24 research outputs found
Efficient rate-power allocation for OFDM in a realistic fading environment
The implementation of practical adaptive resource
allocation scheme remains a key criterion to be satisfied for
realising spectrally efficient multitone wireless communications.
The ever-increasing demand for spectrally efficient broadband
wireless transmission technologies has spurred intensive research
leading towards the implementation of adaptive OFDM and
adaptive MIMO systems. Efforts in this direction have been
frustrated however by the lack of a clear and accurate description
of the fading behaviour typically encountered in the broadband
wireless transmission environment. This has been partially been
overcome by the use of mathematical modelling which captures
certain large-scale characteristics of the channel and facilitates
theoretical research. The “average” channel parameters gleaned
from these processes is typically then used to inform the design
and configuration of wireless networking equipment after the
broad application of generous safety margins. The resulting solu�tion is therefore quite robust to certain transient channel quality
degradation yet the generous safety tolerances render it unable
to exploit other transient transmission quality improvements
We seek to overcome the problems associated with this ap�proach by applying a theoretically sound novel adaptive resource
allocation framework to actual broadband wireless channel
development data. The allocation framework is derived from the
optimal OFDM allocation scheme for a known channel [1]: the
channel development data is obtained from actual measurement
of a broadband wireless mobile environment [2]. Prediction tech�niques are employed to overcome the time lag between channel
assessment and symbol transmission. We present the details of the
predictive resource allocation scheme used and include a broad
characterisation of the transmission environment in terms of the
time-varying fading processes observed. We provide some results
of the application of this scheme as typical performance levels
that may be achieved in an actual transmission environment
Photochemistry of Mycolactone A/B, the Causative Toxin of Buruli Ulcer
Photochemistry of mycolactone A/B and related unsaturated
fatty
acid esters is reported. On exposure to visible light, mycolactone
A/B gave a mixture of four photomycolactones. Pentaenoates and tetraenoates,
representing the unsaturated fatty acid portion of mycolactone A/B,
were found to show the reactivity profile parallel with that of mycolactone
A/B. The structure of the four photomycolactones was elucidated via
(1) structure determination of the four photoproducts in the tetraenoate
series; (2) their transformation to the photoproducts in the pentaenoate
and then mycolactone series. Triplet quenchers did not affect the
photochemical transformation, thereby indicating an event at the singlet
state. A concerted, photochemically allowed [4Ď€s + 2Ď€a]
cycloaddition was suggested to account for the observed result. This
study provided the structurally defined and homogeneous material,
which allowed demonstration that photomycolactones exhibit significantly
reduced cytotoxicity, compared with mycolactone A/B
MnO Nanoparticles Interdispersed in 3D Porous Carbon Framework for High Performance Lithium-Ion Batteries
Interdispersed MnO nanoparticles
that are anchored and encapsulated
in a three-dimensional (3D) porous carbon framework (MnO@CF) have
been constructed, which display nanosphere architecture with rich
porosity, well-defined carbon framework configuration, and excellent
structure stability. When evaluated as an anode material, the MnO@CF
exhibits relatively high specific capacity of 939 mA h g<sup>–1</sup> at current rate of 0.2 A g<sup>–1</sup> over 200 cycles and
excellent rate capability of 560.2 mA h g<sup>–1</sup> at 4
A g<sup>–1</sup>. By virtue of its mechanical stability and
desirable ionic/electronic conductivity, the specific design can be
a promising approach to fabricate high-performance lithium-ion batteries
Simple Synthesis of Mesoporous Carbon Nanofibers with Hierarchical Nanostructure for Ultrahigh Lithium Storage
In this study, a simple and reproducible synthesis strategy was developed to fabricate mesoporous carbon nanofibers (MCNFs) by using dual hard templates, a porous anodic aluminum oxide (AAO) membrane, and colloidal silica (Ludox TM-40). By using commercial templates, and removing AAO and the silica simultaneously, the synthesis procedures for MCNFs are greatly simplified without the need for separate preparation or the removal of templates in sequence. With phenol resin as a carbon precursor, the as-prepared MCNFs material reveals not only high surface area and mesoporous volume but also hierarchical nanostructure composed of hollow macrochannels derived from the AAO template, large mesopores (ca. 22 nm) from the removal of silica particles and micropores from the carbonization of phenol resin. Such unique surface and structural characteristics could provide a large quantity of active sites for Li storage and facilitate fast mass transport. Moreover, a one-dimensional (1D) carbon nanofiber (CNF) nanostructure favors fast electron transfer. The as-prepared MCNF anode demonstrates ultrahigh lithium storage capacity particularly at high rates, which is much higher than that reported for the commercial graphite and also significantly higher than other nanostructured carbon materials, such as ordered mesoporous carbon CMK-3 and ordered multimodal porous carbon (OMPC)
Hierarchical CuO–TiO<sub>2</sub> Hollow Microspheres for Highly Efficient Photodriven Reduction of CO<sub>2</sub> to CH<sub>4</sub>
In
this study, a scalable one-pot template-free synthesis strategy
was employed to fabricate CuO-incorporated TiO<sub>2</sub> hollow
microspheres in large scale. The as-prepared hollow spherical TiO<sub>2</sub> nanoparticles possess unique structural characteristics,
namely, large surface area and a hierarchical nanoarchitecture composed
of a hollow macroporous core connected with large mesopores in the
shell. The large surface area provides a great number of surface active
sites for the reactant adsorption and reaction whereas the hierarchical
nanoarchitecture enables fast mass transport of reactant and product
molecules within the porous framework. In addition, the hollow macroporous
core–mesoporous shell nanostructure favors multilight scattering/reflection,
resulting in enhanced harvesting of exciting light. Furthermore, the
incorporated CuO clusters work efficiently as a cocatalyst to improve
the photocatalytic activity. As a result, the CuO-incorporated TiO<sub>2</sub> hollow microsphere catalyst demonstrates much higher photocatalytic
activity toward photodriven reduction of CO<sub>2</sub> with H<sub>2</sub>O into CH<sub>4</sub> compared with the state-of-the-art photocatalyst,
commercial Degussa P25 TiO<sub>2</sub>. Also, the simple synthesis
strategy would enable large-scale industrial production of CuO–TiO<sub>2</sub> hollow microspheres
Large-Scale Synthesis of TiO<sub>2</sub> Microspheres with Hierarchical Nanostructure for Highly Efficient Photodriven Reduction of CO<sub>2</sub> to CH<sub>4</sub>
In this study, a simple and reproducible
synthesis strategy was employed to fabricate TiO<sub>2</sub> microspheres
with hierarchical nanostructure. The microspheres are macroscopic
in the bulk particle size (several hundreds to more than 1000 ÎĽm),
but they are actually composed of P25 nanoparticles as the building
units. Although it is simple in the assembly of P25 nanoparticles,
the structure of the as-prepared TiO<sub>2</sub> microspheres becomes
unique because a hierarchical porosity composed of macropores, larger
mesopores (ca. 12.4 nm), and smaller mesopores (ca. 2.3 nm) has been
developed. The interconnected macropores and larger mesopores can
be utilized as fast paths for mass transport. In addition, this hierarchical
nanostructure may also contribute to some extent to the enhanced photocatalytic
activity due to increased multilight reflection/scattering. Compared
with the state-of-the-art photocatalyst, commercial Degussa P25 TiO<sub>2</sub>, the as-prepared TiO<sub>2</sub> microsphere catalyst has
demonstrated significant enhancement in photodriven conversion of
CO<sub>2</sub> into the end product CH<sub>4</sub>. Further enhancement
in photodriven conversion of CO<sub>2</sub> into CH<sub>4</sub> can
be easily achieved by the incorporation of metals such as Pt. The
preliminary experiments with Pt loading reveal that there is still
much potential for considerable improvement in TiO<sub>2</sub> microsphere
based photocatalysts. Most interestingly and significantly, the synthesis
strategy is simple and large quantity of TiO<sub>2</sub> microspheres
(i.e., several hundred grams) can be easily prepared at one time in
the lab, which makes large-scale industrial synthesis of TiO<sub>2</sub> microspheres feasible and less expensive
Copper/Manganese Cocatalyzed Oxidative Coupling of Vinylarenes with Ketones
A novel
copper/manganese cocatalyzed direct oxidative coupling
of terminal vinylarenes with ketones via CÂ(sp<sup>3</sup>)–H
bond functionalization following C–C bond formation has been
developed using <i>tert</i>-butyl hydroperoxide as the radical
initiator. Various ketones underwent a free-radical addition of terminal
vinylarenes to give the corresponding 1,4-dicarbonyl products with
excellent regioselectivity and efficiency through one step. A possible
reaction mechanism has been proposed
Unactivated C(sp<sup>3</sup>)–H Bond Functionalization of Alkyl Nitriles with Vinylarenes and Mechanistic Studies
The first example
of a metal-free unactivated CÂ(sp<sup>3</sup>)–H
bond functionalization of alkyl nitriles with terminal vinylarenes
to provide Îł-ketonitrile derivatives is described. This protocol
features simple operations, a broad substrate scope, and atom and
step economy. In addition, Cu-catalyzed CÂ(sp<sup>3</sup>)–H
bond functionalization of azodiÂisobutyroÂnitrile (AIBN)
and analogues with terminal vinylarenes to generate Îł-ketonitriles
was also studied. A preliminary free-radical pathway was confirmed
by capturing an alkyl radical, and a conjugate system was found that
can stabilize radical intermediates and be in favor of this transformation.
Density functional theory (DFT) calculations also provide important
evidence of the free-radical pathway
<i>De Novo</i> Asymmetric Synthesis of Phoracantholide J
A <i>de novo</i> asymmetric total synthesis of the macrolide
natural product (<i>S</i>)-phoracantholide J has been achieved
in 10 steps from the commodity chemicals (1-pentyne, ethyl acrylate,
acetaldehyde, and hydrogen). The asymmetry of the route was introduced
by a Noyori reduction of a 3-yn-2-one, which makes the route equally
amenable to the synthesis of either enantiomer. In addition, this
route relies upon an alkyne zipper, a hydroalkynylation, and a macrolactonization
to complete the synthesis
Efficacy of Rifampin Plus Clofazimine in a Murine Model of <i>Mycobacterium ulcerans</i> Disease
<div><p>Treatment of Buruli ulcer, or <i>Mycobacterium ulcerans</i> disease, has shifted from surgical excision and skin grafting to antibiotic therapy usually with 8 weeks of daily rifampin (RIF) and streptomycin (STR). Although the results have been highly favorable, administration of STR requires intramuscular injection and carries the risk of side effects, such as hearing loss. Therefore, an all-oral, potentially less toxic, treatment regimen has been sought and encouraged by the World Health Organization. A combination of RIF plus clarithromycin (CLR) has been successful in patients first administered RIF+STR for 2 or 4 weeks. Based on evidence of efficacy of clofazimine (CFZ) in humans and mice with tuberculosis, we hypothesized that the combination of RIF+CFZ would be effective against <i>M</i>. <i>ulcerans</i> in the mouse footpad model of <i>M</i>. <i>ulcerans</i> disease because CFZ has similar MIC against <i>M</i>. <i>tuberculosis</i> and <i>M</i>. <i>ulcerans</i>. For comparison, mice were also treated with the gold standard of RIF+STR, the proposed RIF+CLR alternative regimen, or CFZ alone. Treatment was initiated after development of footpad swelling, when the bacterial burden was 4.64±0.14log<sub>10</sub> CFU. At week 2 of treatment, the CFU counts had increased in untreated mice, remained essentially unchanged in mice treated with CFZ alone, decreased modestly with either RIF+CLR or RIF+CFZ, and decreased substantially with RIF+STR. At week 4, on the basis of footpad CFU counts, the combination regimens were ranked as follows: RIF+STR>RIF+CLR>RIF+CFZ. At weeks 6 and 8, none of the mice treated with these regimens had detectable CFU. Footpad swelling declined comparably with all of the combination regimens, as did the levels of detectable mycolactone A/B. In mice treated for only 6 weeks and followed up for 24 weeks, there were no relapses in RIF+STR treated mice, one (5%) relapse in RIF+CFZ-treated mice, but >50% in RIF+CLR treated mice. On the basis of these results, RIF+CFZ has potential as a continuation phase regimen for treatment of <i>M</i>. <i>ulcerans</i> disease.</p></div