Thermal runaway evaluation of α-methylstyrene and trans-β-methylstyrene with benzaldehyde

Styrene is an important chemical in the petrochemical industry. In recent years, there have been sporadic releases, runaway reactions, fires, and thermal explosion accidents incurred by styrene and its derivatives worldwide. The purpose of this study was to estimate the impact of styrene and its derivatives of α-methylstyrene (AMS) and trans-β-methylstyrene (TBMS) contacting with benzaldehyde. Experiments were carried out to evaluate the thermokinetic parameters estimated by differential scanning calorimetry (DSC) and thermal activity monitor III (TAM III). TAM III was used to determine the fundamental thermokinetics under various isothermal temperatures, 80, 90 and 100°C. This autocatalytic reaction was demonstrated in thermal curves. After styrene was contacted with benzaldehyde, the exothermic onset temperature (T ₀) and the total heat of reaction (Q _total) were altered by DSC tests. When benzaldehyde is mixed with AMS and TBMS, the reaction time will be shorter but the enthalpy reduced, as revealed by TAM III tests. As AMS and TBMS, respectively, were contacted with benzaldehyde, both exothermic phenomena were changed during the reaction excursion. According to the results of this research, an operator should dictate the oxygen concentration in order to avoid any potential hazards during handling and transportation.     

Thermal hazard evaluation of carbon nanotubes with sulfuric acid by DSC

Many concerns over unsafe or unknown properties of multi-walled carbon nanotubes (MWNTs) have been raised. The thermal characteristics regarding stability would represent potential hazards during the production or utilization stage and could be determined by calorimetric tests for various thermokinetic parameters. Differential scanning calorimetry (DSC) was employed to evaluate the thermokinetic parameters for MWNTs at various compositions. Thermoanalytical curves showed that the average heat of decomposition (ΔH _d) of the MWNTs samples in a manufacturing process was about 31,723 J g⁻¹, by identifying them as an inherently hazardous material. In this study, significant thermal analysis appeared in the presence of sulfuric acid (H₂SO₄). From the DSC experiments, the purification process of MWNTs could induce an unexpected reaction in the condition of batch addition with reactants of H₂SO₄. The results can be applied for designing emergency relief system and emergency rescue strategies during a perturbed situation or accident.     

A Supramolecular Approach for Preparation of Size‐Controlled Nanoparticles

A supramolecular approach has been developed for the preparation of supramolecular nanoparticles (SNPs) with variable sizes (30–450 nm) from three different molecular building blocks using a cyclodextrin/adamantane recognition system. Positron emission tomography (PET) was employed to study the biodistribution and lymph node drainage of the SNPs in mice. The sizes of the SNPs affect their in vivo characteristics (see picture).

     

The quantum orbifold cohomology of weighted projective spaces

We calculate the small quantum orbifold cohomology of arbitrary weighted projective spaces. We generalize Givental’s heuristic argument, which relates small quantum cohomology to S ¹-equivariant Floer cohomology of loop space, to weighted projective spaces and use this to conjecture an explicit formula for the small J-function, a generating function for certain genus-zero Gromov–Witten invariants. We prove this conjecture using a method due to Bertram. This provides the first non-trivial example of a family of orbifolds of arbitrary dimension for which the small quantum orbifold cohomology is known. In addition we obtain formulas for the small J-functions of weighted projective complete intersections satisfying a combinatorial condition; this condition naturally singles out the class of orbifolds with terminal singularities.     

A hybrid genetic local search algorithm for the permutation flowshop scheduling problem

Traditionally, the permutation flowshop scheduling problem (PFSP) was with the criterion of minimizing makespan. The permutation flowshop scheduling problem to minimize the total flowtime has attracted more attention from researchers in recent years. In this paper, a hybrid genetic local search algorithm is proposed to solve this problem with each of both criteria. The proposed algorithm hybridizes the genetic algorithm and a novel local search scheme that combines two local search methods: the Insertion Search (IS) and the Insertion Search with Cut-and-Repair (ISCR). It employs the genetic algorithm to do the global search and two local search methods to do the local search. Two local search methods play different roles in the search process. The Insertion Search is responsible for searching a small neighborhood while the Insertion Search with Cut-and-Repair is responsible for searching a large neighborhood. Furthermore, the orthogonal-array-based crossover operator is designed to enhance the GA’s capability of intensification. The experimental results show the advantage of combining the two local search methods. The performance of the proposed hybrid genetic algorithm is very competitive. For the PFSP with the total flowtime criterion, it improved 66 out of the 90 current best solutions reported in the literature in short-term search and it also improved all the 20 current best solutions reported in the literature in long-term search. For the PFSP with the makespan criterion, the proposed algorithm also outperforms the other three methods recently reported in the literature.     

Block-Coordinate Gradient Descent Method for?Linearly Constrained Nonsmooth Separable Optimization

We consider the problem of minimizing the weighted sum of a smooth function f and a convex function P of n real variables subject to m linear equality constraints. We propose a block-coordinate gradient descent method for solving this problem, with the coordinate block chosen by a Gauss-Southwell-q rule based on sufficient predicted descent. We establish global convergence to first-order stationarity for this method and, under a local error bound assumption, linear rate of convergence. If f is convex with Lipschitz continuous gradient, then the method terminates in O(n ²/ε) iterations with an ε-optimal solution. If P is separable, then the Gauss-Southwell-q rule is implementable in O(n) operations when m=1 and in O(n ²) operations when m>1. In the special case of support vector machines training, for which f is convex quadratic, P is separable, and m=1, this complexity bound is comparable to the best known bound for decomposition methods. If f is convex, then, by gradually reducing the weight on P to zero, the method can be adapted to solve the bilevel problem of minimizing P over the set of minima of f+δ _X , where X denotes the closure of the feasible set. This has application in the least 1-norm solution of maximum-likelihood estimation. This research was supported by the National Science Foundation, Grant No. DMS-0511283.     

Electrokinetic flow in an elliptic microchannel covered by ion-penetrable membrane

The electrokinetic flow of an electrolyte solution in an elliptical microchannel covered by an ion-penetrable, charged membrane layer is examined theoretically. The present analysis extends previous results in that a two-dimensional problem is considered, and the system under consideration simulates the flow of a fluid, for example, in a microchannel of biological nature such as vein. The electroosmostic volumetric flow rate, the total electric current, the streaming potential, and the electroviscous effect of the system under consideration are evaluated. We show that, for a constant hydraulic diameter, the variations of these quantities as a function of the aspect ratio of a microchannel may have a local minimum or a local maximum at a medium level of ionic strength, which depends on the thickness of the membrane layer. For a constant cross-sectional area, the electroosmostic volumetric flow rate, the total electric current, and the streaming potential increase monotonically with the increase in the aspect ratio, but the reverse is true for the electroviscous effect.     

Preparation of highly porous carbon from fir wood by KOH etching and CO2 gasification for adsorption of dyes and phenols from water

Fir wood was first carbonized for 1.5 h at 450 degrees C, then soaked in a KOH solution KOH/char ratio of 1, and last activated for 1 h at 780 degrees C. During the last hour CO2 was poured in for further activation for 0, 15, 30, and 60 min, respectively. Carbonaceous adsorbents with controllable surface area and pore structure were chemically activated from carbonized fir wood (i.e., char) by KOH etching and CO2 gasification. The pore properties, including the BET surface area, pore volume, pore size distribution, and pore diameter, of these activated carbons were first characterized by the t-plot method based on N2 adsorption isotherms. Fir-wood carbon activated with CO2 gasification from 0 to 60 min exhibited a BET surface area ranging from 1371 to 2821 m2 g(-1), with a pore volume significantly increased from 0.81 to 1.73 m2 g(-1). Scanning electron microscopic (SEM) results showed that the surfaces of honeycombed holes in these carbons were significantly different from those of carbons without CO2 gasification. The adsorption of methylene blue, basic brown 1, acid blue 74, p-nitrophenol, p-chlorophenol, p-cresol, and phenol from water on all the carbons studied was examined to check their chemical characteristics. Adsorption kinetics was in agreement with the Elovich equation, and all equilibrium isotherms were in agreement with the Langmuir equation. These results were used to compare the Elovich parameter (1/b) and the adsorption quantity of the unit area (q(mon)/Sp) of activated carbons with different CO2 gasification durations. This work facilitated the preparation of activated carbon by effectively controlling pore structures and the adsorption performance of the activated carbon on adsorbates of different molecular forms.     

Supramolecular self-assembly of dendronized polymers: reversible control of the polymer architectures through acid-base reactions

Acid-base switchable supramolecular dendronized polyacetylenes (DPAs) with increasing steric bulk on going from generation one [G1] to three [G3], were constructed using multiple self-assembly processes between Fréchet-type [G1]-[G3]-dendritic dialkylammonium salts and a dibenzo[24]crown-8-containing polymer. The formation of the supramolecular systems is acid-base switchable to either an ON (rodlike dendronized polymers) or an OFF (flexible polymers) state. Thus, by controlling the superstructures of the supramolecular polymers with the [G1]-[G3] dendrons, it is possible to induce conformational changes within the polymer backbones. The supramolecular dendronized polymers, as well as their threading-dethreading properties, were characterized by (1)H NMR and UV absorption spectroscopies, gel permeation chromatography (GPC) and light scattering (LS). Independent measures of molecular weight (GPC, LS) indicate that DPAs behave as increasingly rigid macromolecules with each generation in solution. Molecular dynamics simulations of each DPA suggest that the lengths of the polymer backbones increase accordingly. Atomic force microscopy of the [G3]-dendronized polystyrene (DPS), as well as the DPAs, reveal surface morphologies indicative of aggregated superstructures.     

CH...pi interaction for rhenium-based rectangles: an interaction that is rarely designed into a host-guest pair

Alkoxy- and thiolato-bridged Re(I) molecular rectangles [{(CO)3Re(mu-ER)2Re(CO)3}2(mu-bpy)2] (ER = SC4H9, 1a; SC8H17, 1b; OC4H9, 2a; OC12H25, 2b; bpy = 4,4'-bipyridine) exhibit strong interactions with several planar aromatic molecules. The nature of their binding was studied by spectral techniques and verified by X-ray diffraction analysis. Standard absorption and fluorescence titrations showed that a relatively strong 1:1 interaction occurs between aromatic guests such as pyrene and these rectangles. The results of a single-crystal X-ray diffraction analysis show that the recognition of 1 with a pyrene molecule is mainly due to CH...pi interactions and the face of the guest pyrene is located over the edges of the bpy linkers of 1. This is a fairly novel example of an interaction that is rarely designed into a host-guest pair. Furthermore, the interaction of 1 with Ag+ results in the self-organization of supramolecular arrays, as revealed by solid-state data.