Effect of polyaniline (PANI) on efficiency enhancement of dye-sensitized solar cells fabricated with poly(ethylene oxide)-based gel polymer electrolytes

Journal of Solid State Electrochemistry - Ionically conducting gel polymer electrolytes can be used effectively to improve the problems associated with liquid electrolytes in dye-sensitized solar...     

Utilizing Experiment and Theory to Evaluate Rhodamine B ethylenediamine as a Fluorescent Sensor for G-type Nerve Agents

Nerve gas mimic binding with Rhodamine B ethylenediamine (1) was studied in organic media. Binding of the nerve gas mimic, diethyl chlorophosphate (DCP), with the probe generated a non-fluorescent intermediate and a fluorescent product. Fluorescent and non-fluorescent products generated were identified using mass spectrometry and X-ray crystallography. Time-dependent density functional theory calculations were also used to investigate the electronic structure of the fluorescent probe in the ground and lowest lying π?→?π* singlet excited state. Though good agreement between theory and experiment can be obtained for the intense peak in the experimental spectrum using non-hybrid functionals, care must be taken when modelling these complexes due to the appearance of an n?→?π* transition that is too low in energy and appears to fall in the shoulders of the π?→?π* transitions.

     

Optimal buffer size and dynamic rate control for a queueing system with impatient customers in heavy traffic

We address a rate control problem associated with a single server Markovian queueing system with customer abandonment in heavy traffic. The controller can choose a buffer size for the queueing system and also can dynamically control the service rate (equivalently the arrival rate) depending on the current state of the system. An infinite horizon cost minimization problem is considered here. The cost function includes a penalty for each rejected customer, a control cost related to the adjustment of the service rate and a penalty for each abandoning customer. We obtain an explicit optimal strategy for the limiting diffusion control problem (the Brownian control problem or BCP) which consists of a threshold-type optimal rejection process and a feedback-type optimal drift control. This solution is then used to construct an asymptotically optimal control policy, i.e. an optimal buffer size and an optimal service rate for the queueing system in heavy traffic. The properties of generalized regulator maps and weak convergence techniques are employed to prove the asymptotic optimality of this policy. In addition, we identify the parameter regimes where the infinite buffer size is optimal.     

Is cluster evaporation statistical? A comparison of simulation results for Ar13 with exact classical phase space theory

We have simulated the dissociation reactionA _n →A _n?1+A for small clusters (L-J argon) with well defined internal energy and total angular momentum. Reaction rates and kinetic energy release distributions are compared to the predictions of several statistical theories, including RRK, the “Engelking” model, and phase space theory (PST). We have applied classical phase space theory in an essentially exact formulation using accurate anharmonic vibrational densities of states (and no adjustable parameters). We present a critical evaluation of the different theories and sensitivity of the results to the underlying assumptions.     

Convergence of a queueing system in heavy traffic with general patience-time distributions

We analyze a sequence of single-server queueing systems with impatient customers in heavy traffic. Our state process is the offered waiting time, and the customer arrival process has a state dependent intensity. Service times and customer patient-times are independent; i.i.d. with general distributions subject to mild constraints. We establish the heavy traffic approximation for the scaled offered waiting time process and obtain a diffusion process as the heavy traffic limit. The drift coefficient of this limiting diffusion is influenced by the sequence of patience-time distributions in a non-linear fashion. We also establish an asymptotic relationship between the scaled version of offered waiting time and queue-length. As a consequence, we obtain the heavy traffic limit of the scaled queue-length. We introduce an infinite-horizon discounted cost functional whose running cost depends on the offered waiting time and server idle time processes. Under mild assumptions, we show that the expected value of this cost functional for the n-th system converges to that of the limiting diffusion process as n tends to infinity.     

Rhodamine Based Turn-On Sensors for Ni<Superscript>2+</Superscript> and Cr<Superscript>3+</Superscript> in Organic Media: Detecting CN<Superscript>−</Superscript> via the Metal Displacement Approach

Two novel sensors bearing rhodamine B and quinoline units have been synthesized. One of these, 1, allows sensitive and selective detection of Ni²⁺ and Cr³⁺ by forming non-fluorescent (1-Ni²⁺) and fluorescent (1-Cr³⁺) complexes respectively. Both metals trigger the formation of highly colored ring-open spirolactam. These form excellent probes for CN^? which quenches the fluorescence of the 1-Cr³⁺ complex by extracting the Cr³⁺. Both Cr³⁺ and Cu²⁺ gave color changes with 2, but they are easily identified separately via the large fluorescence enhancement that occurs only with Cr³⁺.     

Optimal buffer size for a stochastic processing network in heavy traffic

We consider a one-dimensional stochastic control problem that arises from queueing network applications. The state process corresponding to the queue-length process is given by a stochastic differential equation which reflects at the origin. The controller can choose the drift coefficient which represents the service rate and the buffer size b>0. When the queue length reaches b, the new customers are rejected and this incurs a penalty. There are three types of costs involved: A “control cost” related to the dynamically controlled service rate, a “congestion cost” which depends on the queue length and a “rejection penalty” for the rejection of the customers. We consider the problem of minimizing long-term average cost, which is also known as the ergodic cost criterion. We obtain an optimal drift rate (i.e. an optimal service rate) as well as the optimal buffer size b ^*>0. When the buffer size b>0 is fixed and where there is no congestion cost, this problem is similar to the work in Ata, Harrison and Shepp (Ann. Appl. Probab. 15, 1145–1160, 2005). Our method is quite different from that of (Ata, Harrison and Shepp (Ann. Appl. Probab. 15, 1145–1160, 2005)). To obtain a solution to the corresponding Hamilton–Jacobi–Bellman (HJB) equation, we analyze a family of ordinary differential equations. We make use of some specific characteristics of this family of solutions to obtain the optimal buffer size b ^*>0. A.P. Weerasinghe’s research supported by US Army Research Office grant W911NF0510032.     

Consideration of some sampling problems in the on-line analysis of batch processes by low-field NMR spectrometry

A low-field medium-resolution NMR spectrometer, with an operating frequency of 29 MHz for 1H, has been assessed for on-line process analysis. A flow cell that incorporates a pre-magnetisation region has been developed to minimise the decrease in the signal owing to incomplete polarisation effects. The homogeneous esterification reaction of crotonic acid and 2-butanol was monitored using a simple sampling loop; it was possible to monitor the progression of the reaction through changes in CH signal areas of butanol and butyl crotonate. On-line analysis of heterogeneous water-toluene mixtures proved more challenging and a fast sampling loop system was devised for use with a 5 L reactor. The fast sampling loop operated at a flow rate of 8 L min(-1) and a secondary sampling loop was used to pass a sub-sample through the NMR analyser at a slower (mL min(-1)) rate. It was shown that even with super-isokinetic sampling conditions, unrepresentative sampling could occur owing to inadequate mixing in the reactor. However, it was still possible to relate the 1H NMR signal obtained at a flow rate of 60 mL min(-1) to the composition of the reactor contents.     

Properties of a laser beam generated from an axicon resonator

A high power cw CO₂ laser beam is generated from a resonator configuration having an axicon mirror as its end reflector. The properties of this beam are evaluated in terms of its polarization, focusing capability and temporal stability and the resulting effects on processing materials are presented. A comparison is made between a folded and a straight resonator having a spherical focusing mirror as its end reflector.     

Synthesis of carbapyochelins via diastereoselective azidation of 5-(ethoxycarbonyl)methylproline derivatives

Two configurationally stable carbon-based analogues of pyochelin have been prepared from Boc-pyroglutamic acid-tert-butyl ester in 11 and 13 steps. Introduction of the amino group was achieved by a highly diastereoselective electrophilic azidation reaction to afford novel bis-alpha-amino acid proline derivatives.