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61.
Hierarchical porous silica materials with a trimodal pore system using surfactant templates 总被引:1,自引:0,他引:1
Porous silica exhibiting a hierarchically ordered trimodal pore system with a well-defined reverse opal microstructure and bimodal mesoporosity in the walls has been prepared by using polystyrene latex spheres, a novel block copolymer and an ionic liquid surfactant as templates. The resulting materials exhibit hierarchical order at three length scales (small mesopores: 2-3 nm; large mesopores: 11-12 nm; macropores: 360 nm). 相似文献
62.
Functional MRI using intravascular contrast agents: detrending of the relative cerebrovascular (rCBV) time course 总被引:3,自引:0,他引:3
In pharmacological fMRI experiments in animal models, blood pool contrast agents may be used to map cerebral blood volume change as a surrogate for neural activation. When the background signal drift due to contrast agent washout is non-negligible over the duration of the signal changes of interest, time-course detrending is essential for accurate interpretation of the experiment. Detrending approaches based on estimation of the background signal from a baseline period of the time course prior to pharmacological (or functional) challenge were evaluated with the aim of identifying a robust method of estimating the contrast agent washout contribution to the background signal drift. For fMRI studies in the rat, it was found that a constrained fit of a mono-exponential washout model was more accurate than a constant background approximation and unconstrained fits for experiments investigating the functional response to rapid pharmacological challenges such as cocaine and amphetamine. Moreover, the constrained fitting approach allows shorter baseline periods than unconstrained extrapolation, reducing the required duration of the experiment. 相似文献
63.
Dau T 《The Journal of the Acoustical Society of America》2003,113(2):936-950
A model for the generation of auditory brainstem responses (ABR) and frequency following responses (FFRs) is presented. The model is based on the concept introduced by Goldstein and Kiang [J. Acoust. Soc. Am. 30, 107-114 (1958)] that evoked potentials recorded at remote electrodes can theoretically be given by convolution of an elementary unit waveform (unitary response) with the instantaneous discharge rate function for the corresponding unit. In the present study, the nonlinear computational auditory-nerve model recently developed by Heinz et al. [ARLO 2(3), 91-96 (2001)] was used to calculate the instantaneous discharge rate ri(t) for fibers i in the frequency range from 0.1 and 10 kHz. The summed activity across frequency was convolved with a unitary response which is assumed to reflect contributions from different cell populations within the auditory brainstem, recorded at a given pair of electrodes on the scalp. Predicted potential patterns are compared with experimental data for a number of stimulus and level conditions. Clicks, chirps as defined in Dau et al. [J. Acoust. Soc. Am. 107, 1530-1540 (2000)], long-duration stimuli comprising the chirp, as well as tones and slowly varying tonal sweeps were considered. The results demonstrate the importance of considering the effects of the basilar-membrane traveling wave and auditory-nerve processing for the formation of ABR and FFR. Specifically, the results support the hypothesis that the FFR to low-frequency tones represents synchronized activity mainly stemming from mid- and high-frequency units at more basal sites, and not from units tuned to frequencies around the signal frequency. 相似文献
64.
For aL
∞
(ℝ+)∩L
1
(ℝ+) the truncated Bessel operator B
τ
(a) is the integral operator acting on L
2
[0,τ] with the kernel
where J
ν
stands for the Bessel function with ν>−1. In this paper we determine the asymptotics of the determinant det(I+B
τ
(a)) as τ→∞ for sufficiently smooth functions a for which a(x)≠1 for all x[0,∞). The asymptotic formula is of the form det(I+B
τ
(a))∼G
τ
E with certain constants G and E, and thus similar to the well-known Szeg?-Akhiezer-Kac formula for truncated Wiener-Hopf determinants.
Received: 23 April 2002 / Accepted: 25 September 2002 Published online: 24 January 2003
RID="*"
ID="*" Supported in part by NSF Grant DMS-9970879.
Communicated by J.L. Lebowitz 相似文献
65.
66.
Time-resolved spectroscopic techniques have been used to prepare and to interrogate transient species that are models for reactive intermediates in cobalt-catalyzed hydroformylation. Flash photolysis of acetylcobalt carbonyl complexes of the type RC(O)Co(CO)3(PR'3) (A; R = CH3, CD3, or C2H5; R' = Ph or nBu) leads to CO photodissociation to give the "unsaturated" intermediate [RC(O)Co(CO)2(PR'3)] (I), which decays by two competitive pathways, alkyl migration to the cobalt to give RCo(CO)3PR'3 (M) and reaction with CO to re-form A. With the perdeuterioacetyl complex (R = CD3, R' = Ph), rate constants both of CO trapping (kco) and of methyl migration (kM) were just slightly smaller than those of the perprotio analogue (kh/kd = 1.04 +/- 0.01 and 1.07 +/- 0.09, respectively). Thus, any stabilization of the "vacant" coordination site of I by agostic interactions with the acetyl methyl group appears to be kinetically insignificant, consistent with the previous conclusion (Inorg. Chem. 2000, 39, 3098-3106) that this site is stabilized by an eta 2-coordinated carbonyl. Changing the phosphine ligand has a greater influence on the kinetics of I. The species generated by the flash photolysis of the trialkyl phosphine complex CH3C(O)Co-(CO)3(P(nBu3)) exhibited a much larger kM than was the case for the PPh3 analogue, although there was little difference in the kco values. Similarly, kM proved to be sensitive to the nature of R as demonstrated by the slower alkyl migration (at 298 K) for the intermediate formed by CO photodissociation from the propionyl complex C2H5C(O)Co(CO)3PPh3 relative to the acetyl analogue. Nonetheless, all these intermediates displayed analogous time-resolved infrared spectra and general kinetics behavior in benzene solution (implying common mechanisms for decay), so it is concluded that all are present as the eta 2-chelated acyl structure under these conditions. 相似文献
67.
68.
Dirk Steinhilber Torsten Rossow Dr. Stefanie Wedepohl Florian Paulus Dr. Sebastian Seiffert Prof. Dr. Rainer Haag 《Angewandte Chemie (International ed. in English)》2013,52(51):13538-13543
pH‐Cleavable cell‐laden microgels with excellent long‐term viabilities were fabricated by combining bioorthogonal strain‐promoted azide–alkyne cycloaddition (SPAAC) and droplet‐based microfluidics. Poly(ethylene glycol)dicyclooctyne and dendritic poly(glycerol azide) served as bioinert hydrogel precursors. Azide conjugation was performed using different substituted acid‐labile benzacetal linkers that allowed precise control of the microgel degradation kinetics in the interesting pH range between 4.5 and 7.4. By this means, a pH‐controlled release of the encapsulated cells was achieved upon demand with no effect on cell viability and spreading. As a result, the microgel particles can be used for temporary cell encapsulation, allowing the cells to be studied and manipulated during the encapsulation and then be isolated and harvested by decomposition of the microgel scaffolds. 相似文献
69.
Tobias Krüger Katja Vorndran Dr. Torsten Linker Prof. Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2009,15(44):12082-12091
Arenes with various alkyl side‐chains were synthesized in high yields and excellent regioselectivities. Starting from toluic and naphthoic acids, the carboxylate group was conveniently substituted by alkyl halides by Birch reduction and subsequent decarbonylation. The method is characterized by inexpensive starting materials and reagents, and methylation of arenes was realized. Besides simple alkyl substituents, the scope of arene functionalization was extended by benzyl, fluoro, amino, and ester groups. We were able to control the alkylation of 1‐naphthoic acid during Birch reduction by the addition of tert‐butanol. This allowed the regioselective synthesis of mono and bis‐substituted naphthalenes from the same starting material. 相似文献
70.
Summary. We consider singularly perturbed linear elliptic problems in two dimensions. The solutions of such problems typically exhibit
layers and are difficult to solve numerically. The streamline diffusion finite element method (SDFEM) has been proved to produce
accurate solutions away from any layers on uniform meshes, but fails to compute the boundary layers precisely. Our modified
SDFEM is implemented with piecewise linear functions on a Shishkin mesh that resolves boundary layers, and we prove that it
yields an accurate approximation of the solution both inside and outside these layers. The analysis is complicated by the
severe nonuniformity of the mesh. We give local error estimates that hold true uniformly in the perturbation parameter , provided only that , where mesh points are used. Numerical experiments support these theoretical results.
Received February 19, 1999 / Revised version received January 27, 2000 / Published online August 2, 2000 相似文献