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11.
Enantioselective catalytic epoxidation of olefins is an important problem from both practical and mechanistic points of view. The origins of chiral induction by asymmetric porphyrin and salen complexes were investigated by FT-NMR T1 relaxation techniques. A new chiral vaulted porphyrin (1) that carries (S)-binaphthyl-L-alanine straps across both faces of the porphyrin macrocycle was synthesized and characterized. (R)-styrene oxide was obtained in > 90% ee in the initial stages of styrene epoxidation with F5PhIO catalyzed by 1-Fe(III)Cl. The transition state for olefin epoxidation with high-valent metal-oxo species was modeled by coordinating epoxides to paramagnetic copper complexes of the corresponding ligands. The epoxide enantiomer that better fit the chiral cavity of the catalyst, as revealed by T1 relaxation measurements, was also the major product of catalytic olefin epoxidation. These results are consistent with the "lock-and-key" mechanism of asymmetric catalysis by metalloporphyrins. The copper complex of a chiral salen ligand showed no differentiation in terms of T1 relaxation rates between the enantiomers of cis-beta-methylstyrene oxide in contrast to the high enantioselectivity observed for catalytic epoxidation. 相似文献
12.
Infections due to Lancefield group F and related Streptococci (S. milleri, S. anginosus) 总被引:1,自引:0,他引:1
DM Shlaes PI Lerner E Wolinsky KV Gopalakrishna 《Canadian Metallurgical Quarterly》1981,60(3):197-207
We can no longer accept classification of streptococci solely on the basis of hemolytic reactions or Lancefield agglutinations. While the "viridans" streptococci cannot be serologically differentiated, physiological separation of the species offers a satisfactory method of classifying human isolates. We review the microbiology of Lancefield group F and related streptococci (S. milleri, S. anginosus), emphasizing microbial ecology and current taxonomic considerations. A series of 28 patients infected with these organisms is presented. There was a striking male predominance in the series (6:1) as well as an obvious association with underlying diseases and/or antecedent trauma. The most remarkable feature of these pathogens is their predilection for abscess formation, confirming their overdue recognition as the most common "viridans" streptococcus recovered from abscesses within internal organs. We observed purulent disease of the nervous and skeletal systems, oral cavity, lung and pleural space, abdomen and subcutaneous tissues. Microbial synergy (i.e. polymicrobic infection) was not a requisite for abscess formation. Four of the five deaths in this series occurred in patients 60 years of age of older. Some degree of variability in antimicrobial susceptibility was noted, so speciation alone may not always provide sufficient information on which to base a therapeutic decision. 相似文献
13.
Mark E. Borsuk Craig A. Stow Kenneth H. Reckhow 《Canadian Metallurgical Quarterly》2004,130(6):605-614
The total maximum daily load (TMDL) concept provides the basis for regulating pollution load from riverine sources to impaired water bodies. However, load is comprised of two components: flow and concentration. These two components may have confounding, or even conflicting, effects on waterbody attributes of concern. This is particularly the case for dynamic, advective systems, such as estuaries. Resolving these components is critical for properly predicting the response of impaired systems to watershed management actions. The Neuse River Estuary in North Carolina is an example of such an impaired system. Nitrogen has been identified as the pollutant of concern, and the process of developing a TMDL for nitrogen is underway. We, therefore, analyze the extensive data that have been collected for the Neuse River and estuary to investigate spatiotemporal relationships between river flow, riverine total nitrogen (TN) inputs, water temperature, dissolved inorganic nitrogen concentration, algal density, and primary productivity. Results support the belief that phytoplankton in the estuary are under substantial riverine control. However, the riverine TN concentration alone has only a minor role in determining estuarine chlorophyll concentration. River flow has a stronger influence, likely through its effects on down-estuary nitrogen delivery, residence time, salinity, and turbidity. These results imply that using riverine nitrogen load as the metric to evaluate watershed nutrient management may not be appropriate. While nitrogen controls should reduce loads in the long term, in the short term, river flow is the dominant component of load and has the opposite effect of nitrogen on algae at the up-estuary locations. 相似文献
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PM28A is a major intrinsic protein of the spinach leaf plasma membrane and the major phosphoprotein. Phosphorylation of PM28A is dependent in vivo on the apoplastic water potential and in vitro on submicromolar concentrations of Ca2+. Here, we demonstrate that PM28A is an aquaporin and that its water channel activity is regulated by phosphorylation. Wild-type and mutant forms of PM28A, in which putative phosphorylation sites had been knocked out, were expressed in Xenopus oocytes, and the resulting increase in osmotic water permeability was measured in the presence or absence of an inhibitor of protein kinases (K252a) or of an inhibitor of protein phosphatases (okadaic acid). The results indicate that the water channel activity of PM28A is regulated by phosphorylation of two serine residues, Ser-115 in the first cytoplasmic loop and Ser-274 in the C-terminal region. Labeling of spinach leaves with 32P-orthophosphate and subsequent sequencing of PM28A-derived peptides demonstrated that Ser-274 is phosphorylated in vivo, whereas phosphorylation of Ser-115, a residue conserved among all plant plasma membrane aquaporins, could not be demonstrated. This identifies Ser-274 of PM28A as the amino acid residue being phosphorylated in vivo in response to increasing apoplastic water potential and dephosphorylated in response to decreasing water potential. Taken together, our results suggest an active role for PM28A in maintaining cellular water balance. 相似文献
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Uncertainty, imprecision, and the precautionary principle in climate change assessment. 总被引:1,自引:0,他引:1
Statistical decision theory can provide useful support for climate change decisions made under conditions of uncertainty. However, the probability distributions used to calculate expected costs in decision theory are themselves subject to uncertainty, disagreement, or ambiguity in their specification. This imprecision can be described using sets of probability measures, from which upper and lower bounds on expectations can be calculated. However, many representations, or classes, of probability measures are possible. We describe six of the more useful classes and demonstrate how each may be used to represent climate change uncertainties. When expected costs are specified by bounds, rather than precise values, the conventional decision criterion of minimum expected cost is insufficient to reach a unique decision. Alternative criteria are required, and the criterion of minimum upper expected cost may be desirable because it is consistent with the precautionary principle. Using simple climate and economics models as an example, we determine the carbon dioxide emissions levels that have minimum upper expected cost for each of the selected classes. There can be wide differences in these emissions levels and their associated costs, emphasizing the need for care when selecting an appropriate class. 相似文献
18.
The authors of the present article were the first to work out theoretical foundations and methods of physiological diagnosis of neurocirculatory dystonia. Criteria of tension of myocardial functional structures and central regulatory mechanisms have been identified both in healthy subjects and cardiological patients. It has been ascertained that degree and systematic character of tension cause the physiological risk factors for cardio-pathology to develop, 6 types were identified of loading adaptation of the heart caused by extent of its tension, in individuals with neurocirculatory dystonia. Each of the types disclosed is characterized by a dynamics of the functional volumes proportions as well as by peculiarities of the adaptation mechanisms. Physiological diagnosis of functioning of the heart is one of major methods of the primary prophylaxis of neurocirculatory dystonias as well as prevention of aggravation of their course. 相似文献
19.
AV Demin AV Kolesnikov MA Olfer'ev PV Favorov KV Fegeding AG Gabibov NV Gnuchev 《Canadian Metallurgical Quarterly》1998,34(10):1333-1337
A new system for the expression of a catalytic light chain antibody to the vasoactive intestinal peptide is described. The system made possible the isolation the large amounts of a homogeneous protein without any additional peptide domains. The preparation obtained can be used in further experiments on light chain crystallization and in X-ray-structural analysis of its catalytic center. 相似文献
20.
Necrotizing fasciitis is a rare soft tissue infection with a high rate of mortality. Decreased capacity of the immune response is the overall disposing factor. Necrotizing fasciitis can develop very rapidly, and a rapid diagnosis and aggressive surgery provides the best prognosis. 相似文献