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41.
The metabolism of the selective estrogen receptor modulator toremifene was simulated in an on-line electrochemistry/enzyme
reactor/liquid chromatography/mass spectrometry system. To simulate the oxidative phase I metabolism, toremifene was oxidized
in an electrochemical (EC) flow-through cell at 1,500 mV vs. Pd/H2 to its phase I metabolites, some of which are reactive quinoid species. In the presence of glutathione-S-transferase (GST), these quinoid compounds react with glutathione, which is also the common detoxification mechanism in the
body. While reacting with glutathione, the chlorine atom is eliminated from the toremifene moiety. Due to higher conversion
rates, GST supplied in continuous flow proved to be more efficient than using immobilized GST on magnetic microparticles.
In the absence of GST, not all GSH adducts are formed, proving the necessity of a phase II enzyme to simulate the complete
metabolic pathway of xenobiotics in an on-line EC/LC/MS system.
Figure Mass voltammogram of toremifene 相似文献
42.
Jahn S Lohmann W Bomke S Baumann A Karst U 《Analytical and bioanalytical chemistry》2012,402(1):461-471
In the present study, a method for the analysis of reactive metabolites via liquid chromatography (LC) with inductively coupled
plasma–mass spectrometry (MS) was developed. A ferrocenyl-modified glutathione (GSH) reagent, consisting of GSH and succinimidyl-3-ferrocenylpropionate,
was synthesized. Derivatization of the tripeptide was performed at the N-terminus, leaving the nucleophilic thiol group vacant
for the attack of electrophilic compounds. The potential of ferrocenylpropionate (FP)-GSH as a trapping agent for reactive
metabolites was investigated using an electrochemical flow-through cell for metabolism simulation coupled online to a LC system
with electrospray ionization mass spectrometric detection. The pharmaceuticals amodiaquine, an antimalarial agent, and clozapine,
an antipsychotic compound, served as model substances. By proving the successful adduct formation between the reactive metabolite
and ferrocene-labeled GSH, it could be shown that FP-GSH is an effective trapping agent which eases routine reversed-phase
LC analyses. In contrast to GSH, which is usually used for the conjugation of reactive metabolites and where the resulting
adducts often show no or only very little retention, FP-GSH facilitates the detection of the corresponding metabolite adducts
due to higher retention times. 相似文献
43.
A recent trend in DNA nanotechnology consists of the assembly of architectures with dynamic properties that can be regulated by employing external stimuli. Reversible processes are important for implementing molecular motion into DNA architectures as they allow for the regeneration of the original state. Here we describe two different approaches for the reversible switching of a double-stranded DNA rotaxane architecture from a stationary pseudorotaxane mode into a state with movable components. Both states only marginally differ in their respective topologies but their mechanical properties are fundamentally different. In the two approaches, the switching operation is based on strand-displacement reactions. One of them employs toehold-extended oligodeoxynucleotides whereas in the other one the switching is achieved by light-irradiation. In both cases, multiple back and forth switching between the stationary and the mobile states was achieved in nearly quantitative fashion. The ability to reversibly operate mechanical motion in an interlocked DNA nanostructure opens exciting new avenues in DNA nanotechnology. 相似文献
44.
Bellm SM Builth-Williams JD Jones DB Chaluvadi H Madison DH Ning CG Wang F Ma XG Lohmann B Brunger MJ 《The Journal of chemical physics》2012,136(24):244301
Cross section data for electron scattering from DNA are important for modelling radiation damage in biological systems. Triply differential cross sections for the electron impact ionization of the highest occupied outer valence orbital of tetrahydrofurfuryl alcohol, which can be considered as an analogue to the deoxyribose backbone molecule in DNA, have been measured using the (e,2e) technique. The measurements have been performed with coplanar asymmetric kinematics at an incident electron energy of 250 eV, an ejected electron energy of 20 eV, and at scattered electron angles of -5°, -10°, and -15°. Experimental results are compared with corresponding theoretical calculations performed using the molecular 3-body distorted wave model. Some important differences are observed between the experiment and calculations. 相似文献
45.
Halogenated methyl-phenyl ethers (methoxybenzenes, anisoles) are ubiquitous organics in the environment although they are not produced in industrial quantities. Modelling the fate of organic pollutants such as halogenated anisoles requires a knowledge of the fundamental physico-chemical properties of these compounds. The isomer-specific separation and detection of 60 of the 134 possible congeners allowing an environmental fingerprinting are reported in this study. The vapor pressure p0(L) of more than 60 and further physico-chemical properties of 26 available congeners are given. Vapor pressures p0(L), water solubilities S(L)W, and n-octanol/water partition coefficients Kow were determined by capillary HR-GC (High Resolution Gas Chromatography) on a non-polar phase and by RP-HPLC (Reversed Phase High Performance Liquid Chromatography) on a C18 phase with chlorobenzenes as reference standards. From these experimental data the Henry's law constants H, and the gas/water Kgw and gas/n-octanol Kgo partition coefficients were calculated. We found that vapor pressures, water solubilities, and n-octanol/water partition coefficients of the halogenated anisoles are close to those of the chlorobenzenes. A similar environmental fate of both groups can, therefore, be predicted. 相似文献
46.
47.
Jörg Schreiber Wolfgang Lohmann Dietrich Unverzagt Albert Otten 《Fresenius' Journal of Analytical Chemistry》1986,325(5):473-475
Summary High-performance liquid chromatography with UV-detection at 254 nm was used for determining ascorbic acid, dehydroascorbic acid, and isoascorbic acid in plasma and erythrocytes obtained from healthy volunteers and from patients with coronary infarct, acute lymphatic leukemia (ALL), and acute myeloic leukemia (AML). Deproteinisation was done by a simple ultrafiltration technique. Dehydroascorbic acid (DHA) was determined after reduction to ascorbic acid with dithiothreitol. The separation system chosen allows the search for the stereoisomer isoascorbic acid. To exclude interfering substances which could coelute with ascorbic or isoascorbic acid, several other compounds present in plasma were investigated including e.g. the aromatic amino acids, glutathione, cysteine, and uric acid. The results reveal a drastic decrease in total vitamin C concentration in plasma and erythrocytes with a concomitant increase in rel. DHA concentration in patients with AML. In ALL patients, both the total vitamin C and rel. DHA concentrations were increased.
Bestimmung von Ascorbinsäure, Dehydroascorbinsäure und Isoascorbinsäure in Blut
Zusammenfassung High-performance-liquid-Chromatographie mit UV-Nachweis bei 254 nm wurde zur Bestimmung von Ascorbinsäure, Dehydroascorbinsäure und Isoascorbinsäure in Plasma und Erythrocyten von gesunden Probanden und von Patienten mit Herzinfarkt, akuter lymphatischer Leukämie (ALL) und akuter myeloischer Leukämie (AML) benutzt. Deproteinisierung erfolgte mittels einer einfachen Ultrafiltrationstechnik. Dehydroascorbinsäure wurde nach Reduktion mit Dithiothreitol als Ascorbinsäure bestimmt. Die benutzte Methode erlaubt auch die Bestimmung des Stereoisomers Isoascorbinsäure. Der mögliche Einfluß von im Plasma vorkommenden Substanzen auf die Bestimmung des Vitamin C wurde untersucht. Die Ergebnisse zeigen eine drastische Abnahme der Gesamt-Vitamin C-Konzentration in Plasma und Erythrocyten mit einer parallelen Zunahme der relativen DHA-Konzentration in AML-Patienten. In ALL-Patienten sind sowohl die Gesamt-Vitamin C- als auch die relative DHA-Konzentrationen erhöht.相似文献
48.
49.
A. A. Minaenko T. M. Bryukhanova N. A. Kruglov A. M. Moiseev E. A. Starchenko M. N. Ukhanov R. Barloutaud C. Cochet A. Givernaud C. Lewin M. L. Turluer U. Gensch H. J. Grabosch W. Lohmann J. MacNaughton F. Mandl France Collaboration Soviet Union CERN Collaboration Soviet Union Collaboration 《Zeitschrift fur Physik C Particles and Fields》1984,26(1):27-35
The inclusive production of γ's and πp0's inK ? p-interactions at 32 GeV/c is studied. About 30.000 γ's coming from a Mirabelle bubble chamber experiment with a sensitivity of 6.5 ev/μb have been used for the analysis. Inclusive and topological cross sections of γ's are measured. The γ invariant differential distributions and their scaling properties are investigated. The inclusive cross section of πp0-production is determined and the πp0 invariant differential distributions are evaluated and compared to those of πp±. 相似文献
50.
We report on two tunable, bandstop spatial filters, which are based on the Talbot effect. The light interacts with more than two gratings, arranged in series. The techniques may be considered as the analogues of the Fabry-Perot interferometer and the Lyot-Öhman filter, respectively. Some experimental results are included. 相似文献