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91.
We propose an algorithm for the computation ofL
1 (LAD) smoothing splines in the spacesW
M
(D), with
. We assume one is given data of the formy
i
=(f(t
i
) +
i
, i=1,...,N with {itti}
i=1
N D
, the
i
are errors withE(
i
)=0, andf is assumed to be inW
M
. The LAD smoothing spline, for fixed smoothing parameter0, is defined as the solution,s
, of the optimization problem
(1/N)
i=1
N
¦y
i
–g(t
i
¦+J
M
(g), whereJ
M
(g) is the seminorm consisting of the sum of the squaredL
2 norms of theMth partial derivatives ofg. Such an LAD smoothing spline,s
, would be expected to give robust smoothed estimates off in situations where the
i
are from a distribution with heavy tails. The solution to such a problem is a thin plate spline of known form. An algorithm for computings
is given which is based on considering a sequence of quadratic programming problems whose structure is guided by the optimality conditions for the above convex minimization problem, and which are solved readily, if a good initial point is available. The data driven selection of the smoothing parameter is achieved by minimizing aCV() score of the form
.The combined LAD-CV smoothing spline algorithm is a continuation scheme in 0 taken on the above SQPs parametrized in, with the optimal smoothing parameter taken to be that value of at which theCV() score first begins to increase. The feasibility of constructing the LAD-CV smoothing spline is illustrated by an application to a problem in environment data interpretation. 相似文献
92.
The selectivity of a column system, S, defined by equation 28, includes a variation coefficient (β) of plate number with capacity ratio which has a large influence on the peak capacity, as shown in Fig. 18. Some typical chromatograms are given. In order to predict S for a column system from Kovat's Index, equations 40 and 41 are given to calculate the constant of the carbon number rule for squalane at different temperatures or for different stationary phases. The specific retention value of heptane on squalane at different temperatures can be calculated from equation 42. The nonpolarity index, defined by equation 43, was used to calculate the retention value of heptane on various stationary phases. In liquid chromatography, the order of elution may be reversed by changing the composition of the eluent on the same chemically bonded silica (manufactured in China). The linear relations between the log retention values of different kinds of solutes or of a single solute on the silicas of different surface areas when using the same eluent are given. 相似文献
93.
Klaus Rose Vlastimil MatĚjec Milos Hayer Marie PospiŠilovÁ 《Journal of Sol-Gel Science and Technology》1998,13(1-3):729-733
Various types of UV-curable organically modified siloxanes have been synthesized by the sol-gel method with the aim of fabricating chemically sensitive coatings for silica optical fibers. The refractive index of the coating material can be tailored in the range from 1.46 to 1.56 and sensitivity towards CO2 is achieved by incorporation of amino groups. The interaction of the cured layers with CO2 or with hydrocarbons has been studied in immersion experiments. Both the reaction of CO2 with incorporated amino groups and the penetration of hydrocarbons into the layer induce changes of the light absorption coefficient and the refractive index of the coating which are detected by measuring the output light intensity from the fiber. 相似文献
94.
本文以聚乙烯醇(PVA)、苯胺(ANI)、吡咯(Py)及钛酸丁酯(TBOT)为原料,通过溶胶-凝胶法、原位氧化聚合法及冷冻-融溶法一步得到聚乙烯醇/聚苯胺/聚吡咯/TiO 2(PVA/PANI/PPy/TiO 2)杂化水凝胶。结果表明,该杂化水凝胶具有优异的力学性能和导电性能。当n(ANI)∶[KG-*3/5]n(Py)=8∶[KG-*3/5]2(TBOT体积为100μL)时,其压缩强度高达2.45 MPa。同时,在外加电源的作用下,该凝胶能够使灯泡发光。当n(ANI)∶[KG-*3/5]n(Py)=2∶[KG-*3/5]8(TBOT体积为150μL)时,杂化水凝胶的电导率(0.25 S/m)最好。该杂化水凝胶有望广泛地应用在柔性可穿戴电子器件、安全离子电池、传感器和生物器件等领域。 相似文献
95.
Inorganic-organic hybrids have been synthesized by incorporation of the inorganic component of Ti(OC2H5)4 into the organic polymer of ethyl cellulose. The inorganic-organic hybrids did not dissolve in toluene used as a solvent for the starting materials. The ethanol was formed as a by-product of the alcoholysis condensation reaction between Ti(OC2H5)4 and ethyl cellulose. These results suggest that ethoxy groups of Ti(OC2H5)4 react with hydroxy groups of ethyl cellulose to form cross-linking bonds of –O–Ti–O–. The reaction of Ti(OC2H5)4 with ethyl cellulose was further investigated by Fourier transform infrared (FT-IR) spectroscopy. The FT-IR spectroscopic experiments revealed that the Ti–O bond state of Ti(OC2H5)4 was changed by refluxing a toluene solution of Ti(OC2H5)4 with ethyl cellulose. The inorganic-organic hybrids have an interesting dielectric property; their dielectric constant is higher than that of ethyl cellulose and that of a simple mixture of TiO2 and ethyl cellulose. 相似文献
96.
The kinetics of the surface tension of micellar solutions of nonionic surfactant Triton X-100 is measured experimentally by means of three different techniques: oscillating jet, maximum bubble pressure and inclined plate. They allow to study the micellization kinetics at various time scales (from a few milliseconds to a few seconds) in fairly large concentration region up to 50 times CMC. The experimental data are satisfactorily explained by a theoretical model accounting for the kinetics of micellization, diffusion of surfactant species and expansion of the bubble interface. By this model are computed the characteristic times of diffusion and micellization, which are of comparable magnitude (about 5 to 200 ms), and the Gibbs' elasticity. The micellization time constant corresponds to the slow relaxation process known to coincide with the disintegration of micelles. Comparing our data with other data from literature one can conclude that more realistic information for the micellization kinetics is obtained by the maximum bubble pressure and the oscillating jet method. The inclined plate seems too slow to measure the relaxation processes in micellar solutions of this surfactant. 相似文献
97.
A method has been developed for the preparation of modified silica plates for high performance thin-layer chromatography (HPTLC). Some typical organosilanes were thus allowed to react in situ with the silica of Merck HPTLC-plates. This method was found to be highly reproducible, simple and cheap. Non-polar plates were prepared and compared with commercial plates from Merck, Whatman and Macherey-Nagel. Modification with cyanodecyltrichlorosilane resulted in plates that showed good coverage, efficiency and low residual silica activity. Silica modified with a multifunctional silane has different properties in different organic solvents. It will appear to be non-polar in a polar solvent and vice versa. New advantageous separation systems are thus made feasible by the presence of cyano groups on the plate. The utility of modified thin-layer plates is demonstrated by the separation of some homologues of p-hydroxybenzoic acid esters and of some polycyclic aromatic hydrocarbons. 相似文献
98.
A composite film of ethylenediamine tetraacetic acid (EDTA)‐ZrO2 organic‐inorganic hybrid was prepared based on the chelation between Zr(IV) and EDTA. The direct electrochemical behavior of cytochrome c (cyt. c) at the hybrid film modified glassy carbon electrodes was investigated. The immobilized EDTA can promote the redox of heme in horse heart cyt. c which gives rise to a pair of reversible redox peaks with a formal potential of 40 mV (vs. SCE). The peak current increased linearly with the increase of cyt. c concentration in the range of 1.6 × 10?6—8.0 × 10?5 mol·L?1 with the correlation coefficient of 0.996. Further investigation shows that metal ions can impede the electron transfer of cyt. c. The impediment capability of metal ions depends on their coordination capability with EDTA and their valence number. 相似文献
99.
Motoyuki Toki 《Journal of Sol-Gel Science and Technology》1994,2(1-3):97-101
This paper describes the attempt to prepare a new group of monodispersed silica-polymer hybrid particles, which consists of silica and amide polymer: poly(vinylpyrrolidone) (PVP) and poly(2-ethyloxazoline) (POXZ). Preparation method is based on the growth of hybrid seeds by the addition of TEOS-polymer solution.Monodispersed PVP-silica hybrid particles of 1.24 µm in diameter were prepared by growing the hybrid seeds of 0.54 µm by the addition of TEOS-PVP solution with ammonia catalyst. In the case of POXZ-silica particles, addition of TEOS-POXZ solution to the solution containing 0.54 µm seeds resulted in monodispersed POXZ-silica hybrid particles and four times repetition of the addition for particle growth gave the hybrid particles of the diameter of 1.6 µm.Improvement of mechanical properties of hybrid particles was observed when the particles were heated at 100 200°C. 相似文献
100.
A novel organic-inorganic hybrid compound {[Cu(2,2′-bpy)2]2Mo8O26} has been hydrothermally synthesized and structurally characterized by single-crystal X-ray diffraction. The compound crystallizes in the orthorhombic space group, Pna21,with a=2.4164(5),b=1.8281(4),c=1.1877(2)nm,V=5.247(2)nm^3,Z=4,and final R1=0.0331,wR2=0.0727.The structure consists of discrete {[Cu(2,2′-bpy)2]2Mo8O26} clusters,constructed from a β-octamolybdate subunit[Mo8O26]^4- covalently bonded to two [Cu(2,2′-bpy)2]^2 coordination complex cations via bridging oxo groups.In addition,the spectroscopic properties and thernal behavior of this compound have been investigated by spectroscopic techniques (UV-vis,IR,Raman and EPR spectra) and TG analysis. 相似文献