Photochemical tyrosine oxidation with a hydrogen-bonded proton acceptor by bidirectional proton-coupled electron transfer

Amino acid radical generation and transport are fundamentally important to numerous essential biological processes to which small molecule models lend valuable mechanistic insights. Pyridyl-amino acid-methyl esters are appended to a rhenium(I) tricarbonyl 1,10-phenanthroline core to yield rhenium–amino acid complexes with tyrosine ([Re]–Y–OH) and phenylalanine ([Re]–F). The emission from the [Re] center is more significantly quenched for [Re]–Y–OH upon addition of base. Time-resolved studies establish that excited-state quenching occurs by a combination of static and dynamic mechanisms. The degree of quenching depends on the strength of the base, consistent with a proton-coupled electron transfer (PCET) quenching mechanism. Comparative studies of [Re]–Y–OH and [Re]–F enable a detailed mechanistic analysis of a bidirectional PCET process.National Institutes of Health (U.S.) (GM47274

Roll‐to‐Roll Cohesive, Coated, Flexible, High‐Efficiency Polymer Light‐Emitting Diodes Utilizing ITO‐Free Polymer Anodes

This paper reports solution‐processed, high‐efficiency polymer light‐emitting diodes fabricated by a new type of roll‐to‐roll coating method under ambient air conditions. A noble roll‐to‐roll cohesive coating system utilizes only natural gravity and the surface tension of the solution to flow out from the capillary to the surface of the substrate. Because this mechanism uses a minimally cohesive solution, the roll‐to‐roll cohesive coating can effectively realize an ultra‐thin film thickness for the electron injection layer. In addition, the roll‐to‐roll cohesive coating enables the fabrication of a thicker polymer anode film more than 250 nm at one time by modification of the surface energy and without wasting the solution. It is observed that the standard sheet resistance deviation of the polymer anode is only 2.32 Ω/□ over 50 000 bending cycles. The standard sheet resistance deviation of the polymer anode in the different bending angles (0 to 180°) is 0.313 Ω/□, but the case of the ITO‐PET is 104.93 Ω/□. The average surface roughness of the polymer anode measured by atomic force microscopy is only 1.06 nm. Because the surface of the polymer anode has a better quality, the leakage current of the polymer light‐emitting diodes (PLEDs) using the polymer anode is much lower than that using the ITO‐PET substrate. The luminous power efficiency of the two devices is 4.13 lm/W for the polymer anode and 3.21 lm/W for the ITO‐PET. Consequently, the PLEDs made by using the polymer anode exhibited 28% enhanced performance because the polymer anode represents not only a higher transparency than the ITO‐PET in the wavelength of 560 nm but also greatly reduced roughness. The optimized the maximum current efficiency and power efficiency of the device show around 6.1 cd/A and 5.1 lm/W, respectively, which is comparable to the case of using the ITO‐glass. This roll‐to‐roll cohesive coating method utilizes only the natural gravity and cohesive force of the solutions. The coating film thickness can be effectively reduced for the ultra‐thin electron injection layer. Furthermore, the roll‐to‐roll cohesive coating enables the fabrication of a thicker polymer anode more than 250 nm at one time by modification of the surface energy and without wasting the solution.Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/102247/1/smll_201300382_sm_suppl.pdfhttp://deepblue.lib.umich.edu/bitstream/2027.42/102247/2/4036_ftp.pd

Enhancing the Purity of Reflective Structural Colors with Ultrathin Bilayer Media as Effective Ideal Absorbers

Structural colors of high purity and brightness are desired in various applications. This study presents a general strategy of selecting the appropriate material and thickness of each layer to create high‐purity reflective colors in a classic asymmetric Fabry–Pérot cavity structure based on a dielectric–absorber–dielectric–metal multilayered configuration. Guided by the derived complex refractive index of the ideal absorber layer, an effective absorbing bilayer medium consisting of two ultrathin lossy films is used to improve the color purity of reflective colors by suppressing the reflection of its complementary colors with the enhanced optical absorption. Highly pure red, green, and blue reflective colors are designed and experimentally demonstrated employing different effective bilayer absorbers. Due to the high refractive index of the dielectric material, the colored structures exhibit great angle‐robust appearance (blue and red colors are up to ±60°, and green color is up to ±45°). The generalized design principles and the proposed method of using effective bilayer absorbers open up new avenues for realizing high‐purity thin‐film structural colors with more materials selections.A general strategy for the material and layer thickness selection to produce high‐purity reflective colors in a dielectric–absorber–dielectric–metal multilayered structure is presented. The color purity of red, green and blue reflective colors can be significantly improved by designing different effective absorbing bilayer media to enhance the optical absorption over a broad wavelength range of nontargeted colors.Peer Reviewedhttps://deepblue.lib.umich.edu/bitstream/2027.42/151998/1/adom201900739-sup-0001-S1.pdfhttps://deepblue.lib.umich.edu/bitstream/2027.42/151998/2/adom201900739.pdfhttps://deepblue.lib.umich.edu/bitstream/2027.42/151998/3/adom201900739_am.pd

Optical generation of high frequency ultrasound using two-dimensional gold nanostructure

A two-dimensional (2D) gold nanostructure is used to optically generate high frequency ultrasound. The structure consists of 2D arrangements of gold nanoparticles, sandwiched between a transparent substrate and a 4.5 μm4.5μm thick polydimethylsiloxane (PDMS) layer. The acoustic signal displays significant improvements compared to a bulk black PDMS films (the current state of the art) at frequencies from 50 to 100 MHz50to100MHz. The high optical extinction ratio of the gold nanostructure provides a convenient method to construct an integrated transmit/receive optoacoustic array. These results show that a 2D gold nanostructure can be used to produce high frequency arrays for ultrasound imaging.Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/87823/2/093901_1.pd

Microtubule Acetylation Is Required for Mechanosensation in Drosophila

At the cellular level, alpha-tubulin acetylation alters the structure of microtubules to render them mechanically resistant to compressive forces. How this biochemical property of microtubule acetylation relates to mechanosensation remains unknown, although prior studies have shown that microtubule acetylation influences touch perception. Here, we identify the major Drosophila alpha-tubulin acetylase (dTAT) and show that it plays key roles in several forms of mechanosensation. dTAT is highly expressed in the larval peripheral nervous system (PNS), but it is largely dispensable for neuronal morphogenesis. Mutation of the acetylase gene or the K40 acetylation site in alpha-tubulin impairs mechanical sensitivity in sensory neurons and behavioral responses to gentle touch, harsh touch, gravity, and vibration stimuli, but not noxious thermal stimulus. Finally, we show that dTAT is required for mechanically induced activation of NOMPC, a microtubule-associated transient receptor potential channel, and functions to maintain integrity of the microtubule cytoskeleton in response to mechanical stimulation

Photochemical tyrosine oxidation with a hydrogen-bonded proton acceptor by bidirectional proton-coupled electron transfer

Amino acid radical generation and transport are fundamentally important to numerous essential biological processes to which small molecule models lend valuable mechanistic insights. Pyridyl-amino acid-methyl esters are appended to a rhenium(I) tricarbonyl 1,10-phenanthroline core to yield rhenium–amino acid complexes with tyrosine ([Re]–Y–OH) and phenylalanine ([Re]–F). The emission from the [Re] center is more significantly quenched for [Re]–Y–OH upon addition of base. Time-resolved studies establish that excited-state quenching occurs by a combination of static and dynamic mechanisms. The degree of quenching depends on the strength of the base, consistent with a proton-coupled electron transfer (PCET) quenching mechanism. Comparative studies of [Re]–Y–OH and [Re]–F enable a detailed mechanistic analysis of a bidirectional PCET process.Chemistry and Chemical Biolog

Short Term Development and Fate of MGE-Like Neural Progenitor Cells in Jaundiced and Non-Jaundiced Rat Brain

A grant from the One-University Open Access Fund at the University of Kansas was used to defray the author's publication fees in this Open Access journal. The Open Access Fund, administered by librarians from the KU, KU Law, and KUMC libraries, is made possible by contributions from the offices of KU Provost, KU Vice Chancellor for Research & Graduate Studies, and KUMC Vice Chancellor for Research. For more information about the Open Access Fund, please see http://library.kumc.edu/authors-fund.xml.Neonatal hyperbilirubinemia targets specific brain regions and can lead to kernicterus. One of the most debilitating symptoms of kernicterus is dystonia, which results from bilirubin toxicity to the globus pallidus (GP). Stem cell transplantation into the GP to replace lost neurons and restore basal ganglia circuits function is a potential therapeutic strategy to treat dystonia in kernicterus. In this study we transplanted human medial ganglionic eminence (MGE)-like neural progenitor cells (NPCs) that we differentiated into a primarily gamma-aminobutyric acid (GABA)ergic phenotype, into the GP of non-immunosuppressed jaundiced (jj) and non-jaundiced (Nj) rats. We assessed the survival and development of graft cells at three time-points post-transplantation. While grafted MGE-like NPCs survived and generated abundant fibers in both jj and Nj brains, NPC survival was greater in the jj brain. These results were consistent with our previous finding that excitatory spinal interneuron-like NPCs exhibited a higher survival rate in the jj brain than in the Nj brain. Our findings further support our hypothesis that slightly elevated bilirubin levels in the jj brain served as an antioxidant and immunosuppressant to protect the transplanted cells. We also identified graft fibers growing toward brain regions that receive projections from the GP, as well as host fibers extending toward the graft. These promising findings suggest that MGE-like NPCs may have the capacity to restore the circuits connecting GP and other nuclei.NIH Center of Biomedical Research Excellence program project P20 GM104936Children's Mercy HospitalRonald D. Deffenbaugh FoundationKansas Intellectual and Developmental Disabilities Research Center HD09021

Predicting blunt cerebrovascular injury in pediatric trauma: Validation of the Utah Score

Risk factors for blunt cerebrovascular injury (BCVI) may differ between children and adults, suggesting that children at low risk for BCVI after trauma receive unnecessary computed tomography angiography (CTA) and high-dose radiation. We previously developed a score for predicting pediatric BCVI based on retrospective cohort analysis. Our objective is to externally validate this prediction score with a retrospective multi-institutional cohort. We included patients who underwent CTA for traumatic cranial injury at four pediatric Level I trauma centers. Each patient in the validation cohort was scored using the “Utah Score” and classified as high or low risk. Before analysis, we defined a misclassification rate <25% as validating the Utah Score. Six hundred forty-five patients (mean age 8.6 ± 5.4 years; 63.4% males) underwent screening for BCVI via CTA. The validation cohort was 411 patients from three sites compared with the training cohort of 234 patients. Twenty-two BCVIs (5.4%) were identified in the validation cohort. The Utah Score was significantly associated with BCVIs in the validation cohort (odds ratio 8.1 [3.3, 19.8], p < 0.001) and discriminated well in the validation cohort (area under the curve 72%). When the Utah Score was applied to the validation cohort, the sensitivity was 59%, specificity was 85%, positive predictive value was 18%, and negative predictive value was 97%. The Utah Score misclassified 16.6% of patients in the validation cohort. The Utah Score for predicting BCVI in pediatric trauma patients was validated with a low misclassification rate using a large, independent, multicenter cohort. Its implementation in the clinical setting may reduce the use of CTA in low-risk patients

Angleâ Insensitive and CMOSâ Compatible Subwavelength Color Printing

Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/134900/1/adom201600287_am.pdfhttp://deepblue.lib.umich.edu/bitstream/2027.42/134900/2/adom201600287.pdfhttp://deepblue.lib.umich.edu/bitstream/2027.42/134900/3/adom201600287-sup-0001-S1.pd

Abnormal Spine Morphology and Enhanced LTP in LIMK-1 Knockout Mice

AbstractIn vitro studies indicate a role for the LIM kinase family in the regulation of cofilin phosphorylation and actin dynamics. In addition, abnormal expression of LIMK-1 is associated with Williams syndrome, a mental disorder with profound deficits in visuospatial cognition. However, the in vivo function of this family of kinases remains elusive. Using LIMK-1 knockout mice, we demonstrate a significant role for LIMK-1 in vivo in regulating cofilin and the actin cytoskeleton. Furthermore, we show that the knockout mice exhibited significant abnormalities in spine morphology and in synaptic function, including enhanced hippocampal long-term potentiation. The knockout mice also showed altered fear responses and spatial learning. These results indicate that LIMK-1 plays a critical role in dendritic spine morphogenesis and brain function