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1.
OBJECTIVE: Trials that do not allow rejection of the null hypothesis of no treatment effect may have had an inappropriate design. Trials are virtually never assessed for correlation between responses to different treatment modalities. METHODS: Using a hypothetical example and several published studies we examine the influence of correlation levels between treatment modalities on the sensitivity of testing. RESULTS: The level of correlation between responses to different treatment modalities is a major determinant of the sensitivity both of crossover and parallel group clinical trials. CONCLUSIONS: It is very relevant to assess a priori correlation levels between responses to the different treatment modalities of a trial. If a negative correlation is anticipated, a crossover design is likely to lack sensitivity. If a positive correlation is anticipated a parallel-group design seems less appropriate, because it would lack the extra sensitivity of accounting for the positive correlation. Both designs would seem suitable for approximately zero correlations (e.g. comparison vs baseline or vs placebo under the assumption that the number of placebo responders is negligible.  相似文献   
2.
31P-Nuclear magnetic resonance (NMR) spectroscopy was employed to detect and quantify free glycerol in virgin olive oils originating from various regions of Greece. This analytical method was based on the derivatization of the hydroxyl groups of glycerol with the tagging reagent 2-chloro-4,4,5,5-tetramethyldioxaphospholane, and identification of the phosphitylated compound on the basis of 31P chemical shifts. Quantification of glycerol in olive oils was accomplished by integration of the appropriate signals in the 31P NMR spectrum and the use of the phosphitylated cyclohexanol as internal standard. A linear correlation was observed between the glycerol content and 1,3-diacylglycerols and free acidity indicating that glycerol is the final product of the partial hydrolysis of triacylglycerols.  相似文献   
3.
Photis Dais 《Lipid Technology》2010,22(12):274-276
This short account describes a novel analytical technique for the determination of total, free and esterified sterols in olive oil developed in our laboratory. This methodology is based on 1H and 31P NMR spectroscopy. The latter spectroscopic analysis requires first the derivatization of the sterolic hydroxyl groups with a phosphitylating reagent. This NMR method shows a number of advantages over conventional methods for sterols determination, amongst which speed and simplicity are the most beneficial ones. The possibility of applying the NMR spectroscopy to other food matrices is discussed.  相似文献   
4.
Gel permeation chromatography (GPC) is one of the most important characterization tools of the polymer chemist. The coupling of GPC with ultraviolet (UV) spectroscopy (GPC–UV) increases the power of the tool even further. This article describes the use of GPC–UV to determine the location of functional groups in polymers. This information is important for characterization of functionalized polymers being used as building blocks for making block and graft copolymers, and for the elucidation of polymer degradation mechanisms. The use of GPC–UV for quantitation of the level of functional groups is hampered by the inability to achieve complete conversion of some UV transparent functional groups (e.g., hydroxyl and carbonyl) to the uniquely absorbing derivative needed for the analysis. Attempts to quantitatively derivatize polymer-bound functional groups using conditions developed for model compounds failed. However, the use of GPC–UV to locate functional groups in polymers (pendant vs. chain-end) is clearly demonstrated.  相似文献   
5.
1H and 13C longitudinal relaxation times (T1) and relaxation times in the rotating frame (T) have been measured for poly(N‐vinylcarbazole) in the solid state in air and nitrogen atmospheres in an attempt to elucidate molecular motions. In air, the T1 relaxation of both 1H and 13C was dominated by interaction with absorbed paramagnetic oxygen. In nitrogen, the 13C T1 relaxation times were long (>300 s) and were averaged by 13C–13C spin diffusion. The 13C T relaxation times showed an exponential dependence on the strength of the rotating 13C magnetic field and were thus controlled by spin–spin processes rather than spin–lattice processes. © 2001 Society of Chemical Industry  相似文献   
6.
We present a Byesian test of simple hypotheses on the drift of the observation process Xt = θt + Wtwhere θis a bernouli random variable (wt) is a standard Wiener process. sequential tests δ = (T, d) are used, where T is a (FX t)-stopping time, d is a (FX t+n)-measurable decision function, n is a postive random variable with a given distribution. The cost function V(π, T, d) of any sequential test θ = (T, d) is based on costs of wrong decisions and observation, respectively.  相似文献   
7.
The precise knowledge of current harmonics generated at the input of static pulsewidth modulated (PWM) inverters is essential in designing the input filter and in determining the interaction between the inverter and supply voltage bus. Despite its importance, however, this topic has been given mostly qualitative treatment. A novel harmonic analysis approach is employed with ideal static voltage source inverters to specify the harmonic spectra of their respective input currents. This information is subsequently used to compute the harmonic distortion of the input current and the ripple current for the input filter capacitor.  相似文献   
8.
Sixty samples of milk, Halloumi cheese and local grazing plants (i.e. shrubs) were collected over a year from dairy farms located on three different locations of Cyprus. Major and trace elements were quantified using inductively coupled plasma–atomic emission spectroscopy (ICP‐AES). Milk and Halloumi cheese produced in different geographical locations presented significant differences in the concentration of some of the elements analysed. Principal component analysis showed grouping of samples according to the region of production for both milk and cheese samples. These findings show that the assay of elements can provide useful fingerprints for the characterisation of dairy products.  相似文献   
9.
Three different analytical techniques, namely NMR spectroscopy, mass spectrometry and dynamic light scattering, were used to unravel the structure and morphology of polyglycerol polyricinoleate (PGPR). This material is used as an emulsifier in the preparation of chocolate and other confectionary products. The use of 1D and 2D NMR techniques led to the distinction of two separate entities in commercial ricinoleic acid (RA) and PGPR samples, namely the monomeric and oligomeric RA (estolides). 1H and 13C spectra of PGPR confirmed the presence of polyglycerol moieties of various lengths being esterified by RA and estolides and to a lesser extent by oleic and linoleic acids. 13C-NMR DOSY experiments demonstrated the occurrence of several species in PGPR. Electrospray Ionization and tandem Mass Spectrometry succeeded in identifying the presence of over 30 glycerol/polyglycerol species containing n glycerol moieties with n = 1–6 esterified by monomeric and oligomeric RA molecules. Dynamic light scattering contributed to the characterization of PGPR morphology. The PGPR mixture contains relatively small-sized entities (monomers, dimmers, trimmers) and larger aggregates resulted from chain association. The percentage of larger aggregates is minimal compared to small-sized species.  相似文献   
10.
In this study, the methodology of shift reagents was exploited to distinguish cis and trans unsaturation in oils and fats. The differential binding of silver ions (in the form of AgFOD) to cis and trans double bonds allowed the separation of the allylic and olefinic proton signals in the 1H NMR spectra of mixtures of cis and trans methyl esters of monoene aliphatic acids and unsaturated triacylglycerol mixtures at low frequency spectrometers (300 MHz). Careful integration of the appropriate proton resonances in the recorded quantitative 1H NMR spectra afforded percentage concentrations in very good agreement with the actual values. This 1H NMR methodology was validated by analyzing AOCS Laboratory Proficiency Program GC samples containing various percentages of saturated, cis‐mono unsaturated, and cis‐polyunsaturated fat as well as trans content. This fast and relatively low‐cost NMR methodology could be used on line for obtaining nutrition labeling compositional data (NLCD) required for fat‐containing food products. Attempts to differentiate lipid molecules with different degree of unsaturation and positional distribution of cis double bonds were unsuccessful.  相似文献   
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