Synthesis and Theoretical Study of New Guanylated Cyclophosphazenes and Their Use in the CO2 Fixation into Styrene Carbonate

Three new guanylated cyclophosphazenes G1–G3 have been synthesized through the catalytic guanylation of three different bi, tetra and hexa (p-aminophenoxy)-cyclophosphazenes by using N,N’-diisopropylcarbodiimide as guanylating agent, ZnEt₂ as catalyst and dry tetrahydrofuran as solvent. The resulting products have been characterized by ¹H, ¹³C{¹H} and ³¹P{¹H} NMR spectroscopy. The hexaguanylated cyclophosphazenes exhibit a deep purple colour, unusual for this type of compounds. The electronic structure of these compounds was investigated by carrying out density functional calculations at PBE-D3(BJ)/TZP level of theory. The molecular structural analysis reveals that aromatic rings are stacked and time dependent density functional calculations show that a charge transfer electronic transition occurs between the aromatic rings which absorb light around 500–700 nm. Finally, the catalytic usefulness of guanylated cyclophosphazene compounds G1–G3 has been proven by the preparation of styrene carbonate from the reaction between styrene oxide and carbon dioxide.

     

CHARACTERIZATION AND COMPARISON OF SPECIATED ATMOSPHERIC CARBONACEOUS PARTICULATES AND THEIR POLYCYCLIC AROMATIC HYDROCARBON CONTENTS IN THE CONTEXT OF THE PASO DEL NORTE AIRSHED ALONG THE U.S.-MEXICO BORDER

Carbonaceous particulate matter (PM) was collected by both thermal precipitation and glass fiber filters from specific combustion sources and examined by transmission electron microscopy (TEM) and field emission scanning electron microscopy (FESEM). PM from various natural gas burner combustion regimes (NGPM), burning tires (TPM), a heavy duty diesel truck (DPM), wood burning (WPM), candle burning (CPM), along with commercial black carbon (BC) powder and multiwall carbon nanotube (MWCNT) aggregates material exhibited similarities in PM microstructure, and average primary spherule diameters. The spherule structures consisted of curved graphene fragments and intercalated polycyclic aromatic hydrocarbons (PAH). PAH concentrations were measured and compared for these PMs, including PAH diagnostic ratios. An analysis of PAH carcinogenicity either as a carcinogenicity index or a potency equivalency factor from literature data indicated that only the TPM PAH content would pose any significant long term, carcinogenicity threat.     

Arsenical grafted membranes for immobilization of thioredoxin-like proteins

In this work, we describe the cografting of glycidyl methacrylate and dimethyl acrylamide onto a macroporous polysulfone polymer. Aminophenyl arsenical compounds were covalently attached to the copolymer through epoxy ring add-on reactions followed by a 2-mercaptoethanol activation. Thioredoxin and thioredoxin-fusion proteins were immobilized onto this surface and detected by specific antibody recognition. Preservation of native protein folding was confirmed by the detection of the enzymatic activity of an unstable fusion protein. Immobilized fusion protein onto the modified material maintains the enzymatic activity for a longer time, up to two weeks, against the free protein under the same storage conditions that remains active for 2 days.     

How the free limbs are used by elite high jumpers in generating vertical velocity

The aim of this study was to quantify how elite high jumpers used their free limbs in a competitive high jump and to estimate the contribution that these made to vertical take-off velocity. This was achieved by analysing the competitive performances of six elite male high jumpers using 3D motion analysis and assessing limb function using the relative momentum method. The mean peak relative momentum of the arm nearest to the bar at take-off was 9.4 kg m s(-1), while that of the arm furthest away from the bar was 11.3 kg m s(-1) and these did not differ significantly. The free (lead) leg reached a mean peak relative momentum of 20.9 kg m s(-1). At touch-down the free leg had a large positive relative momentum that was offset by the negative relative momentum of the arms, although their combined value still remained positive. The mean combined free limbs' relative momentum at touch-down was 13.8 kg m s(-1) and reached a peak of 37.6 kg m s(-1). The difference between these two values amounted to 7.1 % of whole-body momentum, which was judged to be the amount by which the free limbs contributed to performance. The arms had a greater influence on performance than had the lead leg. This was because the lead leg increased its relative momentum little during the contact period while the arms had an initial negative value that increased markedly after touch-down. The compressive force exerted by the motion of the free limbs, estimated by the change in the combined free limbs' relative momentum, reached a mean peak of 366 N and was greatest at 37% of the contact period. It was concluded that to maximize the contribution the free limbs can make to performance, given the restraints imposed on technique by other performance requirements, the arms should have a vigorous downward motion at touch-down to make the most use of the high (but little changing) relative momentum of the lead leg.     

Antibacterial activity against Escherichia coli of Cu‐BTC (MOF‐199) metal‐organic framework immobilized onto cellulosic fibers

A strong antimicrobial activity against Escherichia coli of Cu‐BTC metal‐organic frameworks immobilized over cellulosic fibers is hereby reported. The in situ synthesis of Cu‐BTC metal‐organic frameworks, aka MOF‐199 or HKUST‐1, onto cellulosic substrates was carried out by exposing carboxymethylated cellulosic substrates to Cu(OAC)₂, 1,3,5‐benzenetricarboxylic acid and triethylamine solutions following a very specific order. Using an in vitro model, in accordance to ASTM E2149‐13a, we observed that the cellulose‐MOF system was able to completely eliminate the growth of E. coli on agar plates and liquid cultures. The antibacterial activity of the comprising components of MOF‐199 and the cellulosic substrate was also evaluated and determined to be negligible. Since the method used to synthesize MOF‐199 crystals provides a strong bond between the crystals and the cellulosic substrates, the crystals not detach from the anionic cellulosic fibers allowing the modified textile to be washed and reused hence opening a new avenue to fabricate antibacterial clinical fabrics. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40815.     

Density-driven flow and solute transport problems. A 2-D numerical model based on the network simulation method

The network simulation method, based on the formal equivalence between physical systems and electrical networks, solves numerical problems of relatively mathematical complexity in a versatile, efficient and computationally fast way. In this paper, the method is applied for the first time to the design of a general purpose model for simulating two-dimensional transient density-driven flow and solute transport through porous media, a mathematical model made up by coupled, nonlinear differential equations. Using the Boussinesq approximation and the stream function formulation, the model is used to solve two typical problems related with groundwater flows. Isochlor concentration and stream function curves are presented and successfully compared with those of other authors. Simulation is carried out using the digital computer program Pspice with relatively low computing times.     

A toolkit for constructing command driven graphics programs

This paper describes a toolkit designed to construct graphics applications on top of it that are command driven. The aim in its design is to achieve a uniform look-and-feel for the applications developed in the department, and to make it possible to construct demonstration programs or test programs of ongoing research that required a sophisticated user interface with minimal fuss. The present implementation runs under UNIX, but the same philosophy could be used in other environments.     

All-optical AND gate implementation using cross-polarizationmodulation in a semiconductor optical amplifier

We demonstrate experimentally a new design for an all-optical AND gate operating in the gigahertz regime. The efficiency of this effect was estimated by measuring the conversion coefficients C_TETM/ and C_TMTE/ indicating the TE to TM mode conversion and vice versa when the amplifier is perturbed with a wavelength tunable control beam. The all-optical gate here described differ from others developed before using semiconductor optical amplifiers in its ability to operate on nondegenerate input signals and to produce an output signal with an independent wavelength from the wavelengths of the input signals     

Toughened carbon fiber fabric‐reinforced pCBT composites

Toughened carbon fiber‐fabric reinforced polymerized cyclic butylene terephthalate (pCBT) composites were obtained by chemical modification of cyclic butylene terephthalate (CBT) with small amounts of epoxy resin and isocyanates as chain extenders. Homogeneous CBT/epoxy and CBT/isocyanate blends were prepared by melt blending the components in a lab‐scale batch mixer at low temperatures and high shear rate. Melt blending was stopped before the ring‐opening polymerization of CBT could start. The modified CBT was the starting material for carbon fiber fabric‐reinforced pCBT composites (fiber content at about 65 wt%) which were prepared by ring‐opening polymerization during compression molding using a simple powder prepreg method. Interlaminar shear strength, flexural strength, and failure strain of the chemically modified composites increased up to 60% with respect to unmodified pCBT composites. Nevertheless, the flexural moduli slightly decreased due to the toughening effect of the chain extender on the pCBT matrix. Drop weight impact tests revealed that the energy absorption of the modified composites was relatively higher as compared to unmodified pCBT composites. POLYM. COMPOS., 37:1453–1460, 2016. © 2014 Society of Plastics Engineers