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1.
The main drawbacks of today's state-of-the-art lithium–air (Li–air) batteries are their low energy efficiency and limited cycle life due to the lack of earth-abundant cathode catalysts that can drive both oxygen reduction and evolution reactions (ORR and OER) at high rates at thermodynamic potentials. Here, inexpensive trimolybdenum phosphide (Mo3P) nanoparticles with an exceptional activity—ORR and OER current densities of 7.21 and 6.85 mA cm−2 at 2.0 and 4.2 V versus Li/Li+, respectively—in an oxygen-saturated non-aqueous electrolyte are reported. The Tafel plots indicate remarkably low charge transfer resistance—Tafel slopes of 35 and 38 mV dec−1 for ORR and OER, respectively—resulting in the lowest ORR overpotential of 4.0 mV and OER overpotential of 5.1 mV reported to date. Using this catalyst, a Li–air battery cell with low discharge and charge overpotentials of 80 and 270 mV, respectively, and high energy efficiency of 90.2% in the first cycle is demonstrated. A long cycle life of 1200 is also achieved for this cell. Density functional theory calculations of ORR and OER on Mo3P (110) reveal that an oxide overlayer formed on the surface gives rise to the observed high ORR and OER electrocatalytic activity and small discharge/charge overpotentials.  相似文献   
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Ermittlung von Temperaturverteilung, Abkühlungsverlauf, Gefüge, Härte und Eigenspannungen bei mittig erwärmten Stahlplatten aus St 37-3 und StE 70. Einfluß des Umwandlungsverhaltens auf die Eigenspannungen. Deutung der Eigenspannungsentstehung beim Zusammenwirken von Wärme- und Umwandlungsspannungen.  相似文献   
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Untersuchung des Schrumpfungs- und Umwandlungsverhaltens von Schweißproben aus austenitischem und hochfestem Grund- und Schweißzusatzwerkstoff. Messung von Eigenspannungen im Schweißnahtbereich. Erklärung der Eigenspannungen aus Temperaturverläufen und Härtemessungen im Schweißnahtbereich sowie aus Weg-Zeit-Aufschreibungen für das freie Ende einseitig eingespannter Schweißproben. Deutung der Umwandlungsvorgänge durch Zeit-Temperatur-Umwandlungsschaubilder.  相似文献   
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The inability to process many covalent organic frameworks (COFs) as thin films plagues their widespread utilization. Herein, a vapor-phase pathway for the bottom-up synthesis of a class of porphyrin-based COFs is presented. This approach allows integrating electrocatalysts made of metal-ion-containing COFs into the electrodes’ architectures in a single-step synthesis and deposition. By precisely controlling the metal sites at the atomic level, remarkable electrocatalytic performance is achieved, resulting in unprecedentedly high mass activity values. How the choice of metal atoms, i.e., cobalt and copper, can determine the catalytic activities of POR-COFs is demonstrated. The theoretical data proves that the Cu site is highly active for nitrate conversion to ammonia on the synthesized COFs.  相似文献   
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L ‐α‐Aminoadipic acid reductases catalyze the ATP‐ and NADPH‐dependent reduction of L ‐α‐aminoadipic acid to the corresponding 6‐semialdehyde during fungal L ‐lysine biosynthesis. These reductases resemble peptide synthetases with regard to their multidomain composition but feature a unique domain of elusive function—now referred to as an adenylation activating (ADA) domain—that extends the reductase N‐terminally. Truncated enzymes based on NPS3, the L ‐α‐aminoadipic acid reductase of the basidiomycete Ceriporiopsis subvermispora, lacking the ADA domain either partially or entirely were tested for activity in vitro, together with an ADA‐adenylation didomain and the ADA domainless adenylation domain. We provide evidence that the ADA domain is required for substrate adenylation: that is, the initial step of the catalytic turnover. Our biochemical data are supported by in silico modeling that identified the ADA domain as a partial peptide synthetase condensation domain.  相似文献   
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Naive T lymphocytes specific for a given primary antigen occur in low frequencies and require the relevant antigen to be presented by specialist antigen presenting cells (APC), i.e., dendritic cells (DC). For these reasons, the in vitro induction of primary T lymphocyte responses remains a significant technical challenge. We have attempted to improve current strategies for generating in vitro responses by optimising (i) isolation and concomitant activation of DC from peripheral blood, (ii) uptake, processing and presentation of antigen by DC and (iii) antigen driven T lymphocyte proliferation. We established that RPMI 1640 media supplemented with 10% autologous serum resulted in the best yield of CMRF-44+, CD14-, CD19- DC after enrichment over a Nycodenz gradient. Optimal presentation of whole protein and peptide antigen was achieved by addition after the purification of the APC, i.e., at the start of the T lymphocyte proliferation assay. RPMI 1640 supplemented with 10% autologous serum or plasma supported the best antigen driven specific T lymphocyte responses. Using these optimised conditions, we compared the efficacy of PBMC and purified blood DC for priming T lymphocyte responses to the chronic myeloid leukaemia (CML) specific bcr-abl (b3a2) peptide. Peptide specific T lymphocyte responses were generated with both purified DC and whole PBMC, suggesting that T lymphocyte precursor frequency was the limiting factor in these experiments. These results will aid in the generation of human T lymphocyte lines to primary antigens, for in vitro and therapeutic applications.  相似文献   
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Zusammenfassung Während der Incubation von Soja-Lipoxygenase mit Linolsäure entstehen flüchtige Verbindungen, für deren Genese sich mindestens zwei Möglichkeiten abzeichnen: Die eine Möglichkeit besteht darin, daß aus bereits vorgebildeten Linolsäurehydroperoxiden Spaltprodukte auftreten. Zum andern können — je nach äußeren Bedingungen (Temperatur, O2-Druck, Partnerkonzentration, u.a.) — flüchtige Stoffe verschiedener chemischer Natur aus radikalischen Reaktionszwischenstufen entstehen. Durch Versuche mit Hydroperoxid-abbauenden Enzymen (Peroxidasen) und unter Verwendung radioaktiv markierter Linolsäurehydroperoxide wurden die angedeuteten Bildungswege untersucht. Unsere epxerimentellen Ergebnisse zeigen, daß die Bildung der hier untersuchten flüchtigen Verbindungen aus Reaktionszwischenstufen vor sich geht. Festzuhalten ist jedoch, daß n-Hexanal neben der Bildung aus Reaktionszwischenstufen auch aus dem Zerfall vorher gebildeter Hydroperoxide entsteht. Das schon von uns früher angegebene Rekationsschema [2] konnte nunmehr durch diese Untersuchungen experimentell gesichert werden.
Investigations on the development of volatile substances during lipoxygenase-linolic-acid-reaction
Summary During incubation of soja-Lipoxygenase with Linolic acid, volatile compounds are formed the development of which can be seen in two possible ways: from preformed Linolic-acid-hydroperoxides splitproducts arise or volatile substances of different chemical nature are built depending on the reaction conditions like temperature, O2-pressure, partner-concentration etc. By trials with hydroperoxdde-decomposing enzymes (peroxidase) and by means of radioactive labelled Linolic-acid-hydroperoxides the pathways mentioned above were investigated. The results indicate that the volatile compounds are built from by-products; n-hexanal was formed from these by-products as well as from decomposed hydroperoxide. The previously proposed reaction-scheme has this been ascertained by experimental means.


Herrn Prof. Dr. J. Eisenbrand zum 75. Geburtstag gewidmet.  相似文献   
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