gebhart/patrepeval huggingface dataset:
Olefin Substitution in (silox)3M(olefin) (silox = tBu3SiO; M = Nb, Ta):  The Role of Density of States in Second vs Third Row Transition Metal Reactivity (2008)

The substitution chemistry of olefin complexes (silox)3M(ole) (silox = (t)Bu3SiO; M = Nb (1-ole), Ta (2-ole); ole = C2H4 (as 13C2H4 or C2D4), C2H3Me, C2H3Et, cis-2-C4H8, iso-C4H8, C2H3Ph, cC5H8, cC6H10, cC7H10 (norbornene)) was investigated. For 1-ole, substitution was dissociative (deltaG(double dagger)(diss)), and in combination with calculated olefin binding free energies (deltaG(o)(bind)), activation free energies for olefin association (deltaG(double dagger)(assoc)) to (silox)3Nb (1) were estimated. For 2-ole, substitution was not observed prior to rearrangement to alkylidenes. Instead, activation free energies for olefin association to (silox)3Ta (2) were measured, and when combined with deltaG(o)(bind) (calcd), estimates of olefin dissociation rates from 2-ole were obtained. Despite stronger binding energies for 1-ole vs 2-ole, the dissociation of olefins from 1-ole is much faster than that from 2-ole. The association of olefins to 1 is also much faster than that to 2. Linear free energy relationships (with respect to deltaG(o)(bind)) characterize olefin dissociation from 1-ole, but not olefin dissociation from 2-ole, and olefin association to 2, but not olefin association to 1. Calculated transition states for olefin dissociation from (HO)3M(C2H4) (M = Nb, 1'-C2H4; Ta, 2'-C2H4) are asymmetric and have orbitals consistent with either singlet or triplet states. The rearrangement of (silox)3Nb(trans-Vy,Ph-cPr) (1-VyPhcPr) to (silox)3Nb=CHCH=CHCH2CH2Ph (3) is consistent with a diradical intermediate akin to the transition state for substitution. The disparity between Nb and Ta in olefin substitution chemistry is rationalized on the basis of a greater density of states (DOS) for the products (i.e., (silox)3M + ole) where M = Nb, leading to intersystem crossing events that facilitate dissociation. At the crux of the DOS difference is the greater 5dz2/6s mixing for Ta vs the 4dz2/5s mixing of Nb. This rationalization is generalized to explain the nominally swifter reactivities of 4d vs 5d elements.
Generation of Bioartificial Heart Tissue by Combining a Three-Dimensional Gel-Based Cardiac Construct with Decellularized Small Intestinal Submucosa (2013)

The in vitro generation of a bioartificial cardiac construct (CC) represents a promising tool for the repair of ischemic heart tissue. Several approaches to engineer cardiac tissue in vitro have been conducted. The main drawback of these studies is the insufficient size of the resulting construct for clinical applications. The focus of this study was the generation of an artificial three-dimensional (3D), contractile, and suturable myocardial patch by combining a gel-based CC with decellularized porcine small intestinal submucosa (SIS), thereby engineering an artificial tissue of 11 cm² in size. The alignment and morphology of rat neonatal cardiomyocytes (rCMs) in SIS-CC complexes were investigated as well as the re-organization of primary endothelial cells which were co-isolated in the rCM preparation. The ability of a rat heart endothelial cell line (RHE-A) to re-cellularize pre-existing vessel structures within the SIS or a biological vascularized matrix (BioVaM) was determined. SIS-CC contracted spontaneously, uniformly, and rhythmically with an average rate of 200 beats/min in contrast to undirected contractions observed in CC without SIS support. rCM exhibited an elongated morphology with well-defined sarcomeric structures oriented along the longitudinal axis in the SIS-CC, whereas round-shaped and random-arranged rCM were observed in CC. Electric coupling of rCM was demonstrated by microelectrode array measurements. A dense network of CD31⁺/eNOS⁺ cells was detected as permeating the whole construct. Superficial supplementation of RHE-A cells to SIS-CC led to the migration of these cells through the CC, resulting in the re-population of pre-existing vessel structures within the decelluarized SIS. By infusion of RHE-A cells into the BioVaM venous and arterial pedicles, a re-population of the BioVaM vessel bed as well as distribution of RHE-A cells throughout the CC was achieved. Rat endothelial cells within the CC were in contact with RHE-A cells. Ingrowth and formation of a network by endothelial cells infused through the BioVaM represent a promising step toward engineering a functional perfusion system, enabling the engineering of vascularized and well-nourished 3D CC of dimensions relevant for therapeutic heart repair.
Collaborative design of fish habitat enhancement projects in streams and rivers of Washington State (2000)

Thesis (Ph. D.)--University of Washington, 2000
Polyoxometalates and colloidal nanocrystals as building blocks for metal oxide nanocomposite films (2011)

We report the preparation of solution-derived metal oxide nanocomposite films by combining polyoxometalates (POMs) and colloidal oxide nanocrystals. Polyniobates and vanadates were combined with Sn-doped In2O3 (ITO) nanocrystals leading to Nb2O5–ITO, V2O5–ITO and VO2–ITO nanocomposite films. Compared to other solution-phase methodologies, this approach offers excellent control of the nanoinclusion composition, size, morphology, and volume fraction. Two different methodologies have been used, which are based on the ex situ (in solution) and in situ (within the film) ligand exchange of the pristine organic capping ligands of the nanocrystals by POMs. A thorough structural and compositional characterization of the films at different stages of the ligand exchange process is also presented.
Intelligent and Adaptive Mixup Technique for Adversarial Robustness (2021)

Deep neural networks are generally trained using large amounts of data to achieve state-of-the-art accuracy in many possible computer vision and image analysis applications ranging from object recognition to natural language processing. It is also claimed that these networks can memorize the data which can be extracted from the network parameters such as weights and gradient information. The adversarial vulnerability of the deep networks is usually evaluated on the unseen test set of the databases. If the network is memorizing the data, then the small perturbation in the training image data should not drastically change its performance. Based on this assumption, we first evaluate the robustness of deep neural networks on small perturbations added in the training images used for learning the parameters of the network. It is observed that, even if the network has seen the images it is still vulnerable to these small perturbations. Further, we propose a novel data augmentation technique to increase the robustness of deep neural networks to such perturbations.
Ultra-fast microwave enhanced reversible addition-fragmentation chain transfer (RAFT) polymerization: monomers to polymers in minutes (2007)

Microwave mediated RAFT polymerization leads to ultra-fast polymerizations, whilst keeping excellent control over molecular weights and molecular weight distributions; this is the first example of such a dramatic effect of microwaves on living radical polymerization kinetics, and it shows the potential for chemists to produce very well controlled polymers in a matter of minutes.
Impact Attenuation Devices for Racing<xref ref-type="fn" rid="FN1">1</xref> (1998)

&lt;div class="htmlview paragraph"&gt;Preliminary development and testing has been conducted on two energy-absorbing safety devices for racing circuits, termed the Fitch Inertial Barrier and the Compression Barrier. The first is an array of sacrificial modules, filled with sand and/or water progressively weighted. It is a racing version of inertial barriers used for 30 years on highways in 50 States. In its test, the Inertial Barrier recorded a 4.7 average G deceleration in 36 feet, compared with a 70 G deceleration for a car hitting a concrete barrier head-on with 2.3′ of crush. In the test of the compression barrier, 15 avg. longitudinal Gs were recorded in less than 3 feet of energy-absorption. It reduced the speed of the car by nearly half and reduced rebound by 5 degrees. The barrier self-restored after impact.&lt;/div&gt;
Scaffold-Free Spheroids with Two-Dimensional Heteronano-Layers (2DHNL) Enabling Stem Cell and Osteogenic Factor Codelivery for Bone Repair (2022)

Scaffold-free spheroids offer great potential as a direct supply of cells for bottom-up bone tissue engineering. However, the building of functional spheroids with both cells and bioactive signals remains challenging. Here, we engineered functional spheroids with mesenchymal stem cells (MSCs) and two-dimensional heteronano-layers (2DHNL) that consisted of black phosphorus (BP) and graphene oxide (GO) to create a 3D cell-instructive microenvironment for large defect bone repair. The effects of the engineered 2D materials on the proliferation, osteogenic differentiation of stem cells was evaluated in an <i>in vitro</i> 3D spheroidal microenvironment. Excellent <i>in vivo</i> support of osteogenesis of MSCs, neovascularization, and bone regeneration was achieved after transplanting these engineered spheroids into critical-sized rat calvarial defects. Further loading of osteogenic factor dexamethasone (DEX) on the 2DHNL showed outstanding <i>in vivo</i> osteogenic induction and bone regrowth without prior <i>in vitro</i> culture in osteogenic medium. The shortened overall culture time would be advantageous for clinical translation. These functional spheroids impregnated with engineered 2DHNL enabling stem cell and osteogenic factor codelivery could be promising functional building blocks to provide cells and differential clues in an all-in-one system to create large tissues for time-effective <i>in vivo</i> bone repair.
Hemorrhage in Pelvic Fractures Does Not Correlate With Fracture Length (2008)

Pelvic fracture surfaces may be sources of bleeding in pelvic injuries, but the fact that bleeding is similar in fractures and dislocations indicates fracture surfaces do not constitute the primary source. Based on our analysis one cannot reliably predict pelvic hemorrhage based on A/P radiograph assessments, such as fracture type.
Mechanism of nanograting formation on the surface of fused silica (2012)

Nanograting inscription with a tightly focused femtosecond beam on the surface of fused silica was studied. The width and spacing of grooves are shown to decrease with the increase of the number of overlapped shots in both stationary and scanning cases. We propose a model to explain this behavior, based on both the so-called nanoplasmonic model and the incubation effect.
The molecular role of Sigmar1 in regulating mitochondrial function through mitochondrial localization in cardiomyocytes (2021)

Sigmar1 is a widely expressed molecular chaperone protein in mammalian cell systems. Accumulating research demonstrated the cardioprotective roles of pharmacologic Sigmar1 activation by ligands in preclinical rodent models of cardiac injury. Extensive biochemical and immuno-electron microscopic research demonstrated Sigmar1's sub-cellular localization largely depends on cell and organ types. Despite comprehensive studies, Sigmar1's direct molecular role in cardiomyocytes remains elusive. In the present study, we determined Sigmar1's subcellular localization, transmembrane topology, and function using complementary microscopy, biochemical, and functional assays in cardiomyocytes. Quantum dots in transmission electron microscopy showed Sigmar1 labeled quantum dots on the mitochondrial membranes, lysosomes, and sarcoplasmic reticulum-mitochondrial interface. Subcellular fractionation of heart cell lysates confirmed Sigmar1's localization in purified mitochondria fraction and lysosome fraction. Immunocytochemistry confirmed Sigmar1 colocalization with mitochondrial proteins in isolated adult mouse cardiomyocytes. Sigmar1's mitochondrial localization was further confirmed by Sigmar1 colocalization with Mito-Tracker in isolated mouse heart mitochondria. A series of biochemical experiments, including alkaline extraction and proteinase K treatment of purified heart mitochondria, demonstrated Sigmar1 as an integral mitochondrial membrane protein. Sigmar1's structural requirement for mitochondrial localization was determined by expressing FLAG-tagged Sigmar1 fragments in cells. Full-length Sigmar1 and Sigmar1's C terminal-deletion fragments were able to localize to the mitochondrial membrane, whereas N-terminal deletion fragment was unable to incorporate into the mitochondria. Finally, functional assays using extracellular flux analyzer and high-resolution respirometry showed Sigmar1 siRNA knockdown significantly altered mitochondrial respiration in cardiomyocytes. Overall, we found that Sigmar1 localizes to mitochondrial membranes and is indispensable for maintaining mitochondrial respiratory homeostasis in cardiomyocytes.
Ice Formation in Isolated Human Hepatocytes and Human Liver Tissue (1997)

Cryopreservation of isolated cells and tissue slices of human liver is required to furnish extracorporeal bioartificial liver devices with a ready supply of hepatocytes, and to create in vitro drug metabolism and toxicity models. Although both the bioartificial liver and many current biotoxicity models are based on reconstructing organ functions from single isolated hepatocytes, tissue slices offer an in vitro system that may more closely resemble the in vivo situation of the cells because of cell-cell and cell-extracellular matrix interactions. However, successful cryopreservation of both cellular and tissue level systems requires an increased understanding of the fundamental mechanisms involved in the response of the liver and its cells to freezing stress. This study investigates the biophysical mechanisms of water transport and intracellular ice formation during freezing in both isolated human hepatocytes and whole liver tissue. The effects of cooling rate on individual cells were measured using a cryomicroscope. Biophysical parameters governing water transport (Lpg = 2.8 microns/min-atm and ELp = 79 kcal/mole) and intracellular heterogeneous ice nucleation (omega het = 1.08 x 10(9) m-2s-1 and kappa het = 1.04 x 10(9) K5) were determined. These parameters were then incorporated into a theoretical Krogh cylinder model developed to simulate water transport and ice formation in intact liver tissue. Model simulations indicated that the cellular compartment of the Krogh model maintained more water than isolated cells under the same freezing conditions. As a result, intracellular ice nucleation occurred at lower cooling rates in the Krogh model than in isolated cells. Furthermore, very rapid cooling rates (1000 degrees C/min) showed a depression of heterogeneous nucleation and a shift toward homogeneous nucleation. The results of this study are in qualitative agreement with the findings of a previous experimental study of the response to freezing of intact human liver.
Transcutaneous monitoring of oxygen and carbon dioxide using wearable devices (Conference Presentation) (2023)

We present the creation of wearable devices that measure transcutaneous partial oxygen or carbon dioxide pressure (tcpO2 or tcpCO2) non-invasively. The devices are highly sensitive to the physiological pO2/pCO2, and detects changes in luminescence (lifetime or ratiometric brightness) of mellaporphyrins or HPTS dye molecules embedded within breathable, hydrophobic films. Our first in human measurements reveal the devices are able to detect quick and subtle changes in tcpO2 due to local and systemic changes in blood flow of skin or deeper muscle tissue. Models to extract tissue oxygenation and oxygen consumption rate are explored.
Epidemiology of childhood type 2 diabetes in the developing world (2004)

Type 2 diabetes in the young is an increasing problem with potentially serious outcomes. Our understanding of the worldwide burden of this condition is incomplete, with many studies adopting different methodologies to assess the condition and reporting on specific communities or ethnic groups. Most of the data come from developed nations, with few studies from developing nations. The purpose of this review is to bring together the available data on type 2 diabetes in the young from the developing world, in order to highlight deficiencies in the knowledge of the condition and also to promote strategies to deal with it. Noted also are some of the factors associated with the condition, such as family history, genetic influences, intrauterine environment as well as the importance of birth weight, insulin resistance, obesity, and development of complications. These are of relevance in both developed and developing nations.
Packaging Technology of Multi Deflection Arrays for Multi-Shaped Beam Lithography (2011)

Multi-Shaped electron beam lithography is considered a promising approach for high throughput mask and direct writing. Providing multiple apertures and individually controlled electrodes it allows for massive parallelization of exposure shots, thus significantly decreasing write time. A silicon-based micro-structured MEMS multi-beam deflection array (MDA) featuring 8×8 apertures is presented. The hybrid integration of MDA devices in ceramic system carriers utilizing a laser-based Solderjet Bumping process is demonstrated. This flux-free soldering process provides adhesive-free, long term stable and vacuum compatible joints and is used for both mechanical fixation and electrical connection. Electron beam deflection in two perpendicular directions requires the highly accurate placement of two crossed MDA devices, which is carried out by three degrees of freedom alignment procedures and solder joining. Electrical signal routing within the electron optical column using flexible printed circuit boards and flux-free soldering is also reported. The precision adjustment of two carriers is accomplished by fiducial mark detection using image processing. Results on alignment accuracy in the sub-micron range, mechanical and electrical testing of such assemblies are reported.
Spinal and Supraspinal Mechanisms of Neuropathic Pain (2000)

Neuropathic pain is associated with abnormal tactile and thermal responses that may be extraterritorial to the injured nerve. Importantly, tactile allodynia and thermal hyperalgesia may involve separate pathways, since complete and partial spinal cord lesions have blocked allodynia, but not hyperalgesia, after spinal nerve ligation (SNL). Furthermore, lesions of the dorsal column, and lidocaine microinjected into dorsal column nuclei block only tactile allodynia. Conversely, thermal hyperalgesia, but not tactile allodynia was blocked by desensitization of C-fibers with resiniferotoxin. Therefore, it seems that tactile allodynia is likely to be mediated by large diameter A beta fibers, and not susceptible to modulation by spinal opioids, whereas hyperalgesia is mediated by unmyelinated C-fibers, and is sensitive to blockade by spinal opioids. Additionally, abnormal, spontaneous afferent drive in neuropathic pain may contribute to NMDA-mediated central sensitization by glutamate and by non-opioid actions of spinal dynorphin. Correspondingly, SNL elicited elevation in spinal dynorphin content in spinal segments at and adjacent to the zone of entry of the injured nerve along with signs of neuropathic pain. Antiserum to dynorphin A(1-17) or MK-801 given spinally blocked thermal hyperalgesia, but not tactile allodynia, after SNL, and also restored diminished morphine antinociception. Finally, afferent drive may induce descending facilitation from the rostroventromedial medulla (RVM). Blocking afferent drive with bupivicaine also restored lost potency of PAG morphine, as did CCK antagonists in the RVM. This observation is consistent with afferent drive activating descending facilitation from the RVM, and thus diminishing opioid activity, and may underlie the clinical observation of limited responsiveness of neuropathic pain to opioids.
Experimental Efficiency Evaluation of Stacked Transistor Half-Bridge Topologies in 14 nm CMOS Technology (2021)

Different Half-Bridge (HB) converter topologies for an Integrated Voltage Regulator (IVR), which serves as a microprocessor application, were evaluated. The HB circuits were implemented with Stacked Transistors (HBSTs) in a cutting-edge 14 nm CMOS technology node in order to enable the integration on the microprocessor die. Compared to a conventional realization of the HBST, it was found that the Active Neutral-Point Clamped (ANPC) HBST topology with Independent Clamp Switches (ICSs) not only ensured balanced blocking voltages across the series-connected transistors, but also featured a more robust operation and achieved higher efficiencies at high output currents. The IVR achieved a maximum efficiency of 85.3% at an output current of 300 mA and a switching frequency of 50 MHz. At the maximum measured output current of 780 mA, the efficiency was 83.1%. The active part of the IVR (power switches, gate-drivers, and level shifters) realized a high maximum current density of 24.7 A/mm2.
On-The-Fly Programming: Using Code As An Expressive Musical Instrument (2004)

On-the-fly programming is a style of programming in which the programmer/performer/composer augments and modifies the program while it is running, without stopping or restarting, in order to assert expressive, programmable control at runtime. Because of the fundamental powers of programming languages, we believe the technical and aesthetic aspects of on-the-fly programming are worth exploring. In this paper, we present a formalized framework for on-the-fly programming, based on the ChucK synthesis language, which supports a truly concurrent audio programming model with sample-synchronous timing, and a highly on-the-fly style of programming. We first provide a well-defined notion of on-thefly programming. We then address four fundamental issues that confront the on-the-fly programmer: timing, modularity, conciseness, and flexibility. Using the features and properties of ChucK, we show how it solves many of these issues. In this new model, we show that (1) concurrency provides natural modularity for on-the-fly programming, (2) the timing mechanism in ChucK guarantees on-the-fly precision and consistency, (3) the Chuck syntax improves conciseness, and (4) the overall system is a useful framework for exploring on-the-fly programming. Finally, we discuss the aesthetics of on-the-fly performance.
A CALCIUM ACTIVATED PROTEASE IN SQUID AXOPLASM (1979)

Abstract Evidence for a protease in squid axoplasm which is selectively activated by Ca 2+ and blocked by SH‐inhibitors is presented. This protease appears to be particularly effective in degrading squid neurofilament proteins, but also extensively degrades various other major protein components in axoplasm.
Synthesis and Characterization of Novel Fluorescent Nitrogen-Containing Bisphosphonate Imaging Probes for Bone Active Drugs (2011)

Progress in the synthesis of novel fluorescent conjugates of N-heterocyclic bisphosphonate drugs and related analogues, together with some recent applications of these compounds as imaging probes, are briefly discussed.
ChemInform Abstract: Tandem Radical Cyclizations. A General Strategy for the Synthesis of Triquinane Sesquiterpenes (1991)

Abstract ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.