Enhancement of Ce/Cr Codopant Solubility and Chemical Homogeneity in TiO2 Nanoparticles through Sol-Gel versus Pechini Syntheses.

Ce/Cr codoped TiO2 nanoparticles were synthesized using sol-gel and Pechini methods with heat treatment at 400 °C for 4 h. A conventional sol-gel process produced well-crystallized anatase, while Pechini synthesis yielded less-ordered mixed-phase anatase + rutile; this suggests that the latter method enhances Ce solubility and increases chemical homogeneity but destabilizes the TiO2 lattice. Greater structural disruption from the decomposition of the Pechini precursor formed more open agglomerated morphologies, while the lower levels of structural disruption from pyrolysis of the dried sol-gel precursor resulted in denser agglomerates of lower surface areas. Codoping and associated destabilization of the lattice reduced the binding energies in both powders. Cr4+ formation in sol-gel powders and Cr6+ formation in Pechini powders suggest that these valence changes derive from synergistic electron exchange from intervalence and/or multivalence charge transfer. Since Ce is too large to allow either substitutional or interstitial solid solubility, the concept of integrated solubility is introduced, in which the Ti site and an adjacent interstice are occupied by the large Ce ion. The photocatalytic performance data show that codoping was detrimental owing to the effects of reduced crystallinity from lattice destabilization and surface area. Two regimes of mechanistic behavior are seen, which are attributed to the unsaturated solid solutions at lower codopant levels and supersaturated solid solutions at higher levels. The present work demonstrates that the Pechini method offers a processing technique that is superior to sol-gel because the former facilitates solid solubility and consequent chemical homogeneity.

A novel function for the DEAD-box RNA helicase DDX-23 in primary microRNA processing in Caenorhabditis elegans.

Primary microRNAs (pri-miRNAs) are cleaved by the nuclear RNase III Drosha to produce hairpin-shaped precursor miRNAs (pre-miRNAs). In humans, this process is known to be facilitated by the DEAD-box helicases p68 (DDX5) and p72 (DDX17). In this study, we performed a candidate-based RNAi screen in C. elegans to identify DEAD/H-box proteins involved in miRNA biogenesis. In a let-7(mg279) sensitized genetic background, knockdown of a homolog of yeast splicing factor Prp28p, DDX-23, or a homolog of human helicases p68 and p72, DDX-17, enhanced let-7 loss-of-function phenotypes, suggesting that these helicases play a role in let-7 processing and/or function. In both ddx-23(RNAi) and ddx-17(RNAi), levels of mature let-7 were decreased while pri-let-7 was found to accumulate, indicating that the helicases likely act at the level of pri-let-7 processing. DDX-23 and DDX-17 were also required for the biogenesis of other known heterochronic miRNAs, including lin-4 and the let-7 family members miR-48, miR-84 and miR-241. Their function was not confined to the heterochronic pathway, however, since they were both necessary for down-regulation of cog-1 by the spatial patterning miRNA, lsy-6. Here, we present a novel function for C. elegans DDX-23 in pri-miRNA processing, and also suggest a conserved role for DDX-17 in this process.

The use of a milli-whistle as a detector in gas analysis by gas chromatography.

This mini-review introduces a general understanding of the use of a milli-whistle as a gas chromatography (GC) detector in gas analysis, including our research on the methodology and theory associated with a number of different related applications. The milli-whistle is connected to the outlet of a GC capillary, and when the eluted gases and the GC carrier gas pass through it, a sound with a fundamental frequency is produced. The sound wave can be picked up by a microphone or an accelerometer, and after a fast Fourier transform, the online data obtained for frequency-change vs. retention time constitute a new method for detecting gases. The first part of this review discusses the fundamentals of the milli-whistle. Some modifications are also discussed, including various types of whistles and an attempt to maximize the sensitivity and stability of the method. The second part then focuses on several practical applications, including an analysis of hydrogen released from ammonia borane, inorganic gases produced from fireworks, the CO2/O2 ratio from expired human breath and a purity test for alcohols. These studies show that the GC-whistle method has great potential for use as a fast sampling ionization method, and for the direct analysis of biological and chemical samples at under ambient conditions.

Paper spray-MS for bioanalysis.

This Review provides a general understanding of paper spray-MS, including the methodology and theory associated with a number of different related applications. This method has become a direct sampling/ionization method for mass spectrometric analysis at ambient conditions and, as a result, it has greatly simplified and increased the speed of mass-spectrum analysis. It has now become an increasingly popular and important method for MS. The first part of this review discusses the fundamentals of paper spray. Some modifications are also reviewed, including nib-assisted paper spray, droplet monitoring, high-throughput paper spray, leaf spray, tissue spray and wooden tip spray. The second part focuses on recent applications, including the analysis of DBS, foodstuffs, drugs and oil. These studies show that paper spray-MS has great potential for use as a fast sampling ionization method, and for the direct analysis of biological and chemical samples at ambient conditions.

Monitoring temperature and light exposure of biosamples exposed to ultraviolet and low energy radiation.

We previously showed that T-lymphocytes produce catalytic amounts of hydrogen peroxide (H2O2) in a membrane-associated process when irradiated with narrowband ultraviolet B (UVB) light. This form of phototherapy is thought to be highly effective for treatment of inflammatory skin diseases such as psoriasis, but also includes the potential for severe burning and development of skin cancer. Consequently, information on the therapeutic mechanism of narrowband UVB phototherapy and its regulation is warranted. Our laboratory is researching the mechanistic involvement of T-cell H2O2 production and its potential regulation by low energy electromagnetic field (EMF) radiation, which has been shown to beneficially influence inflammatory diseases such as psoriasis. To study photochemical H2O2 production in small samples such as suspensions of T-lymphocyte cell extracts, we use a reactor in which 12 microliter-sized samples are exposed to UVB. We simultaneously operate two identical systems, one for experimental, the other for control samples, within a walk-in environmental chamber maintained at 37 degrees C. The current paper addresses the control of UVB light exposure and temperature in our experimental setup. We quantified UVB light b y radiometric sp ot measurements and by chemical potassium ferrioxalate actinometry. We modified the actinometer so that UVB light of 5-hour experiments could be detected. Temperature was controlled by air convection and remained constant within 0.5 degrees C in air and liquid samples. Preliminary data of the effect of low energy EMF radiation on T-cell H2O2 production are presented.

Endogenous activation of nicotinic receptors underlies sympathetic tone generation in neonatal rat spinal cord in vitro.

Without the brainstem, thoracic spinal cords of neonatal rats in vitro spontaneously generate tonic sympathetic nerve discharge (SND) in the splanchnic nerves. Activation of nicotinic receptors in cords is known to alter a repertoire of neurotransmitter releases to sympathetic preganglionic neurons (SPNs). Using in vitro nerve-cord preparations, we investigated whether endogenous nicotinic receptor activity is essential for SND genesis. Application of mecamylamine, an open-channel nicotinic receptor blocker, reduced SND in a progressive manner. Exogenous activation of nicotinic receptors by application of various nicotinic agonists generally excited SND at low agonistic concentrations. At higher concentrations, however, agonists induced biphasic responses characterized by an initial excitation followed by prolonged SND suppression. Whether ionotropic glutamate, GABA(A), or glycine receptors are downstream signals of nicotinic receptor activation was explored by pretreatment of cords with selective antagonists. The initial excitation of SND persisted in the presence of ionotropic glutamate receptor antagonists. In contrast, the SND suppression was partially reversed by glycine or GABA(A) receptor antagonists. Incubation of the cord in a low Ca(2+)/high Mg(2+) bath solution to block Ca(2+)-dependent synaptic transmission did not affect SND excitation induced by nicotinic agonists, confirming direct activation of postsynaptic nicotinic receptors on SPNs. In conclusion, the endogenous activity of nicotinic receptors is essential for SND genesis in the thoracic spinal cord. Nicotinic activation of glycinergic and GABAergic interneurons may provide a recurrent inhibition of SPNs for homeostatic regulation of sympathetic outflow.