gebhart/patrepeval huggingface dataset:
In Situ Reaction Mechanism Studies on Atomic Layer Deposition of AlxSiyOz from Trimethylaluminium, Hexakis(ethylamino)disilane, and Water (2012)

Reaction mechanisms in the Al(CH3)3–D2O–Si2(NHEt)6–D2O ALD process for AlxSiyOz were studied in situ with a quartz crystal microbalance (QCM) and a quadrupole mass spectrometer (QMS) at 200 °C. Two other pulsing sequences were investigated too to assess the surface reactivity of Si2(NHEt)6 and Al(CH3)3. The resulting films were extensively analyzed with X-ray reflectivity (XRR), X-ray photoelectron spectroscopy (XPS), energy dispersive X-ray (EDX) spectroscopy, and Fourier transform infrared (FT-IR) spectroscopy. The main byproducts observed with QMS were CDH3 and NDHC2H5. The incorporation of methyl groups from TMA into the film through the formation of Si–CH3 bonds was deduced from the results. Several pathways were considered for the adsorption of Si2(NHEt)6 on a hydroxylated surface. According to the results, the pathway where both Si atoms in the dimeric Si2(NHEt)6 precursor molecule bond to the surface with a cleavage of their Si–Si bond is preferred. A model based on the QCM and XPS data was build to better characterize the mechanism. The calculations indicated that 1.3 methyl ligands of Al(CH3)3 and 3.8 NHEt ligands of Si2(NHEt)6 are released in average during their respective metal precursor pulses in reactions with surface hydroxyl groups, the rest being eliminated during the following D2O pulses.
Rhodium-Catalyzed C−C Bond Cleavage: Construction of Acyclic Methyl Substituted Quaternary Stereogenic Centers (2010)

A rhodium-catalyzed enantioselective insertion into the C-C bond of tert-cyclobutanols and subsequent proto-demetalation provides access to methyl substituted quaternary stereogenic centers in excellent yields and enantioselectivities. The reaction was used for a synthesis of (S)-4-ethyl-4-methyl-octane, the simplest saturated hydrocarbon with a quaternary stereogenic center.
Surface Oxidation and Luminescence Properties of Weblike Agglomeration of Silicon Nanocrystals Produced by a Laser Vaporization−Controlled Condensation Technique (1997)

Weblike aggregates of coalesced Si nanocrystals are produced by a laser vaporization−controlled condensation technique. SEM micrographs show particles with ∼10 nm diameter but the Raman shift suggests the presence of particles as small as ∼4 nm. FTIR of the freshly prepared particles shows weak peaks due to the stretching, bending, and rocking vibrations of the Si−O−Si bonds, indicating the presence of a surface oxidized layer, SiOx (x < 2). Further oxidation of the Si core appears to be very slow and inefficient under ambient temperature, but annealing at higher temperatures facilitates the oxidation. The particles show luminescence properties that are similar to those of porous Si and Si nanoparticles produced by other techniques. The nanoparticles do not luminesce unless, by exposure to air, they acquire the SiOx passivated coating. They show a short-lived blue emission characteristic of the SiO2 coating and a biexponential longer-lived red emission. The short lifetime component of the red emission, about 12 μs, does not depend on emission wavelength. The longer-lived component has a lifetime that ranges from 80 to over 130 μs (at 300 K), increasing with emission wavelength. The results are consistent with the quantum confinement mechanism as the source of the red photoluminescence.
Medical approach to weight management. (1999)

The online version contains supplementary material available at 10.1007/s10433-021-00670-2.
Semipolar GaN-based laser diodes for Gbit/s white lighting communication: devices to systems (2018)

We report the high-speed performance of semipolar GaN ridge laser diodes at 410 nm and the dynamic characteristics including differential gain, damping, and the intrinsic maximum bandwidth. To the best of our knowledge, the achieved modulation bandwidth of 6.8 GHz is the highest reported value in the blue-violet spectrum. The calculated differential gain of ~3 x 10<sup>-16</sup> cm<sup>2</sup>, which is a critical factor in high-speed modulation, proved theoretical predictions of higher gain in semipolar GaN laser diodes than the conventional c-plane counterparts. In addition, we demonstrate the first novel white lighting communication system by using our near-ultraviolet (NUV) LDs and pumping red-, green-, and blueemitting phosphors. This system satisfies both purposes of high-speed communication and high-quality white light illumination. A high data rate of 1.5 Gbit/s using on-off keying (OOK) modulation together with a high color rendering index (CRI) of 80 has been measured.
Monoclonal antibodies as probes of conformational changes in protein-engineered cytochrome c. (1988)

Determination of the nature of the antigen-antibody complex has always been the ultimate goal of three-dimensional epitope mapping studies. Various strategies for epitope mapping have been employed which include comparative binding studies with peptide fragments of antigens, binding studies with evolutionarily related proteins, chemical modifications of epitopes, and protection of epitopes from chemical modification or proteolysis by antibody shielding. In this study we report the use of protein engineering to modify residues in horse cytochrome c that are in or near the epitopes of four monoclonal antibodies specific for this protein. The results demonstrate not only that site-specific changes in the antigen binding site dramatically affect antibody binding, but, more importantly, that some of the site-specific changes cause local and long-range perturbations in structure that are detected by monoclonal antibody binding at other surfaces of the antigen. These findings emphasize the role of native conformation in the stabilization of the interaction between protein antigens and high affinity monoclonal antibodies. Furthermore, the results demonstrate that monoclonal antibodies are more sensitive probes of changes in conformation brought about by protein engineering than low resolution spectroscopic methods such as circular dichroism, where similar spectra are observed for all the analogues. These findings suggest a role for monoclonal antibodies in detecting conformational changes invoked by nonconservative amino acid substitutions or substitutions of evolutionarily conserved residues in protein-engineered or recombinant proteins.
Visible light driven reduction of carbon dioxide with water on modified Sr3Ti2O7 catalysts (2014)

XRD, EDXA &amp; XPS studies reveal incorporation of N, S &amp; Fe in Sr<sub>3</sub>Ti<sub>2</sub>O<sub>7</sub> matrix. Doping promotes visible light activity, Fe is the most effective dopant in reducing band gap and recombination Co-doping N, S &amp; Fe together leads to maximum photo reduction activity.
Displacement measurements in air for the calculable capacitor (2014)

The NIST calculable capacitor relies on precision interferometric measurements of displacement to determine absolute capacitance values. These displacement measurements, when made in vacuum, can have uncertainties of δL = 10 pm. Measurements made in air, on the other hand, are more difficult owing to the index of refraction. Here we evaluate two approaches to measure the displacement in air, a brute force one-wavelength method and a more refined two-wavelength method.
Traveling wave model for laser-guided discharges (2010)

We present an easily solvable 1D traveling wave model for laser-guided discharges. By assuming constant propagation speed u, the hydro/electrodynamic/chemistry equations are reduced to ordinary differential equations in retarded time τ. Negative discharges are shown to propagate only if u&amp;gt;μEb, where μ is electron mobility and Eb is the breakdown field; positive discharges propagate only if the channel preconductance exceeds ∼6×10−11 m/Ω. The axial electric field E is shown to spike up to several times Eb and then relax to ∼Eb for as long as the gas remains cold. In this streamer region, the channel conductance, current, and potential all increase linearly with τ. The transition to the leader stage, where E is much smaller, occurs in two steps: excitation of vibrational and low-lying electronic states, then gas heating. The propagation range decreases as a function of initial radius and (for given maximum voltage) of the voltage rise rate. Expansion of the hot channel is shown to increase the range.
Broadly Applicable Methodology for the Rapid and Dosable Small Molecule-Mediated Regulation of Transcription Factors in Human Cells (2013)

Direct and selective small molecule control of transcription factor activity is an appealing avenue for elucidating the cell biology mediated by transcriptional programs. However, pharmacologic tools to modulate transcription factor activity are scarce because transcription factors are not readily amenable to small molecule-mediated regulation. Moreover, existing genetic approaches to regulate transcription factors often lead to high nonphysiologic levels of transcriptional activation that significantly impair our ability to understand the functional implications of transcription factor activity. Herein, we demonstrate that small molecule-mediated conformational control of protein degradation is a generally applicable, chemical biological methodology to obtain small molecule-regulated transcription factors that modulate transcriptional responses at physiologic levels in human cells. Our establishment of this approach allows for the rapid development of genetically encoded, small molecule-regulated transcription factors to explore the biologic and therapeutic impact of physiologic levels of transcription factor activity in cells.
Cloud-scale ice-supersaturated regions spatially correlate with high water vapor heterogeneities (2014)

Abstract. Cirrus clouds have large yet uncertain impacts on Earth's climate. Ice supersaturation (ISS) – where the relative humidity with respect to ice (RHi) is greater than 100% – is the prerequisite condition of ice nucleation. Here we use 1 Hz (~230 m) in situ, aircraft-based observations from 87° N to 67° S to analyze the spatial characteristics of ice-supersaturated regions (ISSRs). The median length of 1-D horizontal ISSR segments is found to be very small (~1 km), which is 2 orders of magnitude smaller than previously reported. To understand the conditions of these small-scale ISSRs, we compare individual ISSRs with their horizontally adjacent subsaturated surroundings and show that 99% and 73% of the ISSRs are moister and colder, respectively. When quantifying the contributions of water vapor (H2O) and temperature (T) individually, the magnitudes of the differences between the maximum RHi values inside ISSRs (RHimax) and the RHi in subsaturated surroundings are largely derived from the H2O spatial variabilities (by 88%) than from those of T (by 9%). These features hold for both ISSRs with and without ice crystals present. Similar analyses for all RHi horizontal variabilities (including ISS and non-ISS) show strong contributions from H2O variabilities at various T, H2O, pressure (P) and various horizontal scales (~1–100 km). Our results provide a new observational constraint on ISSRs on the microscale (~100 m) and point to the importance of understanding how these fine-scale features originate and impact cirrus cloud formation and the RHi field in the upper troposphere (UT).
Pilot Designs with Guard Bands for Channel Estimation of MIMO OFDM Systems with Frequency-Dependent I/Q Imbalances (2009)

All practical OFDM systems insert null guard bands to facilitate easy filter implementation and emission spectrum control. The null guard bands introduce a constraint for optimal pilot designs in MIMO OFDM systems. Semiconductor downscaling and the use of high modulation order have signified the importance of pilot designs for OFDM systems in the presence of I/Q imbalances, but existing designs have not addressed the use of guard bands, the overhead efficiency, the estimation optimality, and general applicability in pilot data multiplexed format and/or MIMO setup. This paper proposes a pilot design for channel estimation of MIMO OFDM systems with guard bands and both transmit and receive frequency-dependent I/Q imbalances, which overcomes the limitations of the existing designs. Simulation and numerical results corroborate better performance, overhead advantage and applicability in pilot-data-multiplexed MIMO setup of the proposed design over the existing MIMO OFDM pilot design with I/Q imbalances.
Challenging the 50‐50 rule for the basal‐bolus insulin ratio in patients with type 2 diabetes who maintain stable glycaemic control (2022)

Our data show that a 50-50 ratio of basal-to-bolus insulin does not generally apply to patients with T2D who successfully maintain stable glycemia. Therefore, the 50-50 ratio should not serve as an ongoing treatment guide. Moreover, our results emphasize the importance of at least weekly insulin titrations.
Pseudopolymorph(s) (2016)

This Glossary of Terms Related to Pharmaceutics is needed by practitioners in the field of pharmaceutics as this field fulfills an important and crucial role, different from the roles of other scientific disciplines involved in the drugmaking process. The glossary contains 168 definitions used in pharmaceutics. These are related to various aspects of this discipline, such as: (1) physicochemical characterization of pharmaceutical preparations and the active ingredients they contain; (2) unit operations used in the practice of pharmaceutics; (3) terms related to the various dosage forms; (4) terms related to the various modes and routes of drug delivery; (5) terms used in pharmacokinetics and biopharmaceutics in general; and additional miscellaneous terms. The field of pharmaceutics itself is of a multidisciplinary nature as its practitioners come from a variety of disciplines, such as chemistry or various biological sciences, thus a glossary containing authoritative definitions would be useful for them. The terms used in pharmaceutics are rarely covered by existing glossaries, and in the cases they are, their definitions are often inappropriate for the field of pharmaceutics and require new or modified definitions to better fit the new context.
A Twisted Road to the Discovery and Chemical Development of BMS-986142: A Reversible Inhibitor of BTK Conformationally Constrained by Two Rotationally Stable Atropisomeric Axes (2022)

This chapter will describe the discovery and synthesis of the clinical compound BMS-986142, a selective, reversible, non-covalent inhibitor of Bruton’s tyrosine kinase. The compound benefits from chirality derived from a tertiary chiral center and two rotationally stable atropoisomeric axes, providing a single atropisomer out of eight possible diastereomers. An iterative medicinal chemistry effort to understand the impact of atropisomerism on potency, selectivity, and tolerability is highlighted. Additionally, the transition to process development and evolution of the route across stages of development leading to the proposed commercial synthesis with a focus on controlling the two chiral axes are reported.
Anisotropic High Electron Mobility and Photodynamics of a Self-Assembled Porphyrin Nanotube Including C60 Molecules (2009)

A cyclic porphyrin dimer (Ni2−CPDPy) linked by butadiyne moieties bearing 4-pyridyl groups includes a C60 molecule inside its cavity in solution to give a 1:1 inclusion complex (C60⊂Ni2−CPDPy). The charge-transfer (CT) band is observed at 645 nm in the UV−vis absorption spectrum of the solution of C60⊂Ni2−CPDPy. In the cyclic voltammogram of C60⊂Ni2−CPDPy, a small anodic shift of the porphyrin oxidation potential and a small cathodic shift of the fullerene reduction potential compared with their original redox potentials are indicative of CT interaction from the porphyrin to C60. In the crystal structure of C60⊂Ni2−CPDPy, a porphyrin nanotube is formed by the self-assembly of Ni2−CPDPy. Ni2−CPDPy molecules link together through nonclassical C−H···N hydrogen bonds and π−π interactions of the pyridyl groups along the crystallographic b axis. The included C60 molecules are linearly arranged in the nanotube to afford a supramolecular peapod. The charge-carrier mobility of the single crystal of C60⊂Ni2−CPDPy was determined by flash-photolysis time-resolved microwave conductivity (FP-TRMC) measurements. It has an anisotropic high electron mobility (∑μ = 0.72 cm2 V−1 s−1) along the linear array of C60 (crystallographic b axis). Femtosecond laser flash photolysis of C60⊂Ni2−CPDPy in the solid state with photoexcitation at the Soret band of the porphyrin shows the formation of a triplet exciplex 3{Ni2−CPDPy···C60}*, which decays with a lifetime of 34 ps to the ground state without observation of a complete charge-separated state.
Enantiomerically Pure Phenanthroline or Bipyridine Containing Macrocycles: A New Class of Ligands for Asymmetric Catalysis. (2003)

Abstract For Abstract see ChemInform Abstract in Full Text.
A novel acoustic cell processing platform for cell concentration and washing (2017)

FloDesign Sonics has developed a technology to enable a single use (gamma irradiated) continuous cell concentration and wash application for manufacturing of cell-based therapies. The device has been designed to be able to process several liters of a suspended cell culture, e.g., T-cells, at concentrations of 1 to 10 M cells/ml. The cell suspension flows through the device and the acoustic radiation force field is used to trap and hold the cells in the acoustic field. After concentrating the cells, one or multiple washing steps are accomplished by flowing the washing fluid through the device, using the acoustic field to trap the cells while displacing the original cell culture fluid. The holdup volume of the device is about 30 ml. Results are shown for prototypes with a 1x0.75 inch flow chamber driven by 2 MHz PZT-8 transducers operating at flow rates of 1-2L/h, measured cell recoveries of 90% have been achieved with concentration factors of 20 to 50 for Jurkat T-cell suspensions, depending on cell concentration and initial volume of the cell suspension. Scaling strategies used previously for cell clarification will be used to scale up the current cell concentration device to accommodate larger volumes.
Review of Transducer Principles for Label-Free Biomolecular Interaction Analysis (2011)

Label-free biomolecular interaction analysis is an important technique to study the chemical binding between e.g., protein and protein or protein and small molecule in real-time. The parameters obtained with this technique, such as the affinity, are important for drug development. While the surface plasmon resonance (SPR) instruments are most widely used, new types of sensors are emerging. These developments are generally driven by the need for higher throughput, lower sample consumption or by the need of complimentary information to the SPR data. This review aims to give an overview about a wide range of sensor transducers, the working principles and the peculiarities of each technology, e.g., concerning the set-up, sensitivity, sensor size or required sample volume. Starting from optical technologies like the SPR and waveguide based sensors, acoustic sensors like the quartz crystal microbalance (QCM) and the film bulk acoustic resonator (FBAR), calorimetric and electrochemical sensors are covered. Technologies long established in the market are presented together with those newly commercially available and with technologies in the early development stage. Finally, the commercially available instruments are summarized together with their sensitivity and the number of sensors usable in parallel and an outlook for potential future developments is given.
Vital Directions for Health and Health Care (2017)

The action priorities and essential infrastructure needs represent major opportunities to improve health outcomes and increase efficiency and value in the health system. As the new US administration and Congress chart the future of health and health care for the United States, and as health leaders across the country contemplate future directions for their programs and initiatives, their leadership and strategic investment in these priorities will be essential for achieving significant progress.
Ruthenium Oxide, a Suitable Redox Catalyst to Mediate Oxygen Production from Water (1979)

RuO2 dispersions were found to catalyze in aqueous solution the one electron reduction of Ce4+ and Ru(bipy)33+ ions under simultaneous evolution of oxygen from water. The reaction is first order with respect to the concentration of oxidants and in the case of Ce4+ the specific rate is 0.3 h-1 at ambient temperature and 2 h-1 at 50 °C. The rate is drastically augmented when colloidal Ru dispersions are employed.
N1-Benzofused Modification of Fluoroquinolones Reduces Activity Against Gram- Negative Bacteria (2019)

The fluoroquinolone class of antibiotics have a well-established structure-activity relationship (SAR) and a long history in the clinic, but the effect of electron-rich benzofused substituents at the N1 position remains poorly explored. Groups at this position are part of the topoisomerase-DNA binding complex and form a hydrophobic interaction with the major groove of DNA. Molecular modelling techniques were employed to select benzofused substituents that were shown to enhance this interaction of fluoroquinolones for the DNA gyrase target. Seven N1-modified fluoroquinolones were synthesised and tested against a panel of Gram-negative pathogens to determine minimum inhibitory concentration (MIC) values. Gram-negative outer membrane penetration was investigated using the membrane permeabiliser polymyxin B nonapeptide (PMBN) and the target affinity of representative compound 6e was determined in a cell-free environment. A correlation between N1 substituent hydrophobicity and activity was observed across the MIC panel, with compound activity decreasing with increased hydrophobicity. Those compounds with highest hydrophobicity were inactive due to poor solubility profiles whereas compounds with intermediate hydrophobicity were inactive due to impaired outer membrane penetration and reduced inhibition for the DNA gyrase target, the latter in contrast to modelling predictions. This study adds new information to the fluoroquinolone SAR and suggests limited utility of large hydrophobic substitution at the N1 position of fluoroquinolones.