Evaluation of 2-hydroxyethyl methacrylate as comonomer in the preparation of water-compatible molecularly imprinted polymers for triazinic herbicides

In this work, the preparation and evaluation of water-compatible molecularly imprinted polymers for triazines using 2-hydroxyethyl methacrylate and methacrylic acid as comonomers is described. Four sets of molecularly imprinted and non-imprinted polymers for propazine were prepared at varying monomer molar ratios (from 4:0 to 1:3), and evaluated for the recognition of several triazines directly in aqueous media. The evaluation was performed by loading 1 mL of an aqueous solution containing 500 ng of each selected triazine, washing with 500 μL of acetonitrile, and eluting with 500 μL of methanol followed by 2 × 500 μL of a solution of methanol containing 10% of acetic acid. Final determinations were performed by high-performance liquid chromatography-ultraviolet detection. Improvement in molecular recognition of triazines in water was obtained on those molecularly imprinted polymers incorporating 2-hydroxyethyl methacrylate in 3:1 or 2:2 molar ratios, being the former selected as optimum providing recoveries for propazine up to 80%. A molecularly imprinted solid-phase extraction protocol was developed to ensure that triazines-selective recognition takes place inside selective binding sites in pure water media. Finally, the developed method was successfully applied to the determination of the selected triazines in environmental waters providing limits of detection from 0.16 and the 0.5 μg/L concentration range.     

Reactions of aminoguanidine with α-dicarbonyl compounds studied by electrospray ionization mass spectrometry

Aminoguanidine possesses extensive pharmacological properties. This drug is recognized as a powerful α-dicarbonyl scavenger. In order to better elucidate the reactivity of aminoguanidine with α-dicarbonyls, aminoguanidine was reacted with several aldehydic and diketonic α-dicarbonyls. Electrospray ionization mass spectrometry is a suitable technique to study chemical and biochemical processes, and was selected for the purpose. In aminoguanidine reactions, triazines were detected and, other compounds that have never been reported before were identified. Triazine precursor forms were detected, namely tetrahydrotriazines and singly dehydrated tetrahydrotriazines. Moreover, species with bicyclic ring structures, and dehydrated forms, were also identified in aminoguanidine reactions. These species appear to result from tetrahydrotriazines and triazines reactions with one dicarbonyl molecule. Experiments revealed that these bicyclic species, in particular the ones resulting from triazines reactivity, could exist in solution, since they were both identified in the reactions of aminoguanidine and of a selected triazine with the dicarbonyls studied. The results obtained, regarding aminoguanidine/triazines reactivities, appear to support the capability of triazines to condensate and form polycyclic ring structures, and also to support literature mechanistic data for dihydroimidazotriazines formation via dihydroxyimidazolidine-triazines. The data obtained in this study may prove to be valuable to complement solution information, concerning the reactivity of amines with α-dicarbonyls, in particular.     

AM1 molecular orbital studies of the structures,conformations, protonation energies,and electronic properties of triazine dihydrofolate reductase inhibitors

The structural, conformational, and electronic properties of three triazine antifolates were determined by AM1 molecular orbital calculations, and the results were compared with other theoretical studies and with X-ray crystallographic studies of these and similar triazines both in the crystalline state and as complexes bound to dihydrofolate reductase. Calculated protonation energies confirm crystal structure data indicating N-protonation analogous to that reported for MTX in similar environments. Overall, the calculated structural and conformational properties are in good agreement with X-ray crystallographic results for these and similar triazines as found in the crystalline state and in enzymebound ternary complexes. However, for one triazine AM1 predicts a conformation with the bulky aromatic substituent twisted about 60° away from coplanarity with the triazine ring, in contrast to the nearly coplanar conformation found in the crystalline state. Intermolecular interactions favoring the coplanar conformation may thus be operative in the crystalline environment. The unique conformational preferences and greater conformation flexibility of triazines in general and of this triazine in particular may provide a key to understanding their biological activity.     

Synthesis and characterization of a new benzobisoxazole/thiophene derivative polymer and the effect of the substituent on the push/pull properties

Conducting polymer synthesis of a new benzobisoxazole/thiophene derivative is reported. The conjugated co-polymer presents the lowest bandgap (1.78 eV) reported for a neutral benzobisoxazole/thiophene polymer. Electrochemical polymerization is carried out by cyclic voltammetry, and the new conducting polymer is characterized by Raman spectroscopy and X-ray photoelectron spectroscopy. The results indicate that the coupling of the monomer unit occurs at the 2,2′ positions of the thiophene ring. Theoretical studies in derivatives of this family of compounds are conducted to validate the effect on the bandgap modulation due to the change in the substituent on the phenyl moiety of the monomer. The comparison between experimental and theoretical properties shows the substituents impact on the optical properties of the system, and its viability to be used in sensors.     

Thermal Properties of E-beam Cured Epoxy/Thermoplastic Matrices for Advanced Composite Materials

The aim of this work is to investigate the possibility to improve the thermal behaviour of epoxy based systems, cured by ionizing radiation, in order to produce matrices for advanced carbon fibres composites. Blends of two epoxy monomers, difunctional and trifunctional, have been polymerized by e-beam irradiation and the dynamic mechanical thermal properties have been investigated. The increase of the concentration of the trifunctional epoxy monomer in the blend causes a marked increase of the Tg, but strongly decreases the reactivity. Subsequently, blends of the same epoxy monomers with a high Tg thermoplastic toughening agent have been considered and their reactivity and the thermal properties of the obtained materials have been also studied. The experimental results show that the thermoplastic component increases the reactivity of the difunctional/trifunctional blends, without a significant decrease of the glass transition temperature which still satisfies the requirements for advanced composite materials.     

Structure and property of the hydrogen bonding complex between triazines and water

The study of the intermolecular interactions that drive the solvation of six-membered nitrogenated aromatic rings is of particular importance since they are known to constitute key building blocks of pro- teins and nucleotides[1―5]. The investigation of the 1:1 adduct of these molecules with water will be the first step in the understanding of such interactions. These molecules possess two different proton-acceptor sites: the ring π cloud and the lone pairs of electrons on the nitrogen atoms…     

Breakthrough in the preparation of irradiated sodium alginate/polyethylene oxide blend films using methacrylate monomer

The present work is an attempt to prepare biodegradable films of sodium alginate (SA)/polyethylene oxide (PEO) blend tailored by methacrylate (MA) and γ irradiation following casting method. The effects of SA/PEO composition, glycerol as a plasticizer, methacrylate as a monomer, and radiation dose were investigated and it was found that the mechanical properties of the films strongly depend on the film-forming parameters. The incorporation of glycerol in the blend is crucial as it creates a suitable environment for monomer addition and points out that tensile strength of the films decreased, while the elongation at break increased. Moreover, it was found that the tensile properties were improved by the application of γ radiation as well as monomer treatment. The mechanical properties of the blend films integrated with MA monomer were higher than that without monomer at the analogous conditions. The structural and morphological features of the films were examined by Fourier transform infrared spectroscopy and scanning electron microscopy, respectively.     

Heterocycles as Structural Units in New Optical Brighteners

Optical brighteners are used in detergents, textiles, paper, plastics, and paints. Most optical brighteners contain heterocycles such as coumarins, 2-pyrazolines, naphthalimides, pyrazoles, triazoles, oxadiazoles, and triazines. In this article the syntheses, properties, and applications of new optical brighteners are described with references to patent literature.     

Influence of the Styrene Ratio on the Copolymerization Kinetics of Dimethacrylate of Diglycidyl Ether of Bisphenol a Vinylester Resins Crosslinked with Styrene

Abstract

Infrared spectroscopy was used in this work to investigate the copolymerization characteristics of systems based on a dimethacrylate of diglycidyl ether of Bisphenol A combined with styrene in variable proportions ranging from 25 to 60% by weight. Particular attention has been paid to determination of the theoretical monomer sequence distributions obtained from copolymerization theory. The results show that the final structure of these materials is probably diphasic, with a first phase consisting of a vinylester network and a second phase rich in polystyrene. The influence of the monomer sequence distribution on the final crosslink density has been evaluated.     

Aromatic polyethers,polysulfones, and polyketones as laminating resins. II

1,3-Bis(p-phenoxybenzenesulfonyl)benzene and 4,4′-bis(p-phenoxybenzenesulfonyl)-diphenyl ether were polymerized with isophthaloyl and terephthaloyl chloride in Friedel-Crafts type polymerizations. These polymers had 5-cyanoisophthaloyl units in the backbone, obtained by using 5-cyanoisophthaloyl chloride as part of the acid chloride monomer. A number of catalysts were screened to effect the trimerization of the pendant nitrile groups in the polymer to the triazines. Model reactions were carried out for each polymer. Physical and thermal properties of the laminates obtained from these polymers are discussed.     

Molecular structure,vibrational spectra and nonlinear optical properties of orthoarsenic acid–tris-(hydroxymethyl)-aminomethane DFT study

In this work, we report a theoretical study on molecular structure, vibrational spectra and nonlinear optical properties of orthoarsenic acid–tris-(hydroxymethyl)-aminomethane (OATA). The theoretical geometrical parameters in the ground state have been investigated by density functional method (B3LYP and BLYP) with 6-311G(d,p) basis set. The influence of intermolecular interactions effects on molecular properties has been considered by calculation performed on (OATA) dimer. The optimized geometric bond lengths and bond angles are in well agreement with the experimental data. As compared to theoretical frequencies of the monomer, the calculated values obtained for (OATA) dimer are in much better agreement with the experiment. All experimental vibrational bands have been discussed and assigned to normal modes on the basis of our theoretical calculations. B3LYP method has shown better fit to experimental ones than BLYP in calculation vibrational frequencies. To investigate nonlinear optical behaviour, the electric dipole moment μ, the polarizability α and the hyperpolarizability β were computed using DFT//B3LYP/6-311G(d,p) method.     

Comparative theoretical studies of energetic azo s-triazines

In this work, the properties of the synthesized high-nitrogen compounds 4,4',6,6'-tetra(azido)azo-1,3,5-triazine (TAAT) and 4,4',6,6'-tetra(azido)hydrazo-1,3,5-triazine (TAHT), and a set of designed bridged triazines with similar bridges were studied theoretically to facilitate further developments for the molecules of interests. The gas-phase heats of formation were predicted based on the isodesmic reactions by using the DFT-B3LYP/AUG-cc-PVDZ method. The estimates of the condensed-phase heats of formation and heats of sublimation were estimated in the framework of the Politzer approach. Calculation results show that the method gives a good estimation for enthalpies, in comparison with available experimental data for TAAT and TAHT. The crystal density has been computed using molecular packing calculations. The calculated detonation velocities and detonation pressures indicate that -NF(2), -NO(2), -N═N-, and -N═N(O)- groups are effective structural units for improving the detonation performance of the bridged triazines. The synthesized TAAT and TAHT are not preferred energetic materials due to their inferior detonation performance. The p→π conjugation effect between the triazine rings and bridges makes the molecule stable as a whole. The electrostatic behavior of the bridged triazines is characterized by an anomalous surface potential imbalance when incorporating the strongly electron-withdrawing -NF(2) and -NO(2) groups into the molecule. An analysis of the bond dissociation energies shows that all these derivatives have good thermal stability over RDX and HMX, and the -NH-NH- bridge is more helpful for improving the stability than -N═N(O)- and -N═N- bridges. Considering the detonation performance and thermal stability, three bridged triazines may be considered as the potential candidates of high-energy density materials (HEDMs).     

Design of PP/EPDM/NBR TPVs with tunable mechanical properties via regulating the core-shell structure

In this work, polypropylene (PP)/ethylene-propylene-diene monomer (EPDM)/butadiene acrylonitrile rubber (NBR) TPVs with different EPDM/NBR ratios were prepared by the core-shell dynamic vulcanization. The relationship between the core-shell structure and mechanical properties of the TPVs were thoroughly investigated. The formation of core-shell structure by adding NBR is conducive to the mechanical properties of the TPVs. The ratio of EPDM to NBR has an important effect on the structure and performances of the final products, and there is a critical ratio for this effect change. Transmission electron microscope (TEM), tensile test, reprocessing test, ageing test, rheological behavior test and stress relaxation were used to characterize the morphology and properties of the TPVs in detail. It was found that when the ratio of EPDM/NBR was 2:4, the tensile strength increased by ~14% compared with PP/EPDM TPV without NBR. Meanwhile, the reprocessing properties, rheological characteristics and instantaneous tensile deformation, etc. all exhibited sudden changes at this critical ratio.     

一种新型硅藻土填充橡胶纳米复合材料研究

橡胶的填料问题一直是人们的研究热点,针对炭黑和白炭黑在橡胶生产中存在的污染问题,本文选用成分结构与白炭黑类似的硅藻土来填充各种橡胶。首先对硅藻土进行了改性,并对不同改性剂改性硅藻土用于填充橡胶进行了研究。结果表明2.5份偶联剂Si69的改性效果最佳。通过机械共混法制备了改性硅藻土/橡胶纳米复合材料,通过力学性能测试确定了比较适合硅藻土填充的橡胶是氟橡胶、三元乙丙橡胶和丙烯酸酯橡胶。绿色环保且价格低廉的硅藻土可以替代白炭黑增强填充氟橡胶、三元乙丙橡胶和丙烯酸酯橡胶。     

On the calculations of interaction energies and induced electric properties within the polarizable continuum model

In this work we investigate the influence of a polarizable environment on the interaction energies and the interaction-induced (excess) static electric dipole properties for the selected model hydrogen-bonded complexes. The excess properties were estimated for water and hydrogen fluoride dimers using the supermolecular approach and assuming the polarizable continuum model (PCM) as a representation of the polarizable environment. We analyze in this context the performance of the counterpoise correction and the consequences of various possible monomer cavity choices. The polarizable environment reduces the absolute magnitudes of interaction energies and interaction-induced dipole moments, whereas an increase is observed for the absolute magnitudes of induced polarizabilities and first hyperpolarizabilities. Our results indicate that the use of either monomeric (MC) or dimeric (DC) cavities in calculations of monomer properties does not change qualitatively the resultant excess properties. We conclude that the DC scheme is more consistent with the definition of the interaction energy and consequently also the interaction-induced property, whereas the MC scheme corresponds to the definition of stabilization energy. Our results indicate also a good performance of the counterpoise correction scheme for the self-consistent methods in the case of all studied properties.     

环丁炔热力学性质及其存在寿命的理论研究

包含一个－CC－键、碳原子数最少的环炔是什么？这一直是物理有机化学界为之费解并颇感兴趣的问题之。从实验方面来说词，光谱已检测到最小的环炔姓是环己炔，至于环戊炔，Miller和ChaPman尝试性地建议其特征红外光谱是2125cm‘和2077cm‘位置的两个强谱带，1646cm－‘位置的一个中强谱带和908cm－‘、627cm－‘位置的两个弱谱带．但环丁炔及其衍生物是否存在？实验上一直未获确证【’，‘1．从理论上说，已经很清楚，单重态的环丙炔是下列重排反应的过渡态：而三重态的环丙炔是一个双自由基怖下结构式】．很明显，它不会三重C。C键＊．…     

Efficient Preparation of Pyridinyl‐1,2,4‐Triazines via Telescoped Condensation with Diversely Functionalized 1,2‐Dicarbonyls

The development of materials for efficient chemoselective extraction of minor actinides remains at the forefront of research efforts in the area of separation science. Lewis basic complexants derived from nitrogen‐donor scaffolds are often employed in this area due to favorable complexation with the transuranic element americium. In the present work an efficient procedure for the preparation of eight useful 3‐pyridin‐2‐yl‐1,2,4‐triazines (2 novel) is demonstrated via telescoped condensation with the requisite 1,2‐dicarbonyl in two‐pots without additives, differentially extractive work‐up procedures, or recrystallization. Additional efforts in this area have demonstrated the utility of polar aprotic solvents for the preparation of nine functionalized pyridinyl‐2,6‐bis‐1,2,4‐triazines (4 novel) directly from the requisite 2,6‐pyridine dicarbonitrile in 49–99% yield over four total steps. The streamlined preparation of these important materials and detailed synthetic procedures is reported herein.     

Theoretical exploration on the vibrational and mechanical properties of M3C2/M3C2T2 MXenes

MXenes have attracted intensive attention in chemistry and material science for their special structures and properties. In order to understand the basic physical properties of the M₃C₂/M₃C₂T₂ (MSc, Ti, V, Cr, Zr, Nb, Mo, Hf, Ta, W; TF, O, OH) MXenes, first-principles calculations are carried out to investigate the structural, vibrational, and mechanical properties in this work. Both the metal atoms and surface groups can significantly influence the configurations or mechanical behaviors of the MXenes. The dehydrogenation tendency is calculated to evaluate the possible forms of the M₃C₂(OH)₂ toward M₃C₂O₂. The work functions of MXenes functionalized by different groups are compared, and the lower work functions for the  OH functionalized ones, which can be as low as 1.358 eV for the Sc₃C₂(OH)₂, suggest potential good performance in electron emission. In addition, the stability, mechanical properties, and the Raman and infrared (IR) activity modes of the MXenes are reported. Generally, functionalized MXenes would present smaller lattice parameters, lower free energies, and stronger mechanical strength compared to their counterparts. The data obtained may provide important theoretical ground for the investigations of the applications of MXenes.     

Unsaturated polyester resins modified with phosphorus-containing groups: Effects on thermal properties and flammability

A novel reactive phosphorus-containing monomer [1-oxo-2,6,7-trioxa-1- phosphabicyclo-[2.2.2]octane-methyl diallyl phosphate, PDAP] was synthesized, and various amounts of PDAP were combined with unsaturated polyester by radical bulk polymerization. The resulting flame-retardant unsaturated polyester resin (FR-UPR) samples were investigated by thermogravimetric analysis (TGA), microscale combustion calorimetry (MCC), and limiting oxygen index (LOI) tests. Due to the relatively high phosphorus content of PDAP (18.2 wt%), incorporation of this monomer into unsaturated polyester resin (UPR) led to a marked decrease in the heat release capacity (HRC), the total heat release (THR), an increase in the LOI and the char yield upon combustion. In order to elaborate the interactions between the UPR and PDAP in degradation, differences between the experimental and theoretical mass losses of a FR-UPR sample were evaluated. Furthermore, thermogravimetry-Fourier transform infrared (TG-FTIR) and real-time Fourier transform infrared (RTIR) spectroscopy were employed to investigate the degradation behavior of UPRs, providing insight into the degradation mechanism.     

Natural rubber–based composites filled with bioglasses from a CaO‐SiO2‐P2O5‐Ag2O system. Effect of Ag2O concentration in the filler on composite properties

Bioactive glass was first synthesized by L. Hench in 1971. There are many studies on the properties of several metals and metal ions dopants used in the SiO₂‐CaO‐P₂O₅ system of bioglasses, such as Ag, Cu, Zn, and Fe. A number of authors have carried out research related to the influence of silver oxide on the properties of bioglasses . However, publications on the properties of elastomer‐based composites containing bioactive glasses are relatively scarce. We have not found in the literature studies discussing how silver oxide concentration in bioglasses of the CaO‐SiO₂‐P₂O₅‐Ag₂O system affects the significant properties of a natural rubber biocomposite. In this regard, the purpose of the present work is to investigate the aforementioned influence on the properties of this type of composites, namely, vulcanization, physicomechanical, thermal, dynamic, dielectric, electric, and thermoconductive characteristics. We have established those parameters of the composites to be impacted considerably by both degree of filling with bioglass and the silver oxide content in the latter. The improvement in the composites thermostability and some of their physicomechanical performance is the most significant. The volume resistance decreases, and the thermal conductivity coefficients increase. Results from scanning electron microscopy and energy‐dispersive X‐ray (EDX) analyses have confirmed the influence of silver oxide initially on the phase composition of the bioglass, hence on the properties of the biocomposites through changes in the bioglass used as filler. The dielectric characteristics of some of the biocomposites suggest that they can be used as substrates and insulating layers in flexible antennas for short‐range wireless communications.