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1.
We discuss an error estimation procedure for the global error of collocation schemes applied to solve singular boundary value problems with a singularity of the first kind. This a posteriori estimate of the global error was proposed by Stetter in 1978 and is based on the idea of Defect Correction, originally due to Zadunaisky. Here, we present a new, carefully designed modification of this error estimate which not only results in less computational work but also appears to perform satisfactorily for singular problems. We give a full analytical justification for the asymptotical correctness of the error estimate when it is applied to a general nonlinear regular problem. For the singular case, we are presently only able to provide computational evidence for the full convergence order, the related analysis is still work in progress. This global estimate is the basis for a grid selection routine in which the grid is modified with the aim to equidistribute the global error. This procedure yields meshes suitable for an efficient numerical solution. Most importantly, we observe that the grid is refined in a way reflecting only the behavior of the solution and remains unaffected by the unsmooth direction field close to the singular point. 相似文献
2.
A method for the deposition of BN onto graphite and other substrates is described. Boron trichloride (BCl3) and ammonia (NH3) diluted with Ar were used as reacting gases. The deposition process was carried out at 1300 K as well as lower temperatures in an open system at pressures of 1 atm. The consequences of the introduction of hydrogen to the system were considered. It was demonstrated that the replacement of argon with hydrogen increases the efficiency of the process as well as the theoretical rate of BN deposition. However, the acceleration of the deposition seems to be unprofitable, because the resulting supersaturation leads to the formation of an amorphous phase. The modification of the experimental conditions were proposed.Dedicated to Professor Dr. rer. nat. Dr. h.c. Hubertus Nickel on the occasion of his 65th birthday 相似文献
3.
JPC – Journal of Planar Chromatography – Modern TLC - Emodin and twelve phenolic acids (ellagic, gallic, protocatechuic, homoprotocatechuic, caffeic, p-hydroxybenzoic, p-coumaric,... 相似文献
4.
Gajdek P Bober B Mej E Bialczyk J 《Journal of photochemistry and photobiology. B, Biology》2004,76(1-3):103-106
UV radiation was applied to degrade cyanobacterial hepatotoxin, microcystin-LR in the presence of phycocyanin as a model natural sensitiser. The concentrations of both the toxin and the pigment used in the experiments were higher by several orders of magnitude than found in the environment. The photoreaction parameters were optimised. The process was found to be of limited use for water treatment due to its low efficacy. Additionally, pronounced UV-induced bleaching of the pigment significantly reducing the photoreaction rates of the toxin was observed for the highest UV radiation intensities applied. 相似文献
5.
The mechanism of the indium electrodeposition on gold from acidic KBr solutions has been investigated by means of the rotating ring-disc electrode technique. The measurements showed that the overall electrode reaction In(III) + 3 e In consists of two successive charge transfer steps, i.e. In(III) + 2 e In(I) and In(I) + e In, with soluble monovalent indium as an intermediate. The current efficiency for In(I) generation under steady-state conditions is 100% in the case of low disc current densities. The disproportionation of In(I) in the bulk of solution occurs in slightly acidified solutions,pH=2, in addition to the In(I) electrochemical reduction. Based on the ring current transients, it was established that the two-electron transfer step is preceded by the formation of a thin passive film of indium metal.
Untersuchung der elektrochemischen Reduktion von In(III)-Ionen an Gold in sauren Bromidlösungen mit der rotierenden Ring-Scheiben-Elektrode
Zusammenfassung Mit Hilfe der rotierenden Ring-Scheiben-Elektrode wurde der Mechanismus der kathodischen Abscheidung von Indium auf Gold in sauren KBr-Lösungen untersucht. Aus den Messungen folgt, daß die Bruttoreaktion In(III) + 3e In über zwei aufeinanderfolgende Durchtrittsreaktionen, In(III) + 2 e In(I) und In(I) + e In, mit löslichem einwertigem Indium als Zwischenprodukt abläuft. Bei kleinen Stromdichten werden die In(I)-Ionen mit 100%iger Stromausbeute erzeugt. In schwächer sauren Lösungen (pH=2) konnte außer der elektrochemischen Reduktion von In(I) zusätzlich dessen Disproportionierung innerhalb der Lösung ermittelt werden. Auf Grund der Ringstrom-Zeit-Kurven wurde auch festgestellt, daß die Bildung von einer dünnen In-Metallschicht, die ein passives Verhalten aufweist, dem Zweielektronenübergang vorangegangen ist.相似文献
6.
Summary Complexation equilibria of the Tl(I) ion with 18-crown-6 and dibenzo-18-crown-6 were studied polarographically in 10 nonaqueous solvents. The stability of the complexes is strongly influenced by the nature of solvents and varies with their Lewis basicities. It has been found that the logK
s value (K
s is the stability constant of the complex) can be well described by empirical relation logK
s=a DN+b, whereDN stands for the Gutmann donor number anda andb mark the regression coefficient. Addition of the second explanatory parameter, the acceptor number, is not statistically significant. This result is in agreement with the predominant role of Tl(I) ion solvation.
Elektrochemische Untersuchungen von Tl(I)-Kronenetherkomplexen in nichtwäßrigen Medien
Zusammenfassung Es wurden die Komplexierungsgleichgewichte des Tl(I)-Ions mit 18-Krone-6 und Dibenzo-18-krone-6 polarographisch in 10 nichtwäßrigen Lösungsmitteln untersucht. Die Stabilität der Komplexe wird sehr stark vom Solvens beeinflußt, wobei eine starke Abhängigkeit von der Lewis-Basizität beobachtet wird. Es wurde festgestellt, daß die logK s-Werte (K s ist die Komplexstabilitätskonstante) gut mit der empirischen Beziehung logK s=a DN+b beschrieben werden können, wobeiDN die Gutmann'sche Donorzahl unda undb die Regressionskonstanten bedeuten. Hinzunahme der Akzeptorzahl als zweiten Parameter bleibt statistisch insignifikant. Dieses Ergebnis stimmt mit dem dominierenden Einfluß der Tl(I)-Ionensolvatation überein.相似文献
7.
Aquation of [Cr(pic)3]0 and [Cr(pic)2(OH)]2
0 in aqueous HClO4 solutions leads to formation of the common product – [Cr(pic)2(H2O)2]+. The first, reversible stage, the ring opening via Cr—N bond breaking in [Cr(pic)3]0 is followed by the second, rate-determining step – one-end bonded pic ligand liberation. In the case of the [Cr(pic)2(OH)]2
0 complex, the first faster stage produces the singly bridged dimer, which undergoes cleavage into the parent monomers in the second, much slower step. The subsequent aquation of [Cr(pic)2(H2O)2]+ is extremely slow and leads to [Cr(pic)(H2O)4]2+ formation, which practically does not undergo further ligand substitution under the conditions applied. Kinetics of the first aquation stage for [Cr(pic)3]0 and of the second step for [Cr(pic)2(OH)]2
0 were studied spectrophotometrically in the 0.1–1.0 M HClO4 range at I = 1.0 M. The observed pseudo-first order rate constant for [Cr(pic)3]0 decreases with [H+] increase according to the rate law: k
obs = k
1 + k
–1
Q
1/[H+], where k
1 and k
–1 are the rate constants of the forward and the reverse processes in the unprotonated substrate and Q
1 is the protonation constant of the pyridine nitrogen atom. In the case of the [Cr(pic)2(OH)]2
0 complex, the rate for the singly bridged dimer cleavage does not depend on [H+]. The activation parameters for the chelate-ring opening in [Cr(pic)3]0 and for the singly bridged dimer cleavage have been determined and discussed. Some kinetic data of the slow, second aquation stage for the [Cr(pic)3]0 complex and of the fast, first aquation stage for the doubly bridged dimer have been studied; for both reactions the rate increases linearly with the increase in [H+]. 相似文献
8.
A new, highly sensitive, fast responding and stable potentiometric biosensor for creatinine determination is developed. The biosensor is based on an ammonium ion-selective electrode. Creatinine deiminase (EC 3.5.4.21) is chemically immobilized on the surface of the polymeric ion-sensitive membrane in the form of monomolecular layer using a simple, one-step carbodiimide covalent attachment method. The resulting enzyme electrodes are useful for measurement under flow injection analysis (FIA) conditions. The biosensors exhibit excellent operational and storage stability. The enzyme electrodes retain over 70% of initial sensitivity after ten weeks of work under FIA conditions. The storage stability at 4 °C is longer than half a year without loss of sensitivity. Under optimized conditions near 30 samples per hour can be analyzed and the determination range (0.02-20.0 mmol l−1) fully covers creatinine concentrations important from clinical and biomedical point of view. The simple biosensor/FIA system has been successfully used for determination of creatinine in urine, serum and posthemodialysate samples. 相似文献
9.
Józef Oleksyszyn Ewa Gruszecka Paweł Kafarski Przemysław Mastalerz 《Monatshefte für Chemie / Chemical Monthly》1982,113(1):59-71
Preparation of the phosphonic analogs of -methylaspartic (4 a–d), glutamic (7 a–b) and -methylpyroglutamic (5 a–b) acids by aminoalkylation of trivalent phosphorus chlorides with ethyl esters of oxoalkyloacids and benzyl carbamate is described. The phosphonic analogs of pyroglutamic acid (8 a–b) was obtained by the cyclization of the corresponding esters (9 a–b). The stability of the phosphonic analogs of pyroglutamic acid in acidic and alkaline media was also studied.
Die Herstellung von neuen Phosphonanalogen der Asparagin- und Glutaminsäure in der Reaktion von trivalenten Phosphorchloriden mit Ethyl-acetyloacetat oder Ethyl-lävulinat bzw. Benzylcarbaminat
Zusammenfassung Es wurde die Darstellung der Phosphonanalogen der -Methylasparaginsäure (4 a–d), Glutamin- (7 a–b) und -Methylpyroglutaminsäure (5 a–b) in der Reaktion der trivalenten Phosphorchloride und der Oxoalkansäureethylester sowie des Benzylcarbaminats beschrieben. In der Ringschlußreaktion der Ester (9 a–b) erhält man Phosphonanaloge der Pyroglutaminsäure. Die Stabilität der Analogen der Pyroglutaminsäure wurde in sauren und alkalischen Medien geprüft.相似文献
10.
Yu JC Krushkova S Lai EP Dabek-Zlotorzynska E 《Analytical and bioanalytical chemistry》2005,382(7):1534-1540
A molecularly-imprinted polymer (MIP) was prepared by electropolymerization of pyrrole (Py) onto a stainless steel frit, using ochratoxin A (OTA) as the template, in order to make a micro solid phase preconcentration (SPP) device. The OTA template was removed with 1% triethylamine (TEA) in methanol. Compared to non-imprinted polypyrrole (PPy), the molecularly-imprinted polypyrrole (MIPPy) enhanced the selective binding of OTA. The percentage recovery improved from 0 to 40% when the OTA sample solution was acidified with 1 M HCl (1% by volume). At a flow rate of 0.2 mL/min, maximum OTA binding was reached in 6 min after a total loading of 3.2 ng OTA. Final elution of the OTA was analyzed by high performance liquid chromatography (HPLC) with fluorescence detection, using 20:80 v/v acetonitrile–ammonia buffer (NH4Cl/NH3, 20 mM, pH 9.2) as the mobile phase. The MIPPy-SPP-HPLC results clearly demonstrated that the MIPPy-SPP device afforded selective preconcentration of OTA from red wine samples, at OTA concentration levels as low as 0.05 ppb, prior to HPLC analysis. 相似文献