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1.
13C-NMR studies of marine natural products II. Total assignment of the 13C-NMR spectrum of asperdiol
13C-nmr spectral assignments for asperdiol are made with the aid of model compounds and T1 relaxation behavior. Overall isotropic tumbling was inferred from the latter providing a supplemental means of multiplicity determination. Utilization of the T1 relaxation times as an assignment criterion for select resonances in asperdiol is also described. 相似文献
2.
Lana G. Kaiser Ma?gorzata Marjańska Gerald B. Matson Isabelle Iltis Seth D. Bush Brian J. Soher Susanne Mueller Karl Young 《Journal of magnetic resonance (San Diego, Calif. : 1997)》2010,202(2):259-266
Glutathione (GSH) is a powerful antioxidant found inside different kinds of cells, including those of the central nervous system. Detection of GSH in the human brain using 1H MR spectroscopy is hindered by low concentration and spectral overlap with other metabolites. Previous MRS methods focused mainly on the detection of the cysteine residue (GSH-Cys) via editing schemes. This study focuses on the detection of the glycine residue (GSH-Gly), which is overlapped by glutamate and glutamine (Glx) under physiological pH and temperature. The first goal of the study was to obtain the spectral parameters for characterization of the GSH-Gly signal under physiological conditions. The second goal was to investigate a new method of separating GSH-Gly from Glx in vivo. The characterization of the signal was carried out by utilization of numerical simulations as well as experiments over a wide range of magnetic fields (4.0–14 T). The proposed separation scheme utilizes J-difference editing to quantify the Glx contribution to separate it from the GSH-Gly signal. The presented method retains 100% of the GSH-Gly signal. The overall increase in signal to noise ratio of the targeted resonance is calculated to yield a significant SNR improvement compared to previously used methods that target GSH-Cys residue. This allows shorter acquisition times for in vivo human clinical studies. 相似文献
3.
Metagenomic and functional analysis of hindgut microbiota of a wood-feeding higher termite 总被引:6,自引:0,他引:6
Warnecke F Luginbühl P Ivanova N Ghassemian M Richardson TH Stege JT Cayouette M McHardy AC Djordjevic G Aboushadi N Sorek R Tringe SG Podar M Martin HG Kunin V Dalevi D Madejska J Kirton E Platt D Szeto E Salamov A Barry K Mikhailova N Kyrpides NC Matson EG Ottesen EA Zhang X Hernández M Murillo C Acosta LG Rigoutsos I Tamayo G Green BD Chang C Rubin EM Mathur EJ Robertson DE Hugenholtz P Leadbetter JR 《Nature》2007,450(7169):560-565
From the standpoints of both basic research and biotechnology, there is considerable interest in reaching a clearer understanding of the diversity of biological mechanisms employed during lignocellulose degradation. Globally, termites are an extremely successful group of wood-degrading organisms and are therefore important both for their roles in carbon turnover in the environment and as potential sources of biochemical catalysts for efforts aimed at converting wood into biofuels. Only recently have data supported any direct role for the symbiotic bacteria in the gut of the termite in cellulose and xylan hydrolysis. Here we use a metagenomic analysis of the bacterial community resident in the hindgut paunch of a wood-feeding 'higher' Nasutitermes species (which do not contain cellulose-fermenting protozoa) to show the presence of a large, diverse set of bacterial genes for cellulose and xylan hydrolysis. Many of these genes were expressed in vivo or had cellulase activity in vitro, and further analyses implicate spirochete and fibrobacter species in gut lignocellulose degradation. New insights into other important symbiotic functions including H2 metabolism, CO2-reductive acetogenesis and N2 fixation are also provided by this first system-wide gene analysis of a microbial community specialized towards plant lignocellulose degradation. Our results underscore how complex even a 1-microl environment can be. 相似文献
4.
High-dimensional, multispectral data on complex physical systems are increasingly common. As the amount of information in data sets increases, the difficulty of effectively utilizing it also increases. For such data, summary information is required for understanding and modeling the underlying dynamics. It is here proposed to use an extension of computational mechanics [C. R. Shalizi and J. P. Crutchfield, J. Stat. Phys. 104, 817 (2001)] to arbitrary spatiotemporal and spectral dimension, for providing such summary information. An example of the use of these tools to identify state evolution in the brain, an archetypal, complex biophysical system, serves as an illustration. 相似文献
5.
Agricultural sustainability and intensive production practices 总被引:121,自引:0,他引:121
A doubling in global food demand projected for the next 50 years poses huge challenges for the sustainability both of food production and of terrestrial and aquatic ecosystems and the services they provide to society. Agriculturalists are the principal managers of global usable lands and will shape, perhaps irreversibly, the surface of the Earth in the coming decades. New incentives and policies for ensuring the sustainability of agriculture and ecosystem services will be crucial if we are to meet the demands of improving yields without compromising environmental integrity or public health. 相似文献
6.
Scott C. Radzinski Jeffrey C. Foster John B. Matson 《Macromolecular rapid communications》2016,37(7):616-621
Bottlebrush polymers are synthesized using a tandem ring‐opening polymerization (ROP) and ring‐opening metathesis polymerization (ROMP) strategy. For the first time, ROP and ROMP are conducted sequentially in the same pot to yield well‐defined bottlebrush polymers with molecular weights in excess of 106 Da. The first step of this process involves the synthesis of a polylactide macromonomer (MM) via ROP of d ,l ‐lactide initiated by an alcohol‐functionalized norbornene. ROMP grafting‐through is then carried out in the same pot to produce the bottlebrush polymer. The applicability of this methodology is evaluated for different MM molecular weights and bottlebrush backbone degrees of polymerization. Size‐exclusion chromatographic and 1H NMR spectroscopic analyses confirm excellent control over both polymerization steps. In addition, bottlebrush polymers are imaged using atomic force microscopy and stain‐free transmission electron microscopy on graphene oxide.
7.
Hydrolytically-labile hydrazones in peptide amphiphiles were studied as degradable tethers for release of the drug nabumetone from nanofiber gels. On-resin addition of the novel compound tri-Boc-hydrazido adipic acid to a lysine ε-amine allowed for precise placement of a hydrazide in a peptide sequence. 相似文献
8.
Nanoparticles containing fluorine-18 were prepared from block copolymers made by ring opening metathesis polymerization (ROMP). Using the fast initiating ruthenium metathesis catalyst (H2IMes)(pyr)2(Cl)2Ru=CHPh, low polydispersity amphiphilic block copolymers were prepared from a cinnamoyl-containing hydrophobic norbornene monomer and a mesyl-terminated PEG-containing hydrophilic norbornene monomer. Self-assembly into micelles and subsequent cross-linking of the micelle cores by light-activated dimerization of the cinnamoyl groups yielded stable nanoparticles. Incorporation of fluorine-18 was achieved by nucleophilic displacement of the mesylates by the radioactive fluoride ion with 31% incorporation of radioactivity. The resulting positron-emitting nanoparticles are to be used as in vivo molecular imaging agents for use in tumor imaging. 相似文献
9.
The reduction of a variety of highly functionalized N-acylated dihydropyrazoles (1) with BH3 x pyridine is described. The process through which this unexpectedly difficult reduction was discovered and developed is reported. A facile atom-efficient route to the N-acylated dihydropyrazole reduction precursors (1) is also illustrated. The resulting acylpyrazolidine products (2) that arise upon reduction were isolated in good to high yields following exposure to reaction conditions which have been shown to tolerate a variety of different functional groups. Finally, this route has been demonstrated on a kilogram scale and provides direct access to potential proline surrogates for peptidomimetic applications. 相似文献
10.
Rachel L. Meyer Dr. Montaha H. Anjass Brittney E. Petel Dr. William W. Brennessel Prof. Carsten Streb Prof. Ellen M. Matson 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(44):9905-9914
The rational control of the electrochemical properties of polyoxovanadate-alkoxide clusters is dependent on understanding the influence of various synthetic modifications on the overall redox processes of these systems. In this work, the electronic consequences of ligand substitution at the heteroion in a heterometal-functionalized cluster was examined. The redox properties of [V5O6(OCH3)12FeCl] ( 1-[V5FeCl] ) and [V5O6(OCH3)12Fe]X ( 2-[V5Fe]X ; X=ClO4, OTf) were compared in order to assess the effects of changing the coordination environment around the iron center on the electrochemical properties of the cluster. Coordination of a chloride anion to iron leads to an anodic shift in redox events. Theoretical modelling of the electronic structure of these heterometal-functionalized clusters reveals that differences in the redox profiles of 1-[V5FeCl] and 2-[V5Fe]X arise from changes in the number of ligands surrounding the iron center (e.g., 6-coordinate vs. 5-coordinate). Specifically, binding of the chloride to the sixth coordination site appears to change the orbital interaction between the iron and the delocalized electronic structure of the mixed-valent polyoxovanadate core. Tuning the heterometal coordination environment can therefore be used to modulate the redox properties of the whole cluster. 相似文献