文
Kayo Ikeda Kazuro Ikawa Satoko Yokoshige Satoshi Yoshikawa Norifumi Morikawa 《Biomedical chromatography : BMC》2014,28(12):1756-1762
A simple and sensitive gas chromatography–electron ionization–mass spectrometry (GC‐EI‐MS) method using dried plasma spot testing cards was developed for determination of valproic acid and gabapentin concentrations in human plasma from patients receiving in‐home medical care. We have proposed that a simple, easy and dry sampling method is suitable for in‐home medical patients for therapeutic drug monitoring. Therefore, in the present study, we used recently developed commercially available easy handling cards: Whatman FTA DMPK‐A and Bond Elut DMS. In‐home medical care patients can collect plasma using these simple kits. The spots of plasma on the cards were extracted into methanol and then evaporated to dryness. The residues were trimethylsilylated using N‐methyl‐N‐trimethylsilyltrifluoroacetamide. For GC‐EI‐MS analysis, the calibration curves on both cards were linear from 10 to 200 µg/mL for valproic acid, and from 0.5 to 10 µg/mL for gabapentin. Intra‐ and interday precisions in plasma were both ≤13.0% (coefficient of variation), and the accuracy was between 87.9 and 112% for both cards within the calibration curves. The limits of quantification were 10 µg/mL for valproic acid and 0.5 µg/mL for gabapentin on both cards. We believe that the present method will be useful for in‐home medical care. Copyright © 2014 John Wiley & Sons, Ltd. 相似文献