Proton-transport catalysis, proton abstraction, and proton exchange in HF+HOC⁺ and H₂O+HOC⁺ and analogous deuterated reactions

Classical simulations of the reactions of HF and H₂O with HOC⁺ have been carried out on interpolatedab initiopotential energy surfaces. Rearrangement (X+HOC⁺→OCH⁺+X), abstraction (X+HOC⁺→XH⁺+OC), (X=HF or H₂O), exchange (e.g., DY+HOC⁺→HY+DOC⁺), and exchange-rearrangement (e.g., DY+HOC⁺→OCD⁺+YH) (Y=F or HO or DO) reactions are observed. However, the abstraction reaction is dominant for both the HF+HOC⁺ and H₂O+HOC⁺ systems

Constructing a Three Credit Hour Information Literacy Course: A Blueprint for Success

Instruction Librarians from the University of North Carolina Wilmington (UNCW) will describe their creation, design, and teaching of a three credit hour undergraduate course that focuses on the development of information literacy skills. The course, “LIB 103: Introduction to Library Research and Technology”, is required for UNCW’s Information Technology minor, which is offered by the university’s Department of Computer Science. This interdisciplinary course exposes students to aspects of media literacy, critical thinking, information evaluation, research skills, various information technologies, and current issues in the information age. The challenges of creating such a course from the ground up will be discussed. For librarians looking to establish credit courses, information about planning, necessary approval processes, and potential roadblocks will be presented. Librarians will discuss their individual experiences teaching the course and their unique approaches to meeting the course’s goals and objectives. Strategies for successful marketing and campus collaborations will also be discussed. LIB 103’s success has led to the expansion of the library’s curriculum to include new credit courses in Business research and Science research and plans for these future endeavors will be given

Teaching Information Evaluation with the Five Ws: An Elementary Method, an Instructional Scaffold, and the Effect on Student Recall and Application

Researchers developed an information evaluation activity used in one-shot library instruction for English composition classes. The activity guided students through evaluation using the “Five Ws” method of inquiry (who, what, when, etc.). A summative assessment determined student recall and application of the method. Findings, consistent over two semesters, include that 66.0 percent of students applied or recalled at least one of the Five Ws, and 20.8 percent of students applied or recalled more than one of its six criteria. Instructors were also surveyed, with 100 percent finding value in the method and 83.3 percent using or planning to use it in their own teaching

Assessment of ab initio models of protein complexes by molecular dynamics.

Determining how proteins interact to form stable complexes is of crucial importance, for example in the development of novel therapeutics. Computational methods to determine the thermodynamically stable conformation of complexes from the structure of the binding partners, such as RosettaDock, might potentially emerge to become a promising alternative to traditional structure determination methods. However, while models virtually identical to the correct experimental structure can in some cases be generated, the main difficulty remains to discriminate correct or approximately correct models from decoys. This is due to the ruggedness of the free-energy landscape, the approximations intrinsic in the scoring functions, and the intrinsic flexibility of proteins. Here we show that molecular dynamics simulations performed starting from a number top-scoring models can not only discriminate decoys and identify the correct structure, but may also provide information on an initial map of the free energy landscape that elucidates the binding mechanism

Computational Modeling of Designed Ankyrin Repeat Protein Complexes with their Targets

Recombinant therapeutic proteins are playing an ever-increasing role in the clinic. High-affinity binding candidates can be produced in a high-throughput manner through the process of selection and evolution from large libraries, but the structures of the complexes with target protein can only be determined for a small number of them in a costly, low-throughput manner, typically by x-ray crystallography. Reliable modeling of complexes would greatly help to understand their mode of action and improve them by further engineering, for example, by designing bi-paratopic binders. Designed ankyrin repeat proteins (DARPins) are one such class of antibody mimetics that have proven useful in the clinic, in diagnostics and research. Here we have developed a standardized procedure to model DARPin–target complexes that can be used to predict the structures of unknown complexes. It requires only the sequence of a DARPin and a structure of the unbound target. The procedure includes homology modeling of the DARPin, modeling of the flexible parts of a target, rigid body docking to ensembles of the target and docking with a partially flexible backbone. For a set of diverse DARPin–target complexes tested it generated a single model of the complex that well approximates the native state of the complex. We provide a protocol that can be used in a semi-automated way and with tools that are freely available. The presented concepts should help to accelerate the development of novel bio-therapeutics for scaffolds with similar properties

Ab-initio-MO-Studie Methyl- und Phenyl-substituierter Allenyl-Kationen

An den Methyl- und Phenyl-substituierten Allenyl-Kationen 3 - 12 (Tab. 1) wurden ab-initio-MO-Berechnungen unter Verwendung des STO-3G Basissatzes durchgeführt. Die berechneten Bindungslängen und Ladungsverteilungen zeigen Delokalisierung der positiven Ladung an, wie in Formel 1 gezeigt. Mit Hilfe isodesmischer Reaktionen werden Stabilisierungsenergien von Substituenten in 1- und 3-Position ermittelt. Diese Werte ermöglichen in Kombination mit der experimentell bekannten Bildungswärme des Stammkörpers 2 die Bestimmung von H sämtlicher Allenyl-Kationen 3 - 12. Der Vergleich dieser Daten mit einigen experimentell bestimmten Bildungswärmen zeigt Übereinstimmung innerhalb von 2 kcal/mol. Es werden Voraussagen für das Reaktionsverhalten gegenüber n-Nucleophilen und -Systemen gemacht

G3-RAD and G3X-RAD: Modified Gaussian-3 (G3) and Gaussian-3X (G3X) procedures for radical thermochemistry

The G3-RAD, G3X-RAD, G3(MP2)-RAD, and G3X(MP2)-RAD, procedures, designed particularly for the prediction of reliable thermochemistry for free radicals, are formulated and their performance assessed using the G2/97 test set. The principal features of the RAD procedures include (a) the use of B3-LYP geometries and vibrational frequencies (in place of UHF and UMP2), including the scaling of vibrational frequencies so as to reproduce ZPVEs, (b) the use of URCCSD(T) [in place of UQCISD(T)] as the highest-level correlation procedure, and (c) the use of RMP (in place of UMP) to approximate basis-set-extension effects. G3-RAD and G3X-RAD are found to perform well overall with mean absolute deviations (MADs) from experiment of 3.96 and 3.65 kJ mol⁻¹, respectively, compared with 4.26 and 4.02 kJ mol⁻¹ for standard G3 and G3X. G3-RAD and G3X-RAD successfully predict heats of formation with MADs of 3.68 and 3.11 kJ mol⁻¹, respectively (compared with 3.93 and 3.60 kJ mol⁻¹ for standard G3 and G3X), and perform particularly well for radicals with MADs of 2.59 and 2.50 kJ mol⁻¹, respectively (compared with 3.51 and 3.18 kJ mol⁻¹ for standard G3 and G3X). The G3(MP2)-RAD and G3X(MP2)-RAD procedures give acceptable overall performance with mean absolute deviations from experiment of 5.17 and 4.92 kJ mol⁻¹, respectively, compared with 5.44 and 5.23 kJ mol⁻¹ for standard G3(MP2) and G3X(MP2). G3(MP2)-RAD and G3X(MP2)-RAD give improved performance over their standard counterparts for heats of formation (MADs=4.73 and 4.44 kJ mol⁻¹, respectively, versus 4.94 and 4.64 kJ mol⁻¹). G3(MP2)-RAD shows similar performance to G3(MP2) for radical heats of formation (MAD=5.10 versus 5.15 kJ mol⁻¹) while G3X(MP2)-RAD performs significantly better than G3X(MP2) (MAD=4.67 versus 5.19 kJ mol⁻¹).The authors gratefully acknowledge generous allocations of computing time on the Compaq Alphaserver of the National Facility of the Australian Partnership for Advanced Computing, Australian National University Supercomputer Facility, and the support of the Australian Research Council

I Never Had to Use the Library in High School : A Library Instruction Program for At-Risk Students

Most academic library instruction is limited to one class period, despite empirical evidence that this approach is likely less effective than more sustained instruction. To determine if additional sessions would boost student learning and reduce library anxiety, the authors collaborated with representatives from a program for at-risk undergraduates to develop a three-workshop model for basic instruction and orientation. They first delivered the program during the summer of 2012 and subsequently offered it to three additional groups of students, including a cohort of doctoral students in the sciences. This article describes the process of designing the workshops and evaluating their effectiveness, with special attention to demonstrating how the program supported the parent institution’s goals and mission

Respiration rate and volume measurements using wearable strain sensors.

Current methods for continuous respiration monitoring such as respiratory inductive or optoelectronic plethysmography are limited to clinical or research settings; most wearable systems reported only measures respiration rate. Here we introduce a wearable sensor capable of simultaneously measuring both respiration rate and volume with high fidelity. Our disposable respiration sensor with a Band-Aid© like formfactor can measure both respiration rate and volume by simply measuring the local strain of the ribcage and abdomen during breathing. We demonstrate that both metrics are highly correlated to measurements from a medical grade continuous spirometer on participants at rest. Additionally, we also show that the system is capable of detecting respiration under various ambulatory conditions. Because these low-powered piezo-resistive sensors can be integrated with wireless Bluetooth units, they can be useful in monitoring patients with chronic respiratory diseases in everyday settings

Hydrogen-atom Attack on Phenol and Toluene is \u3cem\u3eortho\u3c/em\u3e-directed

The reaction of H + phenol and H/D + toluene has been studied in a supersonic expansion after electric discharge. The (1 + 1′) resonance-enhanced multiphoton ionization (REMPI) spectra of the reaction products, at m/z = parent + 1, or parent + 2 amu, were measured by scanning the first (resonance) laser. The resulting spectra are highly structured. Ionization energies were measured by scanning the second (ionization) laser, while the first laser was tuned to a specific transition. Theoretical calculations, benchmarked to the well-studied H + benzene → cyclohexadienyl radical reaction, were performed. The spectrum arising from the reaction of H + phenol is attributed solely to the ortho-hydroxy-cyclohexadienyl radical, which was found in two conformers (syn and anti). Similarly, the reaction of H/D + toluene formed solely the ortho isomer. The preference for the ortho isomer at 100–200 K in the molecular beam is attributed to kinetic, not thermodynamic effects, caused by an entrance channel barrier that is ∼5 kJ mol−1 lower for ortho than for other isomers. Based on these results, we predict that the reaction of H + phenol and H + toluene should still favour the ortho isomer under elevated temperature conditions in the early stages of combustion (200–400 °C)