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31.
Justyna Rechthaler Ernst Pittenauer Tanner M. Schaub Günter Allmaier 《Journal of the American Society for Mass Spectrometry》2013,24(5):701-710
We have studied sample preparation conditions to increase the reproducibility of positive UV-MALDI-TOF mass spectrometry of peptides in the amol range. By evaluating several α-cyano-4-hydroxy-cinnamic acid (CHCA) matrix batches and preparation protocols, it became apparent that two factors have a large influence on the reproducibility and the quality of the generated peptide mass spectra: (1) the selection of the CHCA matrix, which allows the most sensitive measurements and an easier finding of the “sweet spots,” and (2) the amount of the sample volume deposited onto the thin crystalline matrix layer. We have studied in detail the influence of a contaminant, coming from commercial CHCA matrix batches, on sensitivity of generated peptide mass spectra in the amol as well as fmol range of a tryptic peptide mixture. The structure of the contaminant, N,N-dimethylbutyl amine, was determined by applying MALDI-FT-ICR mass spectrometry experiments for elemental composition and MALDI high energy CID experiments utilizing a tandem mass spectrometer (TOF/RTOF). A recrystallization of heavily contaminated CHCA batches that reduces or eliminates the determined impurity is described. Furthermore, a fast and reliable method for the assessment of CHCA matrix batches prior to tryptic peptide MALDI mass spectrometric analyses is presented. Figure
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32.
Lan Yu Qi Wang Lu Dai Wei-Ying Li Rong Chen Mian HR Mahmood Hai-Yang Liu Chi-Kwong Chang 《中国化学快报》2013,24(6):447-449
Pseudo-first order reaction rate constants of 5,10,15-tris(pentafluorophenyl)corrole Mn(V)-oxo (F15CMn(V)-oxo),5,15-bis(pentafluorophenyl)-10-(phenyl)corrole Mn(V)-oxo(F10CMn(V)-oxo),5,15- bis(phenyl)-10-(pentafluorophenyl)corrole Mn(V)-oxo(F5CMn(V)-oxo) and 5,10,15-tris(phenyl)corrole Mn(V)-oxo(F0CMn(V)-oxo) with a series of alkene substrates in different solvents were determined by UV-vis spectroscopy.The results indicated that the oxygen atom transfer pathway between Mn(V)-oxo corrole and alkene is solvent-dependent. 相似文献
33.
Synthesis of Oxacyclic Scaffolds via Dual Ruthenium Hydride/Brønsted Acid‐Catalyzed Isomerization/Cyclization of Allylic Ethers
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Dr. Erhad Ascic Ragnhild G. Ohm Dr. Rico Petersen Dr. Mette R. Hansen Casper L. Hansen Daniel Madsen Prof. Dr. David Tanner Prof. Dr. Thomas E. Nielsen 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(12):3297-3300
A ruthenium hydride/Brønsted acid‐catalyzed tandem sequence is reported for the synthesis of 1,3,4,9‐tetrahydropyrano[3,4‐b]indoles (THPIs) and related oxacyclic scaffolds. The process was designed on the premise that readily available allylic ethers would undergo sequential isomerization, first to enol ethers (Ru catalysis), then to oxocarbenium ions (Brønsted acid catalysis) amenable to endo cyclization with tethered nucleophiles. This methodology provides not only an attractive alternative to the traditional oxa‐Pictet–Spengler reaction for the synthesis of THPIs, but also convenient access to THPI congeners and other important oxacycles such as acetals. 相似文献
34.
Joseph Derosa Taeho Kang Van T. Tran Dr. Steven R. Wisniewski Dr. Malkanthi K. Karunananda Tanner C. Jankins Kane L. Xu Dr. Keary M. Engle 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(3):1217-1221
A nickel-catalyzed conjunctive cross-coupling of alkenyl carboxylic acids, aryl iodides, and aryl/alkenyl boronic esters is reported. The reaction delivers the desired 1,2-diarylated and 1,2-arylalkenylated products with excellent regiocontrol. To demonstrate the synthetic utility of the method, a representative product is prepared on gram scale and then diversified to eight 1,2,3-trifunctionalized building blocks using two-electron and one-electron logic. Using this method, three routes toward bioactive molecules are improved in terms of yield and/or step count. This method represents the first example of catalytic 1,2-diarylation of an alkene directed by a native carboxylate group. 相似文献
35.
Joseph Derosa Taeho Kang Van T. Tran Steven R. Wisniewski Malkanthi K. Karunananda Tanner C. Jankins Kane L. Xu Keary M. Engle 《Angewandte Chemie (International ed. in English)》2020,59(3):1201-1205
A nickel‐catalyzed conjunctive cross‐coupling of alkenyl carboxylic acids, aryl iodides, and aryl/alkenyl boronic esters is reported. The reaction delivers the desired 1,2‐diarylated and 1,2‐arylalkenylated products with excellent regiocontrol. To demonstrate the synthetic utility of the method, a representative product is prepared on gram scale and then diversified to eight 1,2,3‐trifunctionalized building blocks using two‐electron and one‐electron logic. Using this method, three routes toward bioactive molecules are improved in terms of yield and/or step count. This method represents the first example of catalytic 1,2‐diarylation of an alkene directed by a native carboxylate group. 相似文献
36.
37.
Desouza Arun H. G. Tanner Robert D. Effler W. T. 《Applied biochemistry and biotechnology》1991,(1):655-666
Studies were conducted to establish the effect of the variation of environmental factors on the separation occurring in protein
systems, resulting from bubble fractionation in a bioreactor. The measure of separation was selected to be the separation
ratio. This is defined to be the ratio of either the top or the middle position concentration in the vessel to the bottom
concentration of the vessel. Invertase and α-amylase were the two “model” enzymes considered. It was observed that, under
certain conditions, i.e., a combination of the nature of the sparging gas and the medium pH, varying degrees of protein separation
were achieved. The pH of the system dramatically influenced the separation. It was found that the best separation occurred
at a certain pH, assumed to be at or close to thepI of the protein in question. Furthermore, it was observed that systems sparged with CO2 exhibited greater separation than systems sparged with air. In fact, in the case of invertase, almost threefold separation
was observed at the top port when the solution was sparged with CO2. 相似文献
38.
Bernardo Duarte Renato Mamede Irina A. Duarte Isabel Caador Susanne E. Tanner Marisa Silva David Jacinto Teresa Cruz Vanessa F. Fonseca 《Molecules (Basel, Switzerland)》2022,27(4)
The stalked barnacle Pollicipes pollicipes is an abundant species on the very exposed rocky shore habitats of the Spanish and Portuguese coasts, constituting also an important economical resource, as a seafood item with high commercial value. Twenty-four elements were measured by untargeted total reflection X-ray fluorescence spectroscopy (TXRF) in the edible peduncle of stalked barnacles sampled in six sites along the Portuguese western coast, comprising a total of 90 individuals. The elemental profile of 90 individuals originated from several geographical sites (N = 15 per site), were analysed using several chemometric multivariate approaches (variable in importance partial least square discriminant analysis (VIP-PLS-DA), stepwise linear discriminant analysis (S-LDA), linear discriminant analysis (LDA), random forests (RF) and canonical analysis of principal components (CAP)), to evaluate the ability of each approach to trace the geographical origin of the animals collected. As a suspension feeder, this species introduces a high degree of background noise, leading to a comparatively lower classification of the chemometric approaches based on the complete elemental profile of the peduncle (canonical analysis of principal components and linear discriminant analysis). The application of variable selection approaches such as the VIP-PLS-DA and S-LDA significantly increased the classification accuracy (77.8% and 84.4%, respectively) of the samples according to their harvesting area, while reducing the number of elements needed for this classification, and thus the background noise. Moreover, the selected elements are similar to those selected by other random and non-random approaches, reinforcing the reliability of this selection. This untargeted analytical procedure also allowed to depict the degree of risk, in terms of human consumption of these animals, highlighting the geographical areas where these delicacies presented lower values for critical elements compared to the standard thresholds for human consumption. 相似文献
39.
40.
Matthias Schulz Susanne Tanner Haitham Barqawi Wolfgang H. Binder 《Journal of polymer science. Part A, Polymer chemistry》2010,48(3):671-680
The end‐to‐end cyclization of telechelic polyisobutylenes (PIB's) toward cyclic polyisobutylenes is reported, using either ring‐closing metathesis (RCM) or the azide/alkyne‐“click”‐reaction. The first approach uses bisallyl‐telchelic PIB's (Mn = 1650, 3680, 9770 g mol?1) and Grubbs 1st‐, 2nd‐, and 3rd‐generation catalyst leading to cyclic PIB's in 60–80% yield, with narrow polydispersities (Mw/Mn = 1.25). Azide/alkyne‐“click”‐reactions of bisalkyne‐telechelic PIB's (Mn = 3840 and 9820 g mol?1) with excess of 1,11‐diazido‐undecane leads to the formation of mixtures of linear/cyclic PIB's under formation of oligomeric cycles. Subsequent reaction of the residual azide‐moieties in the linear PIB's with excess of alkyne‐telechelic PEO enables the chromatographic removal of the resulting linear PEO‐PIB‐block copolymers by column chromatography. Thus pure cyclic PIB's can be obtained using this double‐“click”‐method, devoid of linear contaminants. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 671–680, 2010 相似文献