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101.
Surface‐Tuned Electron Transfer and Electrocatalysis of Hexameric Tyrosine‐Coordinated Heme Protein 下载免费PDF全文
Dr. Lei Peng Dr. Tillmann Utesch Dr. Aysu Yarman Dr. Jae‐Hun Jeoung Silke Steinborn Prof. Dr. Holger Dobbek Dr. Maria Andrea Mroginski Johannes Tanne Prof. Dr. Ulla Wollenberger Prof. Dr. Frieder W. Scheller 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(20):7596-7602
Molecular modeling, electrochemical methods, and quartz crystal microbalance were used to characterize immobilized hexameric tyrosine‐coordinated heme protein (HTHP) on bare carbon or on gold electrodes modified with positively and negatively charged self‐assembled monolayers (SAMs), respectively. HTHP binds to the positively charged surface but no direct electron transfer (DET) is found due to the long distance of the active sites from the electrode surfaces. At carboxyl‐terminated surfaces, the neutrally charged bottom of HTHP can bind to the SAM. For this “disc” orientation all six hemes are close to the electrode and their direct electron transfer should be efficient. HTHP on all negatively charged SAMs showed a quasi‐reversible redox behavior with rate constant ks values between 0.93 and 2.86 s?1 and apparent formal potentials ${E{{0{^{\prime }}\hfill \atop {\rm app}\hfill}}}$ between ‐131.1 and ‐249.1 mV. On the MUA/MU‐modified electrode, the maximum surface concentration corresponds to a complete monolayer of the hexameric HTHP in the disc orientation. HTHP electrostatically immobilized on negatively charged SAMs shows electrocatalysis of peroxide reduction and enzymatic oxidation of NADH. 相似文献
102.
A polyclonal antibody (Ab) for the progestin levonorgestrel (LNG) was generated, and immunochemical assays for its detection, clean-up and concentration were developed. A highly specific microplate diagnostic assay for the detection of LNG was developed that used the enzyme linked immunosorbent assay (ELISA) method. The LNG ELISA developed was sensitive and reproducible; it exhibited I50 and I20 values of 3.3 ± 1.8 ng mL−1 and 0.6 ± 0.4 ng mL−1, respectively, and the Abs did not cross react with any of the tested steroid hormones. The above Abs were used to develop a sol-gel-based immunoaffinity purification (IAP) method for concentration and clean-up of LNG that is compatible with subsequent immunochemical or instrumental chemical analytical procedures, such as liquid chromatography followed by mass spectrometry (LC-MS/MS). Development of the columns included successful entrapment of Abs within a tetramethoxysilane (TMOS)-based SiO2 polymer network. The Abs could bind the free analyte from solution, and the bound analyte could be easily eluted from the sol-gel matrix at high recoveries. The Ab selectivity towards the antigen was high, in both ELISA and the sol-gel columns, but the entrapped Abs cross-reacted with two other steroid hormones - ethynylestradiol (EE2) and nortestosterone (NT) - which share similar epitopes with LNG, despite the lack of cross reactivity in the ELISA. The validity of the method was investigated by LC-MS/MS and a good analytical correlation was obtained. 相似文献
103.
Margherita Disertori Franz Merkl Silke W. W. Rolles 《Communications in Mathematical Physics》2014,332(2):783-825
We study a lattice sigma model which is expected to reflect Anderson localization and delocalization transition for real symmetric band matrices in 3D, but describes the mixing measure for a vertex reinforced jump process too. For this model we prove exponential localization at any temperature in a strip, and more generally in any quasi-one dimensional graph, with pinning (mass) at only one site. The proof uses a Mermin–Wagner type argument and a transfer operator approach. 相似文献
104.
Markus Gellesch Franziska Hammerath Vicky Süß Marcel Haft Silke Hampel Sabine Wurmehl Bernd Büchner 《Journal of nanoparticle research》2017,19(9):307
The increasing interest in nanoscale materials goes hand in hand with the challenge to reliably characterize the chemical compositions and structural features of nanosized objects in order to relate those to their physical properties. Despite efforts, the analysis of the chemical composition of individual multi-element nanoparticles remains challenging—from the technical point of view as well as from the point of view of measurement statistics. Here, we demonstrate that zero-field solid-state nuclear magnetic resonance (NMR) complements local, single particle transmission electron microscopy (TEM) studies with information on a large assembly of chemically complex nanoparticles. The combination of both experimental techniques gives information on the local composition and structure and provides an excellent measurement statistic through the corresponding NMR ensemble measurement. This analytical approach is applicable to many kinds of magnetic materials and therefore may prove very versatile in the future research of particulate magnetic nanomaterials. 相似文献
105.
O Nikel D Laurencin C Bonhomme GE Sroga S Besdo A Lorenz D Vashishth 《The journal of physical chemistry. C, Nanomaterials and interfaces》2012,116(10):6320-6331
Age-related bone fragility fractures present a significant problem for public health. Measures of bone quality are increasingly recognized to complement the conventional bone mineral density (BMD) based assessment of fracture risk. The ability to probe and understand bone quality at the molecular level is desirable in order to unravel how the structure of organic matrix and its association with mineral contribute to the overall mechanical properties. The (13)C{(31)P} REDOR MAS NMR (Rotational Echo Double Resonance Magic Angle Spinning Nuclear Magnetic Resonance) technique is uniquely suited for the study of the structure of the organic-mineral interface in bone. For the first time, we have applied it successfully to analyze the structure of intact (non-powdered) human cortical bone samples, from young healthy and old osteoporotic donors. Loading problems associated with the rapid rotation of intact bone were solved using a Finite Element Analysis (FEA) approach, and a method allowing osteoporotic samples to be balanced and spun reproducibly is described. REDOR NMR parameters were set to allow insight into the arrangement of the amino acids at the mineral interface to be accessed, and SVD (Singular Value Decomposition) was applied to enhance the signal to noise ratio and enable a better analysis of the data. From the REDOR data, it was found that carbon atoms belonging to citrate/glucosaminoglycans (GAGs) are closest to the mineral surface regardless of age or site. In contrast, the arrangement of the collagen backbone at the interface varied with site and age. The relative proximity of two of the main amino acids in bone matrix proteins, hydroxyproline and alanine, with respect to the mineral phase was analyzed in more detail, and discussed in view of glycation measurements which were carried out on the tissues. Overall, this work shows that the (13)C{(31)P} REDOR NMR approach could be used as a complementary technique to assess a novel aspect of bone quality, the organic-mineral interface structure. 相似文献
106.
Konstantin Laun Dr. Benjamin R. Duffus Dr. Stefan Wahlefeld Dr. Sagie Katz Dr. Dennis Belger Prof. Peter Hildebrandt Prof. Maria Andrea Mroginski Prof. Silke Leimkühler Dr. Ingo Zebger 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(54):e202201091
Biological carbon dioxide (CO2) reduction is an important step by which organisms form valuable energy-richer molecules required for further metabolic processes. The Mo-dependent formate dehydrogenase (FDH) from Rhodobacter capsulatus catalyzes reversible formate oxidation to CO2 at a bis-molybdopterin guanine dinucleotide (bis-MGD) cofactor. To elucidate potential substrate binding sites relevant for the mechanism, we studied herein the interaction with the inhibitory molecules azide and cyanate, which are isoelectronic to CO2 and charged as formate. We employed infrared (IR) spectroscopy in combination with density functional theory (DFT) and inhibition kinetics. One distinct inhibitory molecule was found to bind to either a non-competitive or a competitive binding site in the secondary coordination sphere of the active site. Site-directed mutagenesis of key amino acid residues in the vicinity of the bis-MGD cofactor revealed changes in both non-competitive and competitive binding, whereby the inhibitor is in case of the latter interaction presumably bound between the cofactor and the adjacent Arg587. 相似文献
107.
Tobias J. Moritz James A. Brunberg Denise M. Krol Sebastian Wachsmann‐Hogiu Stephen M. Lane James W. Chan 《Journal of Raman spectroscopy : JRS》2010,41(1):33-39
We report the analysis of the vibrational modes of intranuclear protein inclusions isolated from the brain of human subjects with the Fragile X‐associated tremor/ataxia syndrome (FXTAS). In this preliminary study, Raman spectra of optically trapped inclusions were measured and analysed to determine protein composition and structure. Our main findings are as follows: (1) The spectra of protein inclusions are characteristic of H2A and H2B histones, which correlate with previous mass spectrometry (MS) studies; (2) Tyrosine is present in its OH form and exposed at the protein surface; (3) Zn and to a lesser extent Cu bound to histidine side chains are detected in the inclusions; (4) The tryptophan side‐chain torsion angle is calculated to be 102°; (5) Several potential spectroscopic markers for the inclusions of FXTAS are identified. These results show the capability of using laser tweezers Raman spectroscopy to identify protein inclusions in a non‐perturbative way and to gain further insight into the pathogenesis and progression of FXTAS in human subjects and in experimental models of this disorder. Copyright © 2009 John Wiley & Sons, Ltd. 相似文献
108.
Wenzel SC Williamson RM Grünanger C Xu J Gerth K Martinez RA Moss SJ Carroll BJ Grond S Unkefer CJ Müller R Floss HG 《Journal of the American Chemical Society》2006,128(44):14325-14336
Feeding experiments with isotope-labeled precursors rule out hydroxypyruvate and TCA cycle intermediates as the metabolic source of methoxymalonyl-ACP, the substrate for incorporation of "glycolate" units into ansamitocin P-3, soraphen A, and other antibiotics. They point to 1,3-bisphosphoglycerate as the source of the methoxymalonyl moiety and show that its C-1 gives rise to the thioester carbonyl group (and hence C-1 of the "glycolate" unit), and its C-3 becomes the free carboxyl group of methoxymalonyl-ACP, which is lost in the subsequent Claisen condensation on the type I modular polyketide synthases (PKS). d-[1,2-(13)C(2)]Glycerate is also incorporated specifically into the "glycolate" units of soraphen A, but not of ansamitocin P-3, suggesting differences in the ability of the producing organisms to activate glycerate. A biosynthetic pathway from 1,3-bisphosphoglycerate to methoxymalonyl-ACP is proposed. Two new syntheses of R- and S-[1,2-(13)C(2)]glycerol were developed as part of this work. 相似文献
109.
The surfactants perfluorooctanoate (PFOA), perfluorooctane sulfonate (PFOS), and derivatives of the latter have emerged as globally distributed persistent environmental contaminants. Methods for their reliable quantitative determination at ppt-levels (ng/L) are needed in order to detect their main sources, to elucidate their environmental fate, and to identify potential sinks. The common method for water analysis involves preconcentration by SPE followed by LC coupled to ESI MS/MS (LC-ESI-MS/ MS). All sample preparation steps must be carefully optimized in order to arrive at reliable quantitative data. Two major aspects are important: (i) during SPE, contaminations may arise from materials containing traces of PFOA/S; (ii) during LC-ESI-MS/ MS, ionization yields are suppressed by matrix components and depend upon the analyte concentrations in the extracts. The levels of PFOA/S in the river Roter Main near Bayreuth have been determined using the optimized method. 相似文献
110.
Silke Janitza Ender Celik Anne-Laure Boulesteix 《Advances in Data Analysis and Classification》2018,12(4):885-915
Random forests are a commonly used tool for classification and for ranking candidate predictors based on the so-called variable importance measures. These measures attribute scores to the variables reflecting their importance. A drawback of variable importance measures is that there is no natural cutoff that can be used to discriminate between important and non-important variables. Several approaches, for example approaches based on hypothesis testing, were developed for addressing this problem. The existing testing approaches require the repeated computation of random forests. While for low-dimensional settings those approaches might be computationally tractable, for high-dimensional settings typically including thousands of candidate predictors, computing time is enormous. In this article a computationally fast heuristic variable importance test is proposed that is appropriate for high-dimensional data where many variables do not carry any information. The testing approach is based on a modified version of the permutation variable importance, which is inspired by cross-validation procedures. The new approach is tested and compared to the approach of Altmann and colleagues using simulation studies, which are based on real data from high-dimensional binary classification settings. The new approach controls the type I error and has at least comparable power at a substantially smaller computation time in the studies. Thus, it might be used as a computationally fast alternative to existing procedures for high-dimensional data settings where many variables do not carry any information. The new approach is implemented in the R package vita. 相似文献