Ag(x)VOPO(4): A Demonstration of the Dependence of Battery-Related Electrochemical Properties of Silver Vanadium Phosphorous Oxides on Ag / V Ratios

As a part of our on-going study on silver vanadium phosphorous oxides (Ag_xV_yO_zPO₄), we report here the first study of the electrochemical reduction of a low Ag/V ratio silver vanadium phosphorous oxide, Ag_0.48VOPO₄·1.9H₂O. Reminiscent of Ag₂VO₂PO₄ reduction, in situ formation of silver metal nanoparticles along with an associated increase in conductivity were observed after reduction of Ag_0.48VOPO₄·1.9H₂O with 0.37 electron equivalents. However, in contrast to our lithium/Ag₂VO₂PO₄ cells, our lithium/Ag_0.48VOPO₄·1.9H₂O cells displayed an even higher voltage on discharge and a characteristic multi-plateau voltage profile, where vanadium reduction was the first reduction step.     

Can segmented flow enhance heat transfer in microchannel heat sinks?

Liquid cooling is an efficient way to remove heat fluxes with magnitudes up to 10,000 W/cm². One limitation of current single-phase microchannel heat sinks is the relatively low Nusselt number, due to laminar flow. In this work, we experimentally investigate how to enhance the Nusselt number with the introduction of segmented flow. The segmented flow pattern was created by the periodic injection of air bubbles through a T-junction into water-filled channels. We designed a polycarbonate heat sink consisting of an array of seven parallel microchannels each with a square cross-section 500 μm wide. We show that segmented flow increases the Nusselt number of laminar flow by more than 100%, provided the mass velocity of the liquid is within the range 330–2000 kg/m² s.     

The Role of Dietary Cholesterol in Lipoprotein Metabolism and Related Metabolic Abnormalities: A Mini-review

Cholesterol plays a vital role in cell biology. Dietary cholesterol or “exogenous” cholesterol accounts for approximately one-third of the pooled body cholesterol, and the remaining 70% is synthesized in the body (endogenous cholesterol). Increased dietary cholesterol intake may result in increased serum cholesterol in some individuals, while other subjects may not respond to dietary cholesterol. However, diet-increased serum cholesterol levels do not increase the low-density lipoprotein/high-density lipoprotein (LDL/HDL) cholesterol ratio, nor do they decrease the size of LDL particles or HDL cholesterol levels. Elevated levels of LDL cholesterol, reduced HDL cholesterol levels, and small, dense LDL particles are independent risk factors for coronary artery disease. Dietary cholesterol is the primary approach for treatment of conditions such as the Smith–Lemli–Opitz syndrome. Recent studies have highlighted mechanisms for absorption of dietary cholesterol. These studies have help understand how dietary and/or pharmaceutical agents inhibit cholesterol absorption and thereby reduce LDL cholesterol concentrations. In this article, various aspects of cholesterol metabolism, including dietary sources, absorption, and abnormalities in cholesterol metabolism, have been summarized and discussed.     

First occurrence of the mysid Hemimysis anomala in an inland lake in North America,Oneida Lake,NY

Hemimysis anomala (Crustacea, Mysidae) is a recent invader to North America that until now was reported only from the Laurentian Great Lakes and their immediate embayments, along with the St. Lawrence River. In August 2009, we identified Hemimysis in diets of white perch and yellow perch in Oneida Lake, NY. Night time vertical plankton net tows detected Hemimysis at four sites across the lake. Hemimysis in fish diets (5.5–8.6 mm) were larger than in net tows (2.2–7.0 mm) and reproduction is occurring as some females had brood sacs. This is the first documented introduction of Hemimysis to an inland lake in North America, outside the Great Lakes. Oneida Lake is located 53 river km upstream from Lake Ontario, the nearest known source of Hemimysis. No genetic differences were found between Hemimysis in Oneida Lake and Lake Ontario, indicating this is likely the source of introduction. Several large rapids, locks, and dams separate the two lakes, and as a result the most likely vector of introduction to Oneida Lake is pleasure boat or light commercial traffic via the canal system or overland transport. The presence of Hemimysis in Oneida Lake 3 years after it was first found in Lake Ontario suggests this species may spread rapidly throughout the basin. Despite an intensive monitoring program on Oneida Lake directed at fish, zooplankton, and limnology, Hemimysis was only detected in fish diets and night time zooplankton tows, indicating it may go undetected in lakes for some time using traditional daytime net tows.     

Characterization of water-soluble organic carbon in urban atmospheric aerosols using solid-state 13C NMR spectroscopy

Solid-state 13C nuclear magnetic resonance (NMR) spectroscopy has been used to investigate the distribution of carbon functional groups in urban Atlanta aerosol fine (PM2.5) particles. Carbonaceous aerosol particles comprise a significant fraction of the ambient particle mass and are environmentally significant as they may influence radiative and cloud-nucleating properties and can also produce adverse health effects upon inhalation. The water-soluble organic carbon (WSOC) fraction was extracted from multiple 24 h integrated high-volume quartz filter samples and further separated into recovered hydrophobic and hydrophilic fractions using an approach similar to that used to extract humic and fulvic acids from aqueous samples. Solid-state 13C NMR results indicate that WSOC in urban atmospheric aerosol particles is mostly aliphatic in nature (approximately 95% by C mass) with major contributions from alkyl and oxygenated alkyls (approximately 80%), carboxylic acid (approximately 10%), and aromatic functional groups (approximately 4%). The aromatic C is associated with the recovered hydrophobic fraction of WSOC. These spectra have been compared to the 13C NMR results obtained from Suwannee River humic acid and a fractionated biomass burning sample. WSOC, and more importantly, its recovered hydrophobic fraction, is found to be only qualitatively similar to aqueous humic material. The biomass burning sample is significantly different from urban Atlanta WSOC and is composed of substantial amounts of sugar derivatives and phenolic compounds, as expected. The NMR results demonstrate the potential of this technique to investigate aerosol WSOC composition and to study its variations with changes in parameters such aerosol sources.     

An engineered virus as a bright fluorescent tag and scaffold for cargo proteins--capture and transport by gliding microtubules

We have demonstrated substantial capture and transport of fluorescently-labeled engineered cowpea mosaic virus (CPMV) using Drosophila kinesin-driven microtubules (MTs). The capture occurred through both NeutrAvidin (NA)-biotin and antibody (IgG)-antigen interactions. The MTs were derivatized with rabbit anti-chicken IgG or biotin, and the virus was conjugated with chicken IgG or NA. The CPMV conjugate was introduced into standard MT motility assays via convective flow at concentrations as high as 1.36 nM, and became bound to the MTs in densities as high as one virus per microm of MT length. When the CPMV conjugate was present at 17 pM, the average speed of the MTs bearing the NA-virus was 0.59 +/- 0.08 microm/sec, and that of those bearing IgG-virus was 0.52 +/- 0.15 microm/sec. These speeds are comparable to those of the unladen MTs (0.61 +/- 0.09 microm/sec), the presence of the virus on the MT causing only a small decrease in MT gliding speeds. The fluorescent CPMV appears to be superior to fluorescent polystyrene spheres of the same size, as both a reporter tag and a scaffold for MT-transported cargo proteins, because of its negligible non-specific adsorption and superior brightness. This work is important for the development of sensors based on nanolocomotion and biological recognition, or new strategies for the nanoassembly of biological structures.     

Integrated preconcentration SDS-PAGE of proteins in microchips using photopatterned cross-linked polyacrylamide gels

The potential of integration of functions in microfluidic chips is demonstrated by implementing on-chip preconcentration of proteins prior to on-chip protein sizing by sodium dodecyl sulfate-polyacrylamide gel electrophoresis (SDS-PAGE). Two polymeric elements-a thin (approximately 50 microm) size exclusion membrane for preconcentration and a longer (approximately cm) porous monolith for protein sizing-were fabricated in situ using photopolymerization. Contiguous placement of the two polymeric elements in the channels of a microchip enabled simple and zero dead volume integration of the preconcentration with SDS-PAGE. The size exclusion membrane was polymerized in the injection channel using a shaped laser beam, and the sizing monolith was cast by photolithography using a mask and UV lamp. Proteins injected electrophoretically were trapped on the upstream side of the size exclusion membrane (MW cutoff approximately 10 kDa) and eluted off the membrane by reversing the electric field. Subsequently, the concentrated proteins were separated in a cross-linked polyacrylamide monolith that was patterned contiguous to the size exclusion membrane. The extent of protein preconcentration is easily tuned by varying the voltage during injection or by controlling the sample volume loaded. Electric fields applied across the nanoporous membrane resulted in a concentration polarization effect evidenced by decreasing current over time and irreproducible migration of proteins during sizing. To minimize the concentration polarization effect, sieving gels were polymerized only on the separation side of the membrane, and an alternate electrical current path was employed, bypassing the membrane, for most of the elution and separation steps. Electrophoretically sweeping a fixed sample volume against the membrane yields preconcentration factors that are independent of protein mobility. The volume sweeping method also avoids biased protein loading from concentration polarization and sample matrix variations. Mobilities of the concentrated proteins were log-linear with respect to molecular weight, demonstrating the suitability of this approach for protein sizing. Proteins were concentrated rapidly (<5 min) over 1000-fold followed by high-resolution separation in the sieving monolith. Proteins with concentrations as low as 50 fM were detectable with 30 min of preconcentration time. The integrated preconcentration-sizing approach facilitates analysis of low-abundant proteins that cannot be otherwise detected. Moreover, the integrated preconcentration-analysis approach employing in situ formation of photopatterned polymeric elements provides a generic, inexpensive, and versatile method to integrate functions at chip level and can be extended to lowering of detection limits for other applications such as DNA analysis and clinical diagnostics.     

Exploring crown ethers as shift reagents for ion mobility spectrometry

A series of crown ethers, 12-crown-4, 15-crown-5, 18-crown-6, and dibenzo-30-crown-10, are examined as a possible means of shifting the mobilities of peptide ions. In this approach, a crown ether is added to a solution containing a mixture of peptides and is electrosprayed into the gas phase in order to create distributions of peptide-crown complexes. The ion complexes have different mobilities than the naked peptide ions, and the crown ether molecules appear to interact specifically with basic sites in the peptides thus providing some sequence selectivity. After the peptide-crown complexes are separated by ion mobility spectrometry, the ions can be collisionally activated to dissociate the complex (forming the naked peptide ions) prior to m/z analysis. The overall effect is that complex formation shifts peptide ions to different regions of the mobility spectrum, extending the ability to resolve components. The approach is illustrated by examining isobaric dipeptides as well as a combinatorial library containing 27 tripeptides. Cross sections for the series of crown ether ions and complexes that are observed are reported.     

The Effect of Poly(3‐hexylthiophene) Molecular Weight on Charge Transport and the Performance of Polymer:Fullerene Solar Cells

The time‐of‐flight method has been used to study the effect of P3HT molecular weight (M_n = 13–121 kDa) on charge mobility in pristine and PCBM blend films using highly regioregular P3HT. Hole mobility was observed to remain constant at 10^?4 cm²V^?1s^?1 as molecular weight was increased from 13–18 kDa, but then decreased by one order of magnitude as molecular weight was further increased from 34–121 kDa. The decrease in charge mobility observed in blend films is accompanied by a change in surface morphology, and leads to a decrease in the performance of photovoltaic devices made from these blend films.