Recovery of motor function after traumatic spinal cord injury by using plasma-synthesized polypyrrole/iodine application in combination with a mixed rehabilitation scheme.

Traumatic spinal cord injury (TSCI) can cause paralysis and permanent disability. Rehabilitation (RB) is currently the only accepted treatment, although its beneficial effect is limited. The development of biomaterials has provided therapeutic possibilities for TSCI, where our research group previously showed that the plasma-synthesized polypyrrole/iodine (PPy/I), a biopolymer with different physicochemical characteristics than those of the PPy synthesized by conventional methods, promotes recovery of motor function after TSCI. The present study evaluated if the plasma-synthesized PPy/I applied in combination with RB could increase its beneficial effects and the mechanisms involved. Adult rats with TSCI were divided into no treatment (control); biopolymer (PPy/I); mixed RB by swimming and enriched environment (SW/EE); and combined treatment (PPy/I + SW/EE) groups. Eight weeks after TSCI, the general health of the animals that received any of the treatments was better than the control animals. Functional recovery evaluated by two scales was better and was achieved in less time with the PPy/I + SW/EE combination. All treatments significantly increased ßIII-tubulin (nerve plasticity) expression, but only PPy/I increased GAP-43 (nerve regeneration) and MBP (myelination) expression when were analyzed by immunohistochemistry. The expression of GFAP (glial scar) decreased in treated groups when determined by histochemistry, while morphometric analysis showed that tissue was better preserved when PPy/I and PPy/I + SW/EE were administered. The application of PPy/I + SW/EE, promotes the preservation of nervous tissue, and the expression of molecules related to plasticity as ßIII-tubulin, reduces the glial scar, improves general health and allows the recovery of motor function after TSCI. The implant of the biomaterial polypyrrole/iodine (PPy/I) synthesized by plasma (an unconventional synthesis method), in combination with a mixed rehabilitation scheme with swimming and enriched environment applied after a traumatic spinal cord injury, promotes expression of GAP-43 and ßIII-tubulin (molecules related to plasticity and nerve regeneration) and reduces the expression of GFAP (molecule related to the formation of the glial scar). Both effects together allow the formation of nerve fibers, the reconnection of the spinal cord in the area of injury and the recovery of lost motor function. The figure shows the colocalization (yellow) of ßIII-tubilin (red) and GAP-43 (green) in fibers crossing the epicenter of the injury (arrowheads) that reconnect the rostral and caudal ends of the injured spinal cord and allowed recovery of motor function.

Photo-Induced Atom-Transfer Radical Reactions Using Charge-Transfer Complex between Iodine and Tertiary Amine.

In the presence of charge-transfer complexes between iodine and tertiary amines, the aqueous-medium atom-transfer radical reactions proceeded under visible light irradiation without the typical photocatalysts.

Ab initio studies of ultrafast x-ray scattering of the photodissociation of iodine.

We computationally examine various aspects of the reaction dynamics of the photodissociation and recombination of molecular iodine. We use our recently proposed formalism to calculate time-dependent x-ray scattering signal changes from first principles. Different aspects of the dynamics of this prototypical reaction are studied, such as coherent and noncoherent processes, features of structural relaxation that are periodic in time versus nonperiodic dissociative processes, as well as small electron density changes caused by electronic excitation, all with respect to x-ray scattering. We can demonstrate that wide-angle x-ray scattering offers a possibility to study the changes in electron densities in nonperiodic systems, which render it a suitable technique for the investigation of chemical reactions from a structural dynamics point of view.

Photodissociation of hydrated hydrogen iodide clusters.

Using high-level ab initio calculations and excited state ab initio molecular dynamics simulations, we show that hydrated iodic acids release hydrogen radicals and/or hydrogen molecules as well as iodine radicals upon excitation. Its photoreaction process involving charge transfer to the solvent takes place in four steps: 1) hydration of the acid, 2) charge transfer to water upon excitation of hydrated acid, 3) detachment of the neutral iodine atom, and 4) detachment of the hydrogen radical. The iodine detachment process from excited hydrated hydro-iodic acids is exothermic and the detachment of hydrogen radicals from hydrated hydronium radicals is spontaneous if the initial kinetic energy of the cluster is high enough to get over the activation barrier of the detachment. The complete release of the radicals can be understood in terms of kinetics. This study shows how the hydrogen and halogen radicals are dissociated and released from their hydrated acids. Simple experiments corroborate our predicted mechanism for the release of hydrogen molecules from iodic acid in water by ultraviolet light.

Polymer gel dosimetry for synchrotron stereotactic radiotherapy and iodine dose-enhancement measurements.

Synchrotron stereotactic radiotherapy (SSR) is a radiotherapy technique that makes use of the interactions of monochromatic low energy x-rays with high atomic number (Z) elements. An important dose-enhancement can be obtained if the target volume has been loaded with a sufficient amount of a high-Z element, such as iodine. In this study, we compare experimental dose measurements, obtained with normoxic polymer gel (nPAG), with Monte Carlo computations. Gels were irradiated within an anthropomorphic head phantom and were read out by magnetic resonance imaging. The dose-enhancement due to the presence of iodine in the gel (iodine concentration: 5 and 10 mg ml(-1)) was measured at two radiation energies (35 and 80 keV) and was compared to the calculated factors. nPAG dosimetry was shown to be efficient for measuring the sharp dose gradients produced by SSR. The agreement between 3D gel dosimetry and calculated dose distributions was found to be within 4% of the dose difference criterion and a distance to agreement of 2.1 mm for 80% of the voxels. Polymer gel doped with iodine exhibited higher sensitivity, in good agreement with the calculated iodine-dose enhancement. We demonstrate in this preliminary study that iodine-doped nPAG could be used for measuring in situ dose distributions for iodine-enhanced SSR treatment.

Experimental quantification of cavitation yield revisited: focus on high frequency ultrasound reactors.

Acoustic cavitation plays an important role in enhancing the reaction rate of chemical processes in sonochemical systems. However, quantification of cavitation intensity in sonochemical systems is generally limited to low frequency systems. In this study, an empirical determination of cavitation yield in high frequency ultrasound systems was performed by measuring the amount of iodine liberated from the oxidation of potassium iodide (KI) solution at 1.7 and 2.4 MHz. Experiments for determining cavitation were carried out at various solute (KI) concentrations under constant temperature, obtained by direct cooling of the solution and variable temperature conditions, in the absence of external cooling. Cavitation yield measurements, reported in this work, extend previously reported results and lend credence to the two step reaction pathway in high frequency systems. Additionally, the concentration of KI and temperature affect the cavitation yield of a system such that the iodine production is proportional to both conditions. It is proposed that direct cooling of sonicated KI solution may be advantageous for optimization of cavitation intensity in high frequency sonochemical reactors.

Natural solar photolysis of total organic chlorine, bromine and iodine in water.

Municipal wastewater has been increasingly used to augment drinking water supplies due to the growing water scarcity. Wastewater-derived disinfection byproducts (DBPs) may negatively affect the aquatic ecosystems and human health of downstream communities during water reuse. The objective of this research was to determine the degradation kinetics of total organic chlorine (TOCl), bromine (TOBr) and iodine (TOI) in water by natural sunlight irradiation. Outdoor solar photolysis experiments were performed to investigate photolytic degradation of the total organic halogen (TOX) formed by fulvic acid and real water and wastewater samples. The results showed that TOX degradation by sunlight irradiation followed the first-order kinetics with half-lives in the range of 2.6-10.7 h for different TOX compounds produced by fulvic acid. The TOX degradation rates were generally in the order of TOI > TOBr â‰… TOCl(NH2Cl) > TOCl(Cl2). High molecular weight TOX was more susceptible to solar photolysis than corresponding low molecular weight halogenated compounds. The nitrate and sulfite induced indirect TOX photolysis rates were less than 50% of the direct photolysis rates under the conditions of this study. Fulvic acid and turbidity in water reduced TOX photodegradation. These results contribute to a better understanding of the fate of chlorinated, brominated and iodinated DBPs in surface waters.

Photo-induced halide redistribution in organic-inorganic perovskite films.

Organic-inorganic perovskites such as CH3NH3PbI3 are promising materials for a variety of optoelectronic applications, with certified power conversion efficiencies in solar cells already exceeding 21%. Nevertheless, state-of-the-art films still contain performance-limiting non-radiative recombination sites and exhibit a range of complex dynamic phenomena under illumination that remain poorly understood. Here we use a unique combination of confocal photoluminescence (PL) microscopy and chemical imaging to correlate the local changes in photophysics with composition in CH3NH3PbI3 films under illumination. We demonstrate that the photo-induced 'brightening' of the perovskite PL can be attributed to an order-of-magnitude reduction in trap state density. By imaging the same regions with time-of-flight secondary-ion-mass spectrometry, we correlate this photobrightening with a net migration of iodine. Our work provides visual evidence for photo-induced halide migration in triiodide perovskites and reveals the complex interplay between charge carrier populations, electronic traps and mobile halides that collectively impact optoelectronic performance.

Determination of regional myocardial perfusion by x-ray fluorescence.

Validation studies were performed to demonstrate the effectiveness of an x-ray induced fluorescence system in quantitating regional myocardial perfusion in vivo. In a series of 13 open-chested canines, x-ray induced fluorescence was used to simultaneously monitor iodine concentration transients which arose in the left ventricular lumen and in the myocardium after the intravenous injection of an iodinated flow tracer. Deconvolution of the recorded transients produced a transfer function from which the mean transit time for the tracer to travel between the left ventricular lumen and the myocardium was calculated. Measurements of regional myocardial perfusion (Q) made by radioactive microspheres were compared with the reciprocals of the mean transit times (MTT-1) and gave a linear correlation (n = 38): MTT-1 = 0.033 + 0.069 Q, r = 0.71. Comparison of the percent change in perfusion (dQ) relative to a control study for each dog with the percent change in the respective reciprocals of the mean transit times (dMTT-1) produced a linear correlation coefficient of r = 0.88 for the regression line dMTT-1 = 0.46 dQ - 10.7. The x-ray induced fluorescence system may provide a minimally invasive means for monitoring iodine concentration transients and determining relative, if not absolute, measures of regional myocardial perfusion.

Chernobyl and iodine deficiency in the Russian Federation: an environmental disaster leading to a public health opportunity.

The Chernobyl nuclear disaster of April 26, 1986, triggered a chain of devastating events that later included an unexpected increase in childhood thyroid cancer and evidence of iodine deficiency (ID) in Russia. For the Russian people the Chernobyl event had profound psychological impacts, provoking anxiety about nuclear technology and mistrust of governmental control efforts. Frequently in public health a crisis is required to create the political will to manage longstanding problems, and public health officials must rapidly mobilize to take advantage of the opportunity. In this case, ID, previously not seen as a problem in Russia, was recognized to be potentially serious, and the Russian Federation, assisted by the catalytic bi-national effort of the U.S.-Russian Joint Commission on Economic and Technological Cooperation (Gore-Chernomyrdin Commission (GCC)) established a model salt iodization policy, developed a planning process, and implemented a program to prevent ID through a systematic approach that included the people, government, and private groups using open communication, dissemination of the findings, and action plans. By 1999, political will had been mobilized and over 20% of the nation's salt was being iodized, up from about 1% in 1996. Universal iodization of salt was not a specific objective of the GCC; however, the increasing availability of iodized salt is leading to the elimination of ID, which is now a political goal in Russia. The full realization of this goal will require more time for education, marketing, and possibly legislative action.

[Stability of iodinated contrast media in UV-laser irradiation and toxicity of the photoproducts]. / Stabilität jodhaltiger Röntgenkontrastmittel unter UV-Laser-Bestrahlung und Toxizität der Photoprodukte.

PURPOSE: In XeCl-Excimer laser angioplasty, unintended and possibly harmful interaction of the UV-laser light and the contrast media may occur due to the high concentration of contrast medium proximal to the occlusion or subtotal stenosis. METHODS: One ml of three nonionic monomeric contrast agents (iopromide, iomeprol, iopamidol), one nonionic dimeric (jotrolane), and one ionic monomeric (amidotrizoate) X-ray contrast agent were irradiated with a XeCl excimer laser (lambda = 308 nm, pulse duration 120 ns, 50 Hz) using a 9 French multifiber catheter (12 sectors). Up to 20,000 pulses (106 J) were applied. Using high performance liquid chromatography the amount of liberated iodide as well as the fraction of unchanged contrast media were measured. Cytotoxicity of the photoproducts was tested in a colony formation assay of human skin fibroblasts. The contrast agents were irradiated with 2000 pulses/ml (5.3 mJ/pulse; 10.6 J) and then added to the cell cultures for a period of three hours in a concentration of 10%. RESULTS: Excimer laser irradiation induced iodide liberation of up to 3.3 mg iodide/ml. Up to 19% of the contrast agents changed their original molecular structure. Incubation of irradiated contrast agents resulted in a significantly decreased potential for colony formation (p values ranging from 0.0044 to 0.0102) with significantly higher toxicity of amidotrizoate and iomeprol in comparison to iopromide, iotrolan, and iopamidol. DISCUSSION: Due to the cytotoxic photoproducts and the high level of liberated iodide, it is recommended to flush the artery with physiological saline solution before applying a pulsed excimer laser in human arterial obstructions in order to reduce the contrast agent concentration at the site of irradiation.

TiO2 nanopowder co-doped with iodine and boron to enhance visible-light photocatalytic activity.

An iodine and boron co-doped TiO2 photocatalyst was prepared by the hydrolyzation-precipitation method. X-ray diffraction (XRD), ultraviolet-visible diffuse reflectance spectroscopy (UV-Vis DRS), and X-ray photoelectron spectroscopy (XPS) were applied to characterize the crystalline structure, light absorbing ability, and the chemical state of iodine and boron in the photocatalysts. The results of photocatalytic degradation of methyl orange demonstrated that the I-B-TiO2 catalyst prepared at 400 degrees C for 3 h exhibited the highest photocatalytic activity with a methyl orange degradation ratio of 61% under visible-light (lambda > or = 420 nm) irradiation for 120 min. The characterization results revealed that I-B-TiO2 is in conformity with the anatase TiO2 and that the doping of iodine and boron ions could efficiently inhibit the grain growth. Doped iodine was present in the multivalent forms of 17+, I- and I5+. Doped boron was present as B3+ in an as-prepared sample, forming a possible chemical environment such as B-O-Ti. Overall, the doping of I and B enhanced the ability of TiO2 to absorb visible-light, and it was observed that the photocatalytic activity of I-B-TiO2 was enhanced by the synergistic effect of I and B.

Normoxic polyacrylamide gel doped with iodine: response versus X-ray energy.

The basis of Synchrotron Stereotactic Radio-Therapy (SSRT) is the incorporation of high atomic number atoms (iodine, for example) into the tumour mass followed by an irradiation with a monochromatic, low energy, X-ray beam from a synchrotron source. The purpose of the present study was to determine whether polymer gel dosimetry could be used to measure the enhancement of absorbed energy induced by the iodine in the media. We have used a standard nPAG formulation, loaded with NaI and the irradiations were performed either with monochromatic X-rays at the ESRF medical beamline or with a conventional 6 MV X-ray beam from a linear accelerator at the Grenoble University Hospital. We observed sensitivity increase with iodine loaded gels irradiated at low energies, in good agreement with the theoretical iodine dose-enhancement. As expected, the response of the iodine-doped polymer gel was not increased after irradiation with mega-voltage X-rays. We demonstrate in this study that polymer gel dosimeters can be used for measuring dose-enhancement due to iodine presence in SSR treatment.

On the photochemistry of IONO2: absorption cross section (240-370 nm) and photolysis product yields at 248 nm.

The absolute absorption cross section of IONO(2) was measured by the pulsed photolysis at 193 nm of a NO(2)/CF(3)I mixture, followed by time-resolved Fourier transform spectroscopy in the near-UV. The resulting cross section at a temperature of 296 K over the wavelength range from 240 to 370 nm is given by log(10)(sigma(IONO(2))/cm(2) molecule(-1)) = 170.4 - 3.773 lambda + 2.965 x 10(-2)lambda(2)- 1.139 x 10(-4)lambda(3) + 2.144 x 10(-7)lambda(4)- 1.587 x 10(-10)lambda(5), where lambda is in nm; the cross section, with 2sigma uncertainty, ranges from (6.5 +/- 1.9) x 10(-18) cm(2) at 240 nm to (5 +/- 3) x 10(-19) cm(2) at 350 nm, and is significantly lower than a previous measurement [J. C. Mössinger, D. M. Rowley and R. A. Cox, Atmos. Chem. Phys., 2002, 2, 227]. The photolysis quantum yields for IO and NO(3) production at 248 nm were measured using laser induced fluorescence of IO at 445 nm, and cavity ring-down spectroscopy of NO(3) at 662 nm, yielding phi(IO)

Changes in the iodine content of vegetables following the Chernobyl accident.

In the early phenophases and at maturity the vegetables grown in the goitrogenic area have a lower iodine concentration than in non-goitrogenic areas. Within the same area, the amount of iodine is higher in young than in old vegetables and, in some species, it is higher in the young vegetables of the goitrogenic area than in the nature vegetables of the non-goitrogenic ones. Following the accident at the Chernobyl Nuclear Power Plant in April 1986, the iodine metabolism in plants was disorganized.

Marine aerosol formation from biogenic iodine emissions.

The formation of marine aerosols and cloud condensation nuclei--from which marine clouds originate--depends ultimately on the availability of new, nanometre-scale particles in the marine boundary layer. Because marine aerosols and clouds scatter incoming radiation and contribute a cooling effect to the Earth's radiation budget, new particle production is important in climate regulation. It has been suggested that sulphuric acid derived from the oxidation of dimethyl sulphide is responsible for the production of marine aerosols and cloud condensation nuclei. It was accordingly proposed that algae producing dimethyl sulphide play a role in climate regulation, but this has been difficult to prove and, consequently, the processes controlling marine particle formation remains largely undetermined. Here, using smog chamber experiments under coastal atmospheric conditions, we demonstrate that new particles can form from condensable iodine-containing vapours, which are the photolysis products of biogenic iodocarbons emitted from marine algae. Moreover, we illustrate, using aerosol formation models, that concentrations of condensable iodine-containing vapours over the open ocean are sufficient to influence marine particle formation. We suggest therefore that marine iodocarbon emissions have a potentially significant effect on global radiative forcing.