An Improved Model for Polyether Production from 1,3‐Propanediol

A dynamic mathematical model is developed for production of Cerenol polyether from 1,3‐propanediol in a batch reactor system. The model accounts for polycondensation reactions and side reactions in the liquid phase and for mass transfer of volatile species to the vapor. Parameters are estimated using measured liquid‐phase concentrations of monomer, oligomers, water, and end groups as well as the mass and composition of condensate collected from the overhead condenser system. The proposed model uses novel probability factors to keep the model equations relatively simple while accounting for the complex influence of superacid catalyst on reaction rates. The model is a significant advance over previous Cerenol models because it better accounts for mass‐transfer rates and for the dynamic behavior of the condenser. In addition, the proposed model accounts for the inhibitory influence of water on polycondensation kinetics due to hydration of hydroxyl ends. The model equations and parameter estimates provide a substantial improvement in fit to the data, especially for long reaction times and high catalyst levels, resulting in a 97% reduction in the value of the weighted least squared objective function compared to equations and parameters from a previous model.     

Ein Detektor Langsamer Neutronen

Zusammenfassung Der Scintilationsdetektor für Thermo-und Resonanzneutronen, der in dieser Arbeit beschrieben wird, wurde aus einem geschmolzenen Gemisch von ZnS(Ag) und ₂₃ hergestellt. Bei optimalem Verhältnis beider Komponenten und optimaler Dicke des Detektors kann für Thermoneutronen eine verhältnismässig grosse Wirksamkeit erzielt werden (bis 25%). Der Detektor kann auch bei starkem Hintergrund von -Strahlung benützt werden, da die Wirksamkeit der -Strahlregistrierung durch passende Einstellung des Diskriminators unter 10^–7% herabgesetzt werden kann, bei einer Wirksamkeit für Thermoneutronen von ungefähr 6%.     

Tuning of nanotube mechanical resonances by electric field pulling

We show here that field emission (FE) can be used to directly observe the vibration resonances nu(R) of carbon nanotubes (CNTs) and that the tension created by the applied field allows the tuning of these resonances by up to a factor of 10. The resonances are observable by the changes they create in the FE pattern or the emitted FE current. The tuning is shown to be linear in voltage and to follow from the basic physics of stretched strings. The method allows one to study the mechanical properties of individual multiwall carbon nanotubes within an ensemble and follow their evolution as the CNTs are modified. The tuning and detection should be useful for nanometric resonant devices.     

The existence of asymptotically stable solutions for a nonlinear functional integral equation with values in a general Banach space

Motivated by the recent known results about the solvability and existence of asymptotically stable solutions for nonlinear functional integral equations in spaces of functions defined on unbounded intervals with values in the n-dimensional real space, we establish asymptotically stable solutions for a nonlinear functional integral equation in the space of all continuous functions on R₊ with values in a general Banach space, via a fixed point theorem of Krasnosel’skii type. In order to illustrate the result obtained here, an example is given.     

pH‐sensing nanostar probe using surface‐enhanced Raman scattering (SERS): theoretical and experimental studies

Local pH environment has been considered to be a potential biomarker for tumor diagnosis because solid tumors contain highly acidic environments. A pH‐sensing nanoprobe based on surface‐enhanced Raman scattering (SERS) using nanostars under near‐infrared excitation has been developed for potential biomedical applications. To theoretically investigate the effect of protonation state on SERS spectra of p‐mercaptobenzoic acid (pMBA), we used the density functional theory (DFT) with the B3LYP functional to calculate Raman vibrational spectra of pMBA‐Au/Ag complex in both protonated and deprotonated states. Vibrational spectral bands were assigned with DFT calculation and used to investigate SERS spectral changes observed from experiment when varying pH value between five and nine. The SERS peak position of pMBA at ~1580 cm⁻¹ was identified to be a novel pH‐sensing index, which has small but noticeable downshift with pH increase. This phenomenon is confirmed and well‐explained with theoretical simulation. The study demonstrates that SERS is a sensitive tool to monitor minor structural changes due to local pH environment, and DFT calculations can be used to investigate Raman spectra changes associated with minor differences in molecular structure. Copyright © 2013 John Wiley & Sons, Ltd.     

Existence and Exponential Decay of Solutions for a Wave Equation with Integral Nonlocal Boundary Conditions of Memory Type

In this paper, we consider a wave equation with integral nonlocal boundary conditions of memory type. First, we establish two local existence theorems by using Faedo–Galerkin method and standard arguments of density. Next, we give a su?cient condition to guarantee the global existence and exponential decay of weak solutions. Finally, we present numerical results.     

High‐Quality Three‐Dimensional Nanoporous Graphene

We report three‐dimensional (3D) nanoporous graphene with preserved 2D electronic properties, tunable pore sizes, and high electron mobility for electronic applications. The complex 3D network comprised of interconnected graphene retains a 2D coherent electron system of massless Dirac fermions. The transport properties of the nanoporous graphene show a semiconducting behavior and strong pore‐size dependence, together with unique angular independence. The free‐standing, large‐scale nanoporous graphene with 2D electronic properties and high electron mobility holds great promise for practical applications in 3D electronic devices.     

Theoretical Modelling and Facile Synthesis of a Highly Active Boron‐Doped Palladium Catalyst for the Oxygen Reduction Reaction

A highly active alternative to Pt electrocatalysts for the oxygen reduction reaction (ORR), which is the cathode‐electrode reaction of fuel cells, is sought for higher fuel‐cell performance. Our theoretical modelling reveals that B‐doped Pd (Pd‐B) weakens the absorption of ORR intermediates with nearly optimal binding energy by lowering the barrier associated with O₂ dissociation, suggesting Pd‐B should be highly active for ORR. In fact, Pd‐B, facile synthesized by an electroless deposition process, exhibits 2.2 times and 8.8 times higher specific activity and 14 times and 35 times less costly than commercial pure Pd and Pt catalysts, respectively. Another computational result is that the surface core level of Pd is negatively shifted by B doping, as confirmed by XPS, and implies that filling the density of states related to the anti‐bonding of oxygen to Pd surfaces with excess electrons from B doping, weakens the O bonding to Pd and boosts the catalytic activity.     

Titanium(IV) isopropoxide mediated solution phase reductive amination on an automated platform: application in the generation of urea and amide libraries

Amine libraries and their derivatives are important targets for high throughput synthesis because of their versatility as medicinal agents and agrochemicals. As a part of our efforts towards automated chemical library synthesis, a titanium(IV) isopropoxide mediated solution phase reductive amination protocol was successfully translated to automation on the Trident(TM) library synthesizer of Argonaut Technologies. An array of 24 secondary amines was prepared in high yield and purity from 4 primary amines and 6 carbonyl compounds. These secondary amines were further utilized in a split synthesis to generate libraries of ureas, amides and sulfonamides in solution phase on the Trident(TM). The automated runs included 192 reactions to synthesize 96 ureas in duplicate and 96 reactions to synthesize 48 amides and 48 sulfonamides. A number of polymer-assisted solution phase protocols were employed for parallel work-up and purification of the products in each step.