Noise-enhanced human balance control

Noise can enhance the detection and transmission of weak signals in certain nonlinear systems, via a mechanism known as stochastic resonance. Here we show that input noise can be used to improve motor control in humans. Specifically, we show that the postural sway of both young and elderly individuals during quiet standing can be significantly reduced by applying subsensory mechanical noise to the feet. We further demonstrate with input noise a trend towards the reduction of postural sway in elderly subjects to the level of young subjects. These results suggest that noise-based devices, such as randomly vibrating shoe inserts, may enable people to overcome functional difficulties due to age-related sensory loss.     

Mechanistically inspired design of Fe(III)-TAML peroxide-activating catalysts

Recent broad-ranging mechanistic studies of FeIII-TAML peroxide activators enable a strategy for designing catalysts with improved (i) hydrolytic and (ii) operational stabilities, (iii) faster activation of H2O2 and other peroxides, and (iv) a pH of highest activity closer to 7. Combining all items of insight leads to [Fe{1-NO2C6H3-3,4-(NCOCMe2NCO)2CF2}(OH2)]- (1a) which exhibits the most desirable technical performance in its class.     

Simple Sulfinate Synthesis Enables C?H Trifluoromethylcyclopropanation

A simple method to convert readily available carboxylic acids into sulfinate salts by employing an interrupted Barton decarboxylation reaction is reported. A medicinally oriented panel of ten new sulfinate reagents was created using this method, including a key trifluoromethylcyclopropanation reagent, TFCS‐Na. The reactivity of six of these salts towards C H functionalization was field‐tested using several different classes of heterocycles.     

MCSCF reaction-path energetics and thermal rate-constants for the reaction of3NH with H2

Summary The intrinsic reaction-path, reactants, transition state and products for the reaction of NH (^3–)+H₂ (¹ _g ⁺ ) NH₂ (²B₁)+H (²S) involving the lowest triplet electronic state of NH₃ were calculated using multi-configuration (MC) SCF methods. The calculated change of internal energy for the reaction of 11.0 kcal mol^–1 agrees with the experimental value within 2 kcal mol^–1. The barrier to reaction is 23.4 kcal mol^–1 high. The harmonic MCSCF reaction-path potential was calculated and canonical variational transition state theory calculations of the rate constants performed over a temperature range from 400 to 2500 K. The computed rate constants are generally two orders of magnitude smaller than those of the comparable reaction of OH with H₂, whereas those of the reverse reaction are by a factor of 20 larger than those of OH₂ with H.     

Speciation of metal(loid)s in environmental samples by X-ray absorption spectroscopy: A critical review

Element specificity is one of the key factors underlying the widespread use and acceptance of X-ray absorption spectroscopy (XAS) as a research tool in the environmental and geo-sciences. Independent of physical state (solid, liquid, gas), XAS analyses of metal(loid)s in complex environmental matrices over the past two decades have provided important information about speciation at environmentally relevant interfaces (e.g. solid–liquid) as well as in different media: plant tissues, rhizosphere, soils, sediments, ores, mineral process tailings, etc. Limited sample preparation requirements, the concomitant ability to preserve original physical and chemical states, and independence from crystallinity add to the advantages of using XAS in environmental investigations. Interpretations of XAS data are founded on sound physical and statistical models that can be applied to spectra of reference materials and mixed phases, respectively. For spectra collected directly from environmental matrices, abstract factor analysis and linear combination fitting provide the means to ascertain chemical, bonding, and crystalline states, and to extract quantitative information about their distribution within the data set. Through advances in optics, detectors, and data processing, X-ray fluorescence microprobes capable of focusing X-rays to micro- and nano-meter size have become competitive research venues for resolving the complexity of environmental samples at their inherent scale. The application of μ-XANES imaging, a new combinatorial approach of X-ray fluorescence spectrometry and XANES spectroscopy at the micron scale, is one of the latest technological advances allowing for lateral resolution of chemical states over wide areas due to vastly improved data processing and detector technology.     

NEUROTOXICITY OF TETRAPHENYLPORPHINESULFONATE TPPS4 and ITS RELATION TO PHOTODYNAMIC THERAPY*

Abstract Tetraphenylporphinesulfonate (TPPS₄) is a synthetic porphyrin that localizes in certain tumors to a higher absolute concentration and with more favorable tumor to other tissue ratios than any other porphyrin yet studied. Its utilization for photodynamic therapy and other applications has been inhibited by reported neurotoxicity. We injected TPPS₄ over a broad dose range of 5-150 mg kg^?1 and observed the effects on peripheral nerve in groups of animals sacrificed 35, 70 and 140 days later. No immediate deaths or phototoxic manifestations were seen. Light and electron microscopy, however, revealed cytoskeletal abnormalities and nerve fiber degeneration affecting both myelinated and unmyelinated fibers in all the time and dose groups. These findings have similarities to those of other experimental toxic neuropathies, and may also be related to the preponderance of autonomic manifestations in patients with porphyric neuropathy. The morphological changes consisted of tangles of fibrillar material in the myelinated fibers and loss of neurotubules in the unmyelinated fibers. Our studies indicate a direct interaction of TPPS₄ with tubulin. This biological mechanism may be involved in the selective distribution of certain parenterally administered porphyrins.     

Individual interface states and their implications for low-frequency noise in MOSFETs

We show that the wide distribution of time constants required to explain 1/ƒ noise in MOSFETs arises as a natural consequence of the multi-phonon model of carrier trapping into individual Si-SiO₂ interface states. A new class of random telegraph signal found in the drain current of small-area silicon MOSFETs is described. These signals are a result of defect metastability and are shown to be a source of non-Gaussian noise.