EPR PERSISTENCE MEASUREMENTS OF UV-INDUCED MELANIN FREE RADICALS IN WHOLE SKIN

Electron paramagnetic resonance is used to detect the formation of free radicals caused by exposure to ultraviolet radiation in chemically untreated rabbit skin. A fast jump in EPR signal level, occurring over a few seconds, is observed immediately after a skin sample is exposed to UV. This is followed by a slower increase toward an elevated steady-state signal over a period of hours as the skin is continuously exposed to a UV light source. Upon cessation of UV light exposure, EPR signal levels undergo an abrupt drop followed by a slower decay toward natural levels. Elevated free radical concentrations following UV exposure are found to persist for several hours in whole skin. These results are consistent with time-resolved EPR measurements of photoinduced radicals in various natural melanins.     

Femtosecond laser drilling of alumina ceramic substrates

In the paper, the result on femtosecond laser drilling of alumina ceramic substrate was reported. The effects of various laser parameters such as different focus position, traverse speed, drilling pattern, pausing time, etc. on the drilled hole quality in terms of surface finish, heat affected zone (HAZ), hole circularity, debris, microcracks were studied. The quality of laser-drilled holes on alumina ceramic substrates was evaluated with optical microscope, SEM/EDX, and X-ray μ-CT analysis. The optimum drilling conditions were identified. High-quality laser-drilled holes on alumina ceramic substrates were demonstrated. The developed process has potential application in manufacturing of alumina substrate based electronic devices.     

Prediction of turbulent gas–solids flow in curved ducts using the Eulerian–Lagrangian method

The flow of particulate two‐phase flow mixtures occur in several components of solid fuel combustion systems, such as the pressurised fluidised bed combustors (PFBC) and suspension‐fired coal boilers. A detailed understanding of the mixture characteristics in the conveying component can aid in refining and optimising its design. In this study, the flow of an isothermal, dilute two‐phase particulate mixture has been examined in a high curvature duct, which can be representative of that transporting the gas–solid mixture from the hot clean‐up section to the gas turbine combustor in a PFBC plant. The numerical study has been approached by utilising the Eulerian–Lagrangian methodology for describing the characteristics of the fluid and particulate phases. By assuming that the mixture is dilute and the particles are spherical, the governing particle momentum equations have been solved with appropriately prescribed boundary conditions. Turbulence effects on the particle dispersion were represented by a statistical model that accounts for both the turbulent eddy lifetime and the particle transit time scales. For the turbulent flow condition examined it was observed that mixtures with small particle diameters had low interphase slip velocities and low impaction probability with the pipe walls. Increasing the particle diameters (>50 μm) resulted in higher interphase slip velocities and, as expected, their impaction probability with the pipe walls was significantly increased. The particle dispersion is significant for the smaller sizes, whereas the larger particles are relatively insensitive to the gas turbulence. The main particle impaction region, and locations most prone to erosion damage, is estimated to be within an outer duct length of two to six times the duct diameter, when the duct radius of curvature to the duct diameter ratio is equal to unity. Copyright © 1999 John Wiley & Sons, Ltd.     

Inducing a pH-dependent conformational response by competitive binding to Zn2+ of a series of chiral ligands of disparate basicity

Molecules that change shape in response to environmental conditions are central to biological molecular communication devices and their synthetic chemical analogues. Here we report a molecular system in which a series of chiral anionic ligands of differing basicity are selectively protonated according to the pH of the medium. A cationic circular dichroism (CD) reporter complex responds to anion binding by selecting one of two alternative enantiomeric conformations. Exploiting the principle that less basic anions have, in general, weaker electrostatic interactions than more basic anions, a set of three chiral acids with large (>5 unit) pK_a differences and differing configurations were sequentially deprotonated in acetonitrile by addition of base, allowing the most basic anion in the mixture at any time to bind to the reporter complex. A characteristic CD output resulted, which changed in sign as the next-most basic anion was revealed by the next deprotonation in the series. Four cycles of switching between three ligand-bound states were achieved with minimal changes in signal magnitude, by alternating addition of base and acid. The pH-dependent conformational response was used to transduce a signal by appending to the binding site a 2-aminoisobutyric acid (Aib) oligomer, whose M or P helical conformation depended on the chirality of the bound ligand, and was reported by a remote ¹³C-labelled NMR reporter group. The multicomponent system thus converts a pH signal into a programmable conformational response which induces a remote spectroscopic effect.

A chemical system comprising a series of chiral acids of differing pK_a, a metal, and a conformationally labile chromophore responds to pH with a CD spectrum that reports the absolute stereochemistry of the most basic anion in the mixture.     

Refoldable Foldamers: Global Conformational Switching by Deletion or Insertion of a Single Hydrogen Bond

Small changes in the structure of a foldamer may lead to gross changes in conformational preference. We show that the simple insertion or deletion of a single hydrogen bond by changes in pH or by photochemical deprotection is sufficient to refold a helical oligomer, interconverting M and P screw‐sense preference. As a consequence of the switch, information may be transmitted to a remote catalytic site, selectively directing the formation of either of two enantiomeric products by a reaction involving 1,22‐remote intermolecular asymmetric induction.     

(TMTSF)2(2,5-Tcnqbr2): Structure and Physical Properties

The 2:1 charge-transfer salt (TMTSF)₂(2,5-TCNQBr2) has been prepared and its physical properties investigated. Its crystal structure consists of segregated stacks of TMTSF donors (ring-over-bond overlap pattern; mean interplanar spacing of 3.6A) and chains of edge-on and disordered 2,5-TCNQBr2 acceptors. Infrared data are suggestive of unit charge on the 2,5-TCNQBr2 molecule and, therefore, half charge on the TMTSF donor. Resistivity data are successfully interpreted on the basis of a percolation construction. Magnetic data are also presented.     

Background-Free Detection of Spin-Exchange Dynamics at Ultra-Low Magnetic Field

Ultra-low field nuclear magnetic resonance spectroscopy (NMR) and imaging (MRI) inherently suffer from a low signal-to-noise ratio due to the small thermal polarization of nuclear spins. Transfer of polarization from a pre-polarized spin system to a thermally polarized spin system via the Spin Polarization Induced Nuclear Overhauser Effect (SPINOE) could potentially be used to overcome this limitation. SPINOE is particularly advantageous at ultra-low magnetic field, where the transferred polarization can be several orders of magnitude higher than thermal polarization. Here we demonstrate direct detection of polarization transfer from highly polarized ¹²⁹Xe gas spins to ¹H spins in solution via SPINOE. At ultra-low field, where thermal nuclear spin polarization is close to background noise levels and where different nuclei can be simultaneously detected in a single spectrum, the dynamics of the polarization transfer can be observed in real time. We show that by simply bubbling hyperpolarized ¹²⁹Xe into solution, we can enhance ¹H polarization levels by a factor of up to 151-fold. While our protocol leads to lower enhancements than those previously reported under extreme Xe gas pressures, the methodology is easily repeatable and allows for on-demand enhanced spectroscopy. SPINOE at ultra-low magnetic field could also be employed to study ¹²⁹Xe interactions in solutions.     

Determination of chromium in human serum by electro-thermal atomic absorption spectrometry

An accurate and sensitive method for serum chromium determinations by graphite-furnace atomic absorption spectrometry is described. Samples containing a small amount of magnesium nitrate as an ashing aid/matrix modifier are lyophilized and dry-ashed in silanized quartz tubes; the residue is dissolved in 0.1 M HCl. Because of the very low levels of chromium in serum, strict contamination control measures must be used throughout the procedures for collection, storage, preparation and quantitation. Standard curves are prepared by using a bovine serum pool, which also serves as a quality control measure. The uniform nature of sera obviates the need to use the method of standard additions. The detection limit of the method is about 0.03 ng ml^?1 Cr and the accuracy of the method is evaluated by comparison with stable-isotope-dilution mass spectrometry.     

c(RGDfK)- and ZnTriMPyP-Bound Polymeric Nanocarriers for Tumor-Targeted Photodynamic Therapy

Active targeting strategies are currently being extensively investigated in order to enhance the selectivity of photodynamic therapy. The aim of the present research was to evaluate whether the external decoration of nanopolymeric carriers with targeting peptides could add more value to a photosensitizer formulation and increase antitumor therapeutic efficacy and selectivity. To this end, we assessed PLGA-PLA-PEG nanoparticles (NPs) covalently attached to a hydrophilic photosensitizer 5-[4-azidophenyl]-10,15,20-tri-(N-methyl-4-pyridinium)porphyrinato zinc (II) trichloride (ZnTriMPyP) and also to c(RGDfK) peptides, in order to target α_vβ₃ integrin-expressing cells. In vitro phototoxicity investigations showed that the ZnTriMPyP-PLGA-PLA-PEG-c(RGDfK) nanosystem is effective at submicromolar concentrations, is devoid of dark toxicity, successfully targets α_vβ₃ integrin-expressing cells and is 10-fold more potent than related nanosystems where the PS is occluded instead of covalently bound.