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41.
Consumption of non-steroidal anti-inflammatory drugs (NSAIDs) is increasing and with it the danger of environmental pollution
by pharmaceutical residues. Publications regarding NSAIDs in the environment not only show that they are toxic to many animal
species, but also highlight the need for robust analytical methods for monitoring the level of such contaminants in environmental
matrices. In our study we selected the four most widely used NSAIDs in Slovenia and Central Europe, ibuprofen, naproxen, ketoprofen
and diclofenac, and studied their extraction from sediment samples. We examined several extraction techniques (ultrasonic
extraction, Soxhlet extraction, pressurized liquid extraction, supercritical fluid extraction and microwave-assisted extraction)
using a spiked sediment sample and determined optimal extraction conditions. After extraction we applied a clean-up step,
derivatisation of the analytes and gas chromatography with mass spectrometric detection (GC-MSD) and selected the most appropriate
extraction procedure. The optimised analytical method chosen for analysis of sediment samples consisted of microwave-assisted
extraction, clean-up of the extract with SPE, derivatisation with MSTFA and determination with GC-MSD. The optimised procedure
was applied to the analysis of two environmental river samples taken from the vicinity of Novo mesto, the biggest town in
the south eastern part of Slovenia with 62,000 inhabitants, a hospital and a pharmaceutical factory in its vicinity. While
analysis of the sample taken upstream of the town showed no detectable amounts of NSAIDs, analysis of samples taken downstream
showed quantifiable levels of two of the studied NSAIDs (naproxen and ketoprofen). Besides these two NSAIDs, river water samples
sampled at the same time and location on the River Krka also showed the presence of diclofenac. Sampling on the River Krka
and other Slovene rivers will in the future be repeated at different sampling points in order to track down the main sources
of pollution. 相似文献
42.
Concern is growing over the contamination of the environment with pharmaceutical residues, among which non-steroidal anti-inflammatory
drugs (NSAIDs) are one of the most abundant groups. Their widespread appearance in the aquatic environment is because of their
high consumption and their incomplete removal during wastewater treatment. Because effective operation of wastewater-treatment
plants is important for minimising the release of xenobiotic compounds, for example pharmaceutical products, into the aquatic
environment, our study focuses on removal of commonly used NSAIDs (ibuprofen, naproxen, ketoprofen, diclofenac) and clofibric
acid in a specially designed small-scale pilot wastewater treatment plant (PWWTP). This study shows that, except for diclofenac,
steady-rate removal of NSAIDs over a two-year monitoring period has been achieved. Elimination of the compounds in the PWWTP
was ≥87% for ibuprofen, naproxen and ketoprofen but only 49–59% for diclofenac. We also studied clofibric acid. Results after
one month of operation revealed 30% elimination with no sign of adaptation by the biomass. Also described are degradation
products of diclofenac, which we were able to identify because of the similarity of their mass spectra with those in the NIST
library and by comparing the retention times of different compounds. Although the structures of these compounds were confirmed
with a high probability (99%), we still need to compare the fragmentation of authentic compounds with degradation products
formed under our experimental conditions. Degradation products of ibuprofen, naproxen, ketoprofen, and clofibric acid were
found but these must be identified by use of high-resolution mass spectrometry and analysis of authentic compounds. 相似文献
43.
Graham Wigley John Heath Graham Pitcher Adam Whybrew 《Particle & Particle Systems Characterization》2001,18(4):169-178
This work describes a systematic approach adopted to establish Laser and Phase Doppler Anemometry, LDA/PDA, experimental techniques that would allow velocity and dropsize measurements to be made over wide velocity and size ranges with confidence in partially atomized sprays. The analysis considers the sprays generated by different gasoline direct injection (GDI) systems injecting into air under atmospheric conditions. The upper limit to the dropsize range in the fuel sprays was confirmed using (a) an Oxford Lasers' VisiSizer and (b) droplets of a known size produced by a mono‐dispersed droplet generator. GDI fuel sprays are highly transient, optically dense and provide a high degree of penetration and atomization. The measurement problem is therefore one of the detection of small, high speed droplets inside a dense cloud of surrounding droplets. Furthermore, under the transients found at the start and end of injection and during high fuel loads, fuel elements in the form of sheets, ligaments and filaments are also injected. These liquid fuel elements subsequently break‐up, downstream from the nozzle, to form droplets of a much larger size class but with a much lower number density [1]. The co‐existence of these liquid fuel elements and the widely different size classes in the spray are considered to pose a problem for dropsize measurements by the PDA technique. In particular: the wide dynamic range of light intensities scattered by the fuel elements and droplets; the trajectory of large drops through the edges of the PDA measurement volume with its Gaussian intensity distribution [2] and the high probability of non spherical droplets. The work concludes that the LDA/PDA measurement technique, as applied here, is robust. It can discriminate between partially and fully atomized sprays, has a high probability of accurately measuring dropsizes larger than the measurement volume and give a realistic indication of ‘sizes’ for non spherical droplets. However, specification of the PDA system parameters must be strictly compatible with the measurement task to yield unambiguous results. 相似文献
44.
45.
Graham Wigley Graham K. Hargrave John Heath 《Particle & Particle Systems Characterization》1999,16(1):11-19
A new generation LDA/PDA transmitter system has been designed and constructed. The heart of the optical system is a new type of Bragg cell. Advances in laser power handling and symmetrical splitting at high Bragg angles of the shifted and unshifted beams have made it possible to construct a simple yet elegant LDA/PDA transmitter. The optical system integrates the Bragg cell with a laser beam expander to offer variable beam separation and high beam expansion ratios to produce a measurement volume with a high spatial resolution and at high power levels. The transmitter is proving to be a significant contribution to LDA/PDA optical system design and, not only applicable as a research tool for use in flows of a demanding nature but, due to its simplicity, flexibility and cost, an asset to teaching. The LDA/PDA system is being applied to characterise the atomization of fuel by high pressure automotive injectors as found in Gasoline Direct Injection (GDI) engines. Although the PDA system was configured to measure two orthogonal velocity components (2D) and size, its operation was not restricted to this configuration. An analysis of the spray with the PDA system in 1D and size and the LDA system in 2D and 1D configurations indicated the complexity of the atomization and break-up processes occurring in the spray. Single-shot imaging was used to study the spatial structure of the spray as a function of time. Use of the light sheet imaging technique alone could lead to false impressions of the atomization process. 相似文献
46.
Timothy G. Heath Dennis O. Scott 《Journal of the American Society for Mass Spectrometry》1997,8(4):371-379
A method based on liquid chromatography-tandem mass spectrometry and microbore column separation was developed for the quantification of a potent 5-HT2a receptor antagonist (R)-(+)-α-(2,3-dimethoxyphenyl)-1-[2-(4-fluorophenyl)etnyl]-4-piperidine-methanol (I) and the desmethyl metabolite (II) in rat brain extracellular fluid (ECF) following microdialysis sampling. The analytical method was also applied to determining plasma concentrations of these compounds. The lower limit of quantification (LLQ) for each compound in microdialysis perfusate is 500 pg/mL, which translates to <7 fmol (injected). The recovery of I and II for the microdialysis probe in brain ECF was 18.5 and 22.7%, respectively. The LLQ for each compound in plasma is 1 ng/mL. The inherent selectivity offered by tandem mass spectrometry eliminated chemical noise, thereby improving the detectability of these compounds. These methods were used to confirm that I and II penetrated the blood-brain barrier following administration of I to rats and enabled comparison of plasma and brain ECF concentrations. 相似文献
47.
Bunimovich YL Shin YS Yeo WS Amori M Kwong G Heath JR 《Journal of the American Chemical Society》2006,128(50):16323-16331
The quantitative, real-time detection of single-stranded oligonucleotides with silicon nanowires (SiNWs) in physiologically relevant electrolyte solution is demonstrated. Debye screening of the hybridization event is circumvented by utilizing electrostatically adsorbed primary DNA on an amine-terminated NW surface. Two surface functionalization chemistries are compared: an amine-terminated siloxane monolayer on the native SiO2 surface of the SiNW, and an amine-terminated alkyl monolayer grown directly on a hydrogen-terminated SiNW surface. The SiNWs without the native oxide exhibit improved solution-gated field-effect transistor characteristics and a significantly enhanced sensitivity to single-stranded DNA detection, with an accompanying 2 orders of magnitude improvement in the dynamic range of sensing. A model for the detection of analyte by SiNW sensors is developed and utilized to extract DNA-binding kinetic parameters. Those values are directly compared with values obtained by the standard method of surface plasmon resonance (SPR) and demonstrated to be similar. The nanowires, however, are characterized by higher detection sensitivity. The implication is that SiNWs can be utilized to quantitate the solution-phase concentration of biomolecules at low concentrations. This work also demonstrates the importance of surface chemistry for optimizing biomolecular sensing with silicon nanowires. 相似文献
48.
Dichtel WR Miljanić OS Spruell JM Heath JR Stoddart JF 《Journal of the American Chemical Society》2006,128(32):10388-10390
The mild reaction conditions, remarkable functional group compatibility, and complete regioselectivity of the Cu-catalyzed Huisgen 1,3-dipolar cycloaddition ("click chemistry") between organic azides and terminal alkynes have led to a threading-followed-by-stoppering approach to the synthesis of donor-acceptor rotaxanes incorporating cyclobis(paraquat-p-phenylene) (CBPQT4+) as the pi-accepting ring component. Rotaxane formation is initiated by reacting azide-functionalized pseudorotaxanes containing pi-donating 1,5-dioxynaphthalene (DNP) recognition units with appropriate alkyne-functionalized stoppers. The high yields obtained in this efficient, kinetically controlled post-assembly covalent modification, as well as the excellent convergence of the synthetic protocol, are demonstrated by the preparation of [2]-, [3]-, and [4]rotaxanes containing multiple DNP/CBPQT4+ donor-acceptor recognition motifs. 相似文献
49.
Single molecule fluorescence measurements have recently been used to probe the orientation of fluorescent lipid analogs doped into lipid films at trace levels. Using defocused polarized total internal reflection fluorescence microscopy (PTIRF-M), these studies have shown that fluorophore orientation responds to changes in membrane surface pressure and composition, providing a molecular level marker of membrane structure. Here we extend those studies by characterizing the single molecule orientations of six related BODIPY probes doped into monolayers of DPPC. Langmuir-Blodgett monolayers transferred at various surface pressures are used to compare the response from fluorescent lipid analogs in which the location of the BODIPY probe is varied along the length of the acyl chain. For each BODIPY probe location along the chain, comparisons are made between analogs containing phosphocholine and smaller fatty acid headgroups. Together these studies show a general propensity of the BODIPY analogs to insert into membranes with the BODIPY probe aligned along the acyl chains or looped back to interact with the headgroups. For all BODIPY probes studied, a bimodal orientation distribution is observed which is sensitive to surface pressure, with the population of BODIPY probes aligned along the acyl chains increasing with elevated surface pressure. Trends in the single molecule orientations for the six analogs reveal a configuration where optimal placement of the BODIPY probe within the acyl chain maximizes its sensitivity to the surrounding membrane structure. These results are discussed in terms of balancing the effects of headgroup association with acyl chain length in designing the optimal placement of the BODIPY probe. 相似文献
50.
David G. Parker 《中国颗粒学报》2009,7(2)
This paper describes the operation and outcome of one of the United Kingdom's largest multi-partner research activities in nanoparticles.The research covers the discovery and development of organic and inorganic crystals/nanoparticles,nanoparticle properties towards specific product applications,The research also encompassed bespoke measurement technology for nanoparticles and structure interactions.Significant research outcomes are summarised.The paper illustrates the advantages from industrially motivated research and value of collective action between a broad group of researchers in a nation. 相似文献