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131.
Summary In this study a new approach is presented for on-line radiometric detection in reversed phase LC of medium to low polarity
compounds labelled with14C.
The test compounds,14C-carbaryl and14C-parathion, are extracted post-column into a non-water miscible liquid scintillation cocktail. The segmented two-phase system
formed is introduced into the beta-detector without phase separation and collected in a capillary storage tube.
After completion of the LC separation and detection process, the direction of the flow in the storage system is reversed and
the segmented contents of the loop led at lower flow-rates through the beta-detector again. An enhanced signal, corresponding
to the increase in counting time is obtained without measurable peak broadening.
The lowest possible detection limit of the system is 9 counts per peak corresponding to subnanogram quantities of tested pesticides.
Calibration curves are linear over at least 2 orders of magnitude and have the expected theoretical slopes.
The reproducibility of the system is better than 4 % rel. S.D. An application to a recovery study of parathion shows the practical
potential of this technique.
Presented at the 15th International Symposium on Chromatography, Nürnberg, October 1984 相似文献
132.
The interaction of ethidium bromide (2,7-diamino-10-ethyl-9-phenylphenanthridinium bromide; EB) with double stranded (ds) calf thymus DNA and thermally denatured single stranded (ss) DNA was studied in solution and at the electrode surface by means of transfer voltammetry using a carbon paste electrode (CPE) as working electrode in 0.2 M acetate buffer, pH 5.0. As a result of intercalation of this dye between the base pairs of dsDNA, the characteristic peak of dsDNA, due to the oxidation of guanine residues, decreased and after a particular concentration of EB a new peak at +0.81 V appeared, probably due to the formation of a complex between dsDNA and EB. The non-intercalated EB gives another peak, but at an increased concentration of the dye. A similar behaviour was observed during the interaction of the dye with ssDNA.Furthermore, the interaction of EB with ds, ss and supercoiled (sc) DNA was studied at the hanging mercury drop electrode (HMDE) surface by means of alternating current voltammetry in 0.3 M NaCl and 50 mM sodium phosphate buffer (pH 8.5) as supporting electrolyte. dsDNA yields a smaller peak at −1.42 V (peak III) compared to the one yielded by ssDNA, since the latter is a relaxed and more accessible form. By addition of EB into the buffer solution an increase of peak III was observed in the dsDNA form as well as in ssDNA resulting from their interaction with EB. Furthermore, the appearance of peak III in covalently closed circular scDNA after exposure to increasing concentrations of EB is a result of the introduction of ‘free ends’ in DNA affecting its structural integrity. 相似文献
133.
Group separation of organohalogenated compounds by means of comprehensive two-dimensional gas chromatography 总被引:1,自引:0,他引:1
Separations of 12 compound classes, polychlorinated biphenyls (PCBs), diphenyl ethers (PCDEs), naphthalenes (PCNs), dibenzothiophenes (PCDTs), dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs), terphenyls (PCTs) and alkanes (PCAs), toxaphene, organohalogenated pesticides (OCPs), and polybrominated biphenyls (PBBs) and diphenyl ethers (PBDEs) by comprehensive two-dimensional gas chromatography were evaluated. Five column combinations, DB-1 x 007-210, DB-1 x HT-8, DB-1 x LC-50, DB-1 x 007-65HT and DB-1 x VF-23ms were used to study, primarily, group-type separations, but attention was devoted also to within-class separation, especially for those classes which were not addressed in much detail before, the PCNs, OCPs, PBBs and PCTs. The DB-1 x 007-210 column set did not offer any extra separation compared to one-dimensional GC. For the DB-1 x HT-8 column combination, the useful principle of congener separation on the basis of number of halogen substituents in a molecule was confirmed (PCBs, toxaphene) and extended (PCTs, PBDEs). No practically useful group-type separation was observed for this column combination. The DB-1 x LC-50 set provides group separation based on planarity: planar compounds such as PCDDs, PCDFs, PCDTs and PCNs are much more retained than, and therefore separated from, non-planar analytes. Within the classes of PCBs, PBBs and PCTs highly useful separation of planar from non-planar compounds was also observed. The DB-1 x 007-65HT column set effectively separates PCAs and PBDEs from all other compound classes, and provides a good separation of brominated and chlorinated analogue classes from each other. This column set was the most efficient one for within-class separation of OCPs and PCNs. Finally, DB-1 x VF-23ms yields excellent within-class separations, especially of non-aromatic compounds, viz. OCPs, toxaphene and PCAs. No group separation was observed here. The applicability of the approach was demonstrated for a sediment extract and a dust extract. In the sediment extract, PCDDs, PCDFs, PCAs and PCNs were identified and their efficient separation was achieved. In the dust sample, separation of PCAs and PBDEs was achieved and several new PBDE congeners were identified. 相似文献
134.
The charge-transfer (CT) transition of complexes involving alkylated aromatic electron donors shifts hypsochromically upon benzylic deuteration. This is attributed to hyperconjugative effects. 相似文献
135.
Tetrabromo-p-benzoquinone reacted with excess aromatic amines to give 2,5-dirylamino-3,6-dibromo-p-benzoquinones. The latter molecules on heating with sodium sulfide in alcohol in the presence of air gave triphenodithiazinediones.
Heating with copper powder in nitrobenzene transformed these compounds into the respective indolocarbazolediones. Comparative
antimicrobial and antifungal activities of the studied compounds were determined and discussed. 相似文献
136.
Zusammenfassung Der zeitliche Verlauf der Farbstoffaufnahme an den beiden aufeinanderliegenden Al2O3-Schichten bei anodisch oxydiertem Aluminium wird in beiden F?llen durch die „Anlaufparabel“ dargestellt.
Die Gültigkeit dieser Gleichung best?tigt die Bildung eines Lackes zwischen dem benutzten Farbstoff und dem Aluminiumoxyd
bei beiden Schichten.
Die Geschwindigkeitskonstante für die erste Schicht desx
1-Al2O3 ist der Stromdichte proportional, mit welcher die Oxydation vorgenommen wurde; für die zweite Schicht desx
2-Al2O3 ist dasK″ unabh?ngig von der Stromdichte.
In dem Diagramm desK″ gegen die Stromdichte zeigt sich ein Sprung in den Eigenschaften der beiden Schichten bei 8600 Coul/dm2 (9,55 A/dm2 · 15 · 60), d.h. an demselben Punkt, an dem er sich auch in der Arbeit (1) gezeigt hatte. Diese Lage des Sprunges best?tigt
die Messungen und die Ergebnisse der beiden Arbeiten.
Au?erdem wurde so von neuem bewiesen, da? an der Grundschicht anliegendesx
1-Al2O3 por?s ist und infolgedessen die Geschwindigkeit der Farbstoffaufnahme von seiner Gesamtoberfl?che abh?ngt, d. h. von seiner
Dicke (1) und deshalb von der Stromdichte.
Im Gegensatz dazu ist die daraufliegende Schicht vonx
2-Al2O3 weniger por?s; infolgedessen ist die Geschwindigkeit der Farbstoffaufnahme unabh?ngig von seiner Dicke (1) und von der Stromdichte,
mit der die Oxydation durchgeführt worden ist (1).
Die Gültigkeit der Arrheniusschen Gleichung für beide Schichten erlaubt auch die Bestimmung der Aktivierungsenergie, deren
Wert (identisch für beide Schichten), auf Grund der Theorie der Fehlordnung und der Gültigkeit der Anlaufparabel, den Ablauf
einer Platzwechselreaktion beweist.
Durch die vorliegende Arbeit im Zusammenhang mit der Arbeit (1) wurde das Bild von der anodischen Oxydation des Aluminiums
und von der Farbstoffaufnahme vervollst?ndigt, sowohl vom Standpunkt der Sekund?rstruktur des Oxyds (hier wurde zum erstenmal
die Anwesenheit von zwei übereinanderliegenden Oxydschichten in der Zone der Hauptschicht mit deutlich verschiedenen Eigenschaften
bewiesen), als auch vom Standpunkt der Reaktionskinetik aus (hier wurde der Reaktionsmechanismus aufgedeckt). 相似文献
137.
138.
G. J. De Jong U. A. Th. Brinkman W. Th. Kok 《Journal of Radioanalytical and Nuclear Chemistry》1977,35(2):245-252
An investigation has been made on the system liquid anion-exchanger-Cd(II)-NCS−. The influence of the acidity and thiocyanate concentration of the aqueous phase on the extraction has been studied. Using
various methods of analysis, it has been shown that the complex anion present in the organic extracts is Cd(NCS)
4
2−
. Details are given concerning the removal of traces of Zn(II) from Cd(II)-containing solutions, and the quantitative separation
of Cd(II) from Cr(III). 相似文献
139.
Stress fields between interacting small particles ( approximately 100 nm) have been investigated by transmission electron microscopy. The background for these TEM observations is discussed in terms of adhesion stress fields (due to surface forces), the action of an applied point force, possibly magnetic, and dislocations or misfit strains due to an unfavorable matching of crystal lattices at the grain boundary. A further explanation might be sought along the line "squeezed-in oxide" which can be visualized as a coherent particle or a dislocation loop. Accompanying theoretical calculations have been performed and compared with the experimental results. 相似文献
140.
Summary The pozzolanic reactivity of thermally treated zeolites was studied on the basis of the Chapelle test combined with X-ray
diffraction (XRD) and Fourier Transform (FTIR) spectroscopy, as well as thermogravimetric analysis (TG/DTG) and differential
thermal analysis (DTA). The raw zeolite samples are from the Pentalofos area, Thrace, NE Greece. Their main mineral constituent
is 'heulandite type-II', an intermediate type of the heulandite-clinoptilolite isomorphous series. Calcination of the samples
was carried out up to 400, 500, 600, 700 and 1000°C for 15 h. The changes were recorded using the above methods. The deformation
of the zeolite crystal lattice starts at about 400°C and proceeds as the temperature of thermal treatment rises. The thermal
treatment of zeolite at 400°C improves its pozzolanic reactivity and accelerates the reaction with Ca(OH)2. 相似文献