全文获取类型
收费全文 | 861篇 |
免费 | 54篇 |
国内免费 | 144篇 |
专业分类
化学 | 914篇 |
晶体学 | 5篇 |
力学 | 1篇 |
综合类 | 16篇 |
数学 | 15篇 |
物理学 | 108篇 |
出版年
2024年 | 1篇 |
2023年 | 14篇 |
2022年 | 49篇 |
2021年 | 63篇 |
2020年 | 47篇 |
2019年 | 39篇 |
2018年 | 24篇 |
2017年 | 33篇 |
2016年 | 50篇 |
2015年 | 35篇 |
2014年 | 40篇 |
2013年 | 59篇 |
2012年 | 85篇 |
2011年 | 40篇 |
2010年 | 31篇 |
2009年 | 36篇 |
2008年 | 50篇 |
2007年 | 31篇 |
2006年 | 33篇 |
2005年 | 39篇 |
2004年 | 43篇 |
2003年 | 23篇 |
2002年 | 32篇 |
2001年 | 25篇 |
2000年 | 14篇 |
1999年 | 9篇 |
1998年 | 21篇 |
1997年 | 12篇 |
1996年 | 12篇 |
1995年 | 10篇 |
1994年 | 4篇 |
1993年 | 6篇 |
1992年 | 8篇 |
1991年 | 8篇 |
1990年 | 5篇 |
1989年 | 2篇 |
1988年 | 3篇 |
1987年 | 2篇 |
1986年 | 1篇 |
1985年 | 6篇 |
1984年 | 1篇 |
1983年 | 2篇 |
1982年 | 5篇 |
1981年 | 2篇 |
1978年 | 2篇 |
1976年 | 2篇 |
排序方式: 共有1059条查询结果,搜索用时 15 毫秒
61.
62.
《Analytical letters》2012,45(14):2883-2899
ABSTRACT|The catalytic activity of various mimetic enzymes instead of the peroxidase have been investigated by 4-aminoantipyrine (4-AAP) and 2, 3, 4-trichlorophenol (TCP) to form a dye utilizing hydrogen peroxide as hydrogen acceptor. The different Chlorophenolic derivatives, which act as a substrate in β-CD-hemin-H2O2-4-AAP catalytic reaction, have been systematically studied.|Meanwhile, the relationship of structure-effect for the β-CD-hemin as catalyst, and chlorphenols as substrate has been respectively discussed. The mechanism of catalytic reaction has been investigated. The results showed that β-CD-hemin was the best mimetic enzyme for peroxidase among those tested and TCP was a good substrate for the determination of hydrogen peroxide with β-CD-hemin. The method for the determination of hydrogen peroxide was proposed using 4-AAP-TCP system with β-CD-hemin as catalyst. A linear calibration graph was obtained over the H2O2 concentration of 4.8×10-?8-7.7×10-?5M, and the relative standard deviation at a H2O2 concentration of 2.8×10-?5M was 2.5%. The apparent molar absorptivity of the chromogenic reaction for H2O2 was 1.54× 104 L.mol-?1.cm?1. Satisfactory results were obtained in the determination of H2O2 in synthetic samples by this method. Also, the method was coupled with the glucose oxidation reaction to determination glucose in human serum. 相似文献
63.
《Analytical letters》2012,45(13):1157-1165
Abstract Acidification of a solution of glucose oxidase in 35 percent glycerol with 10 percent sulfuric acid and a gel filtration of this acidified glucose oxidase solution yielded apo-glucose oxidase with low residual enzyme activity. Further treatment with charcoal gave apo-glucose oxidase which is devoid of enzyme activity. Using this apo-glucose oxidase, it was possible to measure flavin adenine dinucleotide amperometrically at extremely low concentrations (10?12 M) with ease, rapidity, and convenience. 相似文献
64.
《Analytical letters》2012,45(8):1622-1631
Abstract Catalyzed determination of glucose with mimic glucose oxidase is constructed by the reaction of β‐cyclodextrin, maleic anhydride, and chloroacetic acid with iron trichloride in hydrogen peroxide. The method is simple and convenient, and sensitivity and repeatability are ideal. Beer's law is obeyed in a concentration range of 30–197 µg · ml?1 glucose with an excellent correlation coefficient (r=0.9994), while the detection limit is 4.10 µg · ml?1, the RSD is 0.98% (n=8). The recovery of sample is 95.8–103.1%. 相似文献
65.
Cellulase retention and sugar removal by membrane ultrafiltration during lignocellulosic biomass hydrolysis 总被引:1,自引:0,他引:1
Technologies suitable for the separation and reuse of cellulase enzymes during the enzymatic saccharification of pretreated
corn stover are investigated to examine the economic and technical viability of processes that promote cellulase reuse while
removing inhibitory reaction products such as glucose and cellobiose. The simplest and most suitable separation is a filter
with relatively large pores on the order of 20–25 mm that retains residual corn stover solids while passing reaction products
such as glucose and cellobiose to form a sugar stream for a variety of end uses. Such a simple separation is effective because
cellulase remains bound to the residual solids. Ultrafiltration using 50-kDa polyethersulfone membranes to recover cellulase
enzymes in solution was shown not to enhance further the saccharification rate or overall conversion. Instead, it appears
that the necessary cellulase enzymes, including β-glucosidase, are tightly bound to the substrate; when fresh corn stover
is contacted with highly washed residual solids, without the addition of fresh enzymes, glucose is generated at a high rate.
When filtration was applied multiple times, the concentration of inhibitory reaction products such as glucose and cellobiose
was reduced from 70 to 10 g/L. However, an enhanced saccharification performance was not observed, most likely because the
concentration of the inhibitory products remained too high. Further reduction in the product concentration was not investigated,
because it would make the reaction unnecessarily complex and result in a product stream that is much too dilute to be useful.
Finally, an economic analysis shows that reuse of cellulase can reduce glucose production costs, especially when the enzyme
price is high. The most economic performance is shown to occur when the cellulase enzyme is reused and a small amount of fresh
enzyme is added after each separation step to replace lost or deactivated enzyme. 相似文献
66.
Su‐Juan Li Chen Wang Zeng‐Qiang Wu Jing‐Juan Xu Prof. Xing‐Hua Xia Prof. Hong‐Yuan Chen Prof. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2010,16(33):10186-10194
To understand the fundamentals of enzymatic reactions confined in micro‐/nanosystems, the construction of a small enzyme reactor coupled with an integrated real‐time detection system for monitoring the kinetic information is a significant challenge. Nano‐enzyme array reactors were fabricated by covalently linking enzymes to the inner channels of a porous anodic alumina (PAA) membrane. The mechanical stability of this nanodevice enables us to integrate an electrochemical detector for the real‐time monitoring of the formation of the enzyme reaction product by sputtering a thin Pt film on one side of the PAA membrane. Because the enzymatic reaction is confined in a limited nanospace, the mass transport of the substrate would influence the reaction kinetics considerably. Therefore, the oxidation of glucose by dissolved oxygen catalyzed by immobilized glucose oxidase was used as a model to investigate the mass‐transport‐related enzymatic reaction kinetics in confined nanospaces. The activity and stability of the enzyme immobilized in the nanochannels was enhanced. In this nano‐enzyme reactor, the enzymatic reaction was controlled by mass transport if the flux was low. With an increase in the flux (e.g., >50 μL min?1), the enzymatic reaction kinetics became the rate‐determining step. This change resulted in the decrease in the conversion efficiency of the nano‐enzyme reactor and the apparent Michaelis–Menten constant with an increase in substrate flux. This nanodevice integrated with an electrochemical detector could help to understand the fundamentals of enzymatic reactions confined in nanospaces and provide a platform for the design of highly efficient enzyme reactors. In addition, we believe that such nanodevices will find widespread applications in biosensing, drug screening, and biochemical synthesis. 相似文献
67.
Mika Tiainen Hannu Maaheimo Pasi Soininen Reino Laatikainen 《Magnetic resonance in chemistry : MRC》2010,48(2):117-122
The one‐ and two‐bond 13C isotope shifts, typically ?1.5 to ?2.5 ppb and ?0.7 ppb respectively, in non‐cyclic aliphatic systems and up to ?4.4 ppb and ?1.0 ppb in glucose cause effects that need to be taken into account in the adaptive NMR spectral library‐based quantification of the isotopomer mixtures. In this work, NMR spectral analyses of some 13C‐labelled amino acids, D ‐glucose and other small compounds were performed in order to obtain rules for prediction of the 13C isotope effects on 1H chemical shifts. It is proposed that using the additivity rules, the isotope effects can be predicted with a sufficient accuracy for amino acid isotopomer applications. For glucose the effects were found strongly non‐additive. The complete spectral analysis of fully 13C‐labelled D ‐glucose made it also possible to assign the exocyclic proton signals of the glucose. Copyright © 2009 John Wiley & Sons, Ltd. 相似文献
68.
A need for rapid toxicity techniques has seen recent research into developing new microbiological assays and characterising their toxicity responses using a range of substances. A microbiological bioassay that determines changes in ferricyanide-mediated respiration for toxicity measurement (FM-TOX) shows particular promise. The development and optimisation of an improved FM-TOX method, incorporating novel features, is described using Escherichia coli as the biocatalyst. Omission of an exogenous carbon source, used in previously described FM-TOX assays, substantially improves the assay sensitivity. In addition, the development of a two-step procedure (toxicant exposure followed by determination of microbial respiratory activity) was found to enhance the inhibition of E. coli by 3,5-dichlorophenol and four other toxicants, compared to single-step procedures. Other assay parameters, such as the ferricyanide concentration, exposure times and optical density of the biocatalyst were also optimised, sometimes based on practical aspects. Toxicity tests were carried out using the adopted technique on both organic and inorganic toxicants, with classic sigmoid-shaped dose-response curves observed, as well as some non-standard responses. IC50 data is presented for a number of common toxicants. The optimised assay provides a good foundation for further toxicity testing using E. coli, as well as the potential for expanding the technique to utilise other bacteria with complementary toxicity responses, thereby allowing use of the assay in a range of applications. 相似文献
69.
W. Russ Algar 《Analytica chimica acta》2010,673(1):1-25
A comprehensive review of the development of assays, bioprobes, and biosensors using quantum dots (QDs) as integrated components is presented. In contrast to a QD that is selectively introduced as a label, an integrated QD is one that is present in a system throughout a bioanalysis, and simultaneously has a role in transduction and as a scaffold for biorecognition. Through a diverse array of coatings and bioconjugation strategies, it is possible to use QDs as a scaffold for biorecognition events. The modulation of QD luminescence provides the opportunity for the transduction of these events via fluorescence resonance energy transfer (FRET), bioluminescence resonance energy transfer (BRET), charge transfer quenching, and electrochemiluminescence (ECL). An overview of the basic concepts and principles underlying the use of QDs with each of these transduction methods is provided, along with many examples of their application in biological sensing. The latter include: the detection of small molecules using enzyme-linked methods, or using aptamers as affinity probes; the detection of proteins via immunoassays or aptamers; nucleic acid hybridization assays; and assays for protease or nuclease activity. Strategies for multiplexed detection are highlighted among these examples. Although the majority of developments to date have been in vitro, QD-based methods for ex vivo biological sensing are emerging. Some special attention is given to the development of solid-phase assays, which offer certain advantages over their solution-phase counterparts. 相似文献
70.