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11.
Analyte transfer from the matrix in a thin layer distillation (TLD) cell and its subsequent measurement were investigated in a flow injection configuration. We designed the cell such that the donor and acceptor streams flowed in parallel channels separated by a thin dividing wall. The matrix transfer process involved room-temperature distillation of the analyte into the headspace of the TLD cell and its subsequent condensation/uptake by a concurrently flowing acceptor stream. There are no membranes; hence there are no membrane-related problems. The TLD system design was optimized with respect to its dimensions and operational parameters. Throughput and sensitivity were compared with a conventional pervaporation flow injection (PFI) system for ammonia and five different amines. For the higher molecular mass amines, the TLD approach provided comparable or superior performance. The TLD technique should be an attractive approach for online analysis of volatile chemical species in ‘dirty’ samples, especially for volatile analytes of higher molecular mass. 相似文献
12.
A fluorimetric flow-injection procedure with a single reagent solution containing p-hydroxyphenylacetic acid, peroxidase and ammonia permits the determination of aqueous hydrogen peroxide in the range 10?8?10?4 M; 30–60 samples can be processed per hour. The method exhibits a wide linear range and is insensitive to sample pH within the range 2–6. 相似文献
13.
Amino Acid based cationic surfactants in aqueous solution: physicochemical study and application of supramolecular chirality in ketone reduction 总被引:2,自引:0,他引:2
Roy S Das D Dasgupta A Mitra RN Das PK 《Langmuir : the ACS journal of surfaces and colloids》2005,21(23):10398-10404
The present study provides a molecular understanding of the origin of the chirality in aqueous micelles and its correlation with the proficiency of stereoselective ketone reduction. The effects of varied headgroup architecture on the surface-active properties as well as on other microstructural parameters were studied and correlated to the structural differences of these naturally occurring amino acid containing surfactants (1-4). Micropolarity sensed by pyrene showed that the micelles prepared using 1-4 are mostly hydrated; particularly large headgroup size surfactant produces more polar environment. A theoretical study was done to quantify the varied spatial dissymmetry for all four surfactants. Asymmetric reduction of prochiral ketones was carried out at the aqueous micellar interface of these chiral amphiphiles by exploiting the supramolecular chirality as evidenced from a circular dichroism study. The enantioselectivity of the reduction process is rationally improved through increase in spatial dissymmetry and steric constraint imposed at the micellar interface by the polar head of surfactants. 相似文献
14.
A system of sequential injection analysis (SIA) in capillary format based on an electroosmotic pump is introduced. The system exhibits excellent reliability and reproducibility (relative standard deviation 0.6-0.8%) for both simple and complex chemical reaction systems. The simplicity and flexibility of the field-decoupled electroosmotic pump has been found to be ideally suited for SIA. There is significant potential for miniaturizing the necessary instrumentation. 相似文献
15.
A spectrophotometric flow injection method for the determination of H(2)O(2) in aqueous solution is presented. The technique is based on the oxidative condensation reaction between 1-anilinonaphthalene-8-sulfonic acid (ANSA) and 4-aminoantipyrine (AAP) in the presence of H(2)O(2). Hematin is a good peroxidatic catalyst for this reaction; its effectiveness is significantly enhanced in an ammoniacal medium. If the yellow product formed in the alkaline medium is acidified, a blue chromophore (lambda(max) 592 nm) is formed; a surfactant is necessary to keep the blue compound in solution. Chemical and instrumental parameters for FIA were evaluated and optimized. A detection limit of 0.3muM was achieved with a linear dynamic range extending to 50muM. The typical relative standard deviation is 1.5% or better. The structure of the reaction product has been identified. 相似文献
16.
Chemical synthesis of the trisaccharide of the steroid glycoside Sokodoside B isolated from Erylus placenta is reported. Stereoselective, high-yielding glycosylation strategies through thioglycoside activation using H2SO4 immobilized on silica in conjunction with N-iodosuccinimide are used for better results. A late stage TEMPO-mediated oxidation was performed for the formation of required uronic acid moiety. An analog of the target trisaccharide is also prepared by using a bis-glycosylation approach. 相似文献
17.
An air-carrier continuous analysis system (ACCAS) is introduced that permits the reaction of a fixed volume of a sample with fixed volumes of one or more reagents, either simultaneously or sequentially. ACCAS is envisioned as a complement to segmented continuous-flow analysis (SCFA) and flow-injection analysis (FIA). ACCAS is capable of high throughput rates ( approximately 3600 samples/hr) and low waste generation. 相似文献
18.
Jyotirmoy Chakravarty Rupak Dasgupta Jayanta K Ray Usha R Ghatak 《Proceedings Mathematical Sciences》1977,86(3):317-325
The gross structures of the cyclised products from the acid-catalysed cyclisations of 2-benzyl-1, 3-dimethylcyclohexanol (6) and 1-benzyl-3, 5-dimethylcyclohexanol (11) revealing the influence of the structure of the benzylcyclohexanol derivative, and of the cyclisation reagent, have been evaluated. Polyphosphoric acid and aluminium chloride catalysed cyclisations of (6) result in the formation of predominantly 1, 4a-dimethyl-1, 2, 3, 4, 4a, 9a-hexahydrofluorene (7) and 4, 9-dimethyl-7, 8-benzobicyclo [3.3.1] non-7-ene (9) respectively. Under the same conditions, (11) produced cyclised products consisting mostly the benzobicyclo [3.3.1] non-7-ene derivative (12), characterised through 1,3-dimethyl-7,8-benzobicyclo [3.3.1] non-6-oxo-7-ene (14) by oxidation with chromium trioxide. Phosphorus pentoxide induced cyclisation of (6), followed by oxidation gave a mixture of the bridged-ring ketone (10) and the 9-oxohydrofluorene (8) in a ratio ofca. 3 : 2, whereas 2-benzyl-5-methylcyclohexanol (19) resulted in mostly 2-methyl-7,8-benzobicyclo [3.3.1] non-6-oxo-7-ene (19). 相似文献
19.
This review summarizes progress in capillary ion chromatography. Theoretical aspects and practical limitations of packed and open tubular capillary columns are considered. Applications of packed and open tubular capillary IC are described. Emerging technologies such chip-scale IC and the use of monolithic columns are discussed. 相似文献
20.
This work describes the modification of the chelating agent 1,4,7,10-tetraazacyclododecane-N,N',N' ',N' "-tetraacetic acid (DOTA) to improve the rate of metal loading for radioimmunotherapy applications. Previous ab initio calculations predicted that the compounds 1,4,7,10-tetra(carboxyethyl)-1,4,7,10-tetraazacyclododecane (DO4Pr) and 1,4,7-tris(carboxymethyl)-10-(carboxyethyl)-1,4,7,10-tetraazacyclododecane (DO3A1Pr) have a ca. 2000-fold improvement in yttrium metal loading rates compared to those of DOTA (Jang, Y. H.; Blanco, M.; Dasgupta, S.; Keire, D. A.; Shively, J. E.; Goddard, W. A., III. J. Am. Chem. Soc. 1999, 121, 6142-6151). In this study, we report the synthesis, purification, (1)H-NMR chemical shift assignments, pK(a) values, metal loading rate measurements, and additional ab initio calculations of these two compounds. The yttrium loading rates of DO3A1Pr are approximately twice those of DOTA, at pH 4.6 and 37 degrees C. The NMR data indicates that the DO4Pr analogue forms a stable type I complex but does not form a type II complex. The new ab initio calculations performed on DO4Pr and DO3A1Pr indicate that the rate-determining step is the deprotonation of the first macrocycle amine proton, not the second proton as assumed in the previous calculations. The new calculations predict an improvement in the rate of metal loading that more closely matches the experimentally observed change in the rate. 相似文献