Synthesis and Characterization of Mono‐, Di‐, and Tetranitrated 7,8‐Disubstituted Glycolurils

Three 7,8‐disubstitited glycolurils were synthesized and subjected to various nitration conditions yielding the corresponding mono‐, di‐, and tetranitro derivatives. Prior to their synthesis, these nitrated compounds were evaluated computationally to determine their densities and heats of formation, from which explosive performance was predicted. Details on the methods used for the synthesis as well as the results from their computational analysis are discussed.     

Eu‐, Tb‐, and Dy‐Doped Oxyfluoride Silicate Glasses for LED Applications

Luminescence glass is a potential candidate for the light‐emitting diodes (LEDs) applications. Here, we study the structural and optical properties of the Eu‐, Tb‐, and Dy‐doped oxyfluoride silicate glasses for LEDs by means of X‐ray diffraction, photoluminescence spectra, Commission Internationale de L'Eclairage (CIE) chromaticity coordinates, and correlated color temperatures (CCTs). The results show that the white light emission can be achieved in Eu/Tb/Dy codoped oxyfluoride silicate glasses under excitation by near‐ultraviolet light due to the simultaneous generation of blue, green, yellow, and red‐light wavelengths from Tb, Dy, and Eu ions. The optical performances can be tuned by varying the glass composition and excitation wavelength. Furthermore, we observed a remarkable emission spectral change for the Tb³⁺ single‐doped oxyfluoride silicate glasses. The ⁵D₃ emission of Tb³⁺ can be suppressed by introducing B₂O₃ into the glass. The conversion of Eu³⁺ to Eu²⁺ takes place in Eu single‐doped oxyfluoride aluminosilicate glasses. The creation of CaF₂ crystals enhances the conversion efficiency. In addition, energy transfers from Dy³⁺ to Tb³⁺ and Tb³⁺ to Eu³⁺ ions occurred in Eu/Tb/Dy codoped glasses, which can be confirmed by analyzing fluorescence spectra and energy level diagrams.     

Synthesis of 3′,4′‐disubstituted terthiophenes. Characterization and electropolymerization. I. 3′,4′‐dibromo‐2,2′:5′,2″‐terthiophene in photovoltaic display

Recent studies on conducting polymers have demonstrated that polymers of 3‐substituted thiophene produce very stable compounds. Although this kind of substitution improves the regularity, structural defects still exist. To overcome this drawback, the polymerization of 3,4‐disubstituted thiophene is proposed as a convenient way of synthesizing regular, highly conjugated conductive polymers. Our interest is thus focused on the synthesis of tetra‐substituted thiophene derivatives, their polymerization, electrochemical properties, spectral characteristics, oxidizing potential, and the feasibility of photocells development. In this article, we report the synthesis and characterization of 3′,4′‐dibromo‐2,2′:5′,2″‐terthiophene which, as such or modified, may be a good starting product for obtaining new monomers of 3′,4′‐disubstituted terthiophenes, that would allow the effect of the substituents on the properties of the respective polymers to be studied. In addition, the monomer was electropolymerized and the resulting deposit was electrochemically and morphologically characterized. Two conclusions were drawn: first, more uniform and homogeneous layers than those of polythiophene are obtained; second, the thin layers of the polymer, electron acceptors, absorb in the visible. Finally, photocells were assembled to investigate their photovoltaic effect. Although the so prepared solar cells showed some photovoltaic effect, the yield was low.© 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 5314–5321, 2006     

Biodegradation of 2‐, 3‐ and 4‐iodobenzoic acids

The biodegradation of 2‐iodobenzoic acid (2IBA), 3‐iodobenzoic acid (3IBA) and 4‐iodobenzoic acid (4IBA) was investigated. Substrate disappearance was monitored in conjunction with product formation (ie iodide production) in order to verify complete mineralisation. Samples from SmithKline Beecham (SB) Wastewater Treatment Plants (WWTP) were employed to test their ability to degrade the iodinated aromatics listed above. Complete mineralisation of 3IBA was observed and the initial pathway(s) of biotransformation (via hydroxybenzoic acid formation) was proposed based on the comparison with standards of metabolites previously elucidated for similar halogenated benzoic acids. Evidence for co‐metabolism of 4IBA was observed since biodegradation only occurred in the presence of 3IBA. No evidence of biodegradation of 2IBA was observed over a period of 20 days, neither when fed individually nor as a mixture of substrates. © 1999 Society of Chemical Industry     

Conductivity Studies of Silver‐, Potassium‐, and Magnesium‐Doped Hydroxyapatite

We report the electrical transport properties of silver‐, potassium‐, and magnesium‐doped hydroxyapatites (HAs). While Ag+ or K⁺ doping to HA enhances the conductivity, Mg⁺² doping lowers the conductivity when compared with undoped HA. The mechanism behind the observed differences in ionic conductivity has been discussed using the analysis of high‐temperature frequency‐dependent conductivity data, Cole–Cole plots of impedance data as well as on the basis of the frequency dependence of the imaginary part (M″) of the complex electric modulus. The f_max of modulus M″ decreased in silver‐ and potassium‐doped samples in comparison with the undoped HA.     

Development of Fe‐, Sb‐, Bi‐ and Al‐impregnated silica catalysts using rice husk silica as a support for Friedel–Crafts benzylation of arenes

The milling by‐product of rice, rice husk, constitutes a major waste of the agricultural industry. It is mainly used as a fuel additive for various purposes, leaving behind residual ash which is rich in silica (Biogenic silica). In the present project, rice husk silica was impregnated with Fe³⁺, Sb³⁺, Bi³⁺ and Al³⁺ from both their aqueous and organic solutions. The resultant catalysts were activated at 120 °C and 550 °C and used for the Friedel–Crafts benzylation of benzene using benzyl chloride. Copyright © 2003 Society of Chemical Industry     

Composition‐Dependent Microstructures and Properties of La‐, Zn‐, and Cr‐Modified 0.675BiFeO3–0.325BaTiO3 Ceramics

Pure and 1.0 mol% La₂O₃, ZnO, and Cr₂O₃‐modified 0.675BiFeO₃–0.325BaTiO₃ (BF–BT) multiferroic ceramics were prepared and comparatively investigated. For pure and La‐, Zn‐, and Cr‐modified BF–BT, the average grain size is 415, 325, 580, and 395 nm, and the maximum dielectric constant temperature is 460°C, 430°C, 465°C, and 445°C, respectively. All additives weaken the ferroelectricity slightly. Zn‐ and Cr‐modifications dramatically enhance the room‐temperature magnetic properties, whereas La‐modification has almost no effect on magnetic property. Especially, the Cr‐modified BF–BT ceramics show switchable polarization and magnetization of 4.9 μC/cm² and 0.27 emu/g at room temperature, the magnetoelectric coupling is confirmed by the magnetization‐magnetic field curves measured on ceramics before and after electric poling. The mechanism responsible for the different effects of additive on microstructures and properties are discussed based on additive‐induced point defect and second phase as well as diffusion‐induced substitution. These results not only provide a promising room‐temperature multiferroic material candidate, but also are helpful to design new multiferroic materials with enhanced properties.     

Polyurethane coatings from liquefied wood containing remains of a copper‐, chromium‐, and boron‐based wood preservative

Preparation of polyurethane wood coatings based on copper‐, chromium‐, and boron (CCB) containing liquefied wood was performed, as an alternative way to manage postconsumed preservative‐contaminated wood. Additionally, we examined the possibility of improvement of selected properties of the liquefied wood‐based coatings by an addition of silica nanoparticles. The constituents of the CCB wood preservative do not exhibit an influence on a liquefaction process and on composition of the liquefied mixture. CCB also does not affect curing of the formulations containing liquefied wood and an isocyanate‐type hardener. Furthermore, influence of CCB on adhesion strength of liquefied wood‐based coatings on a wooden substrate, their hardness, and resistance to scratching and to water, acetone, and alcohol, is not exhibited. However, apart from these, from the applicative point of view, positive results, any improvement of the coating properties by the addition of silica nanoparticles is not shown. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40865.     

Mono‐, Di‐ and Tetra‐Cationic Surfactants as Carbon Steel Corrosion Inhibitors

Corrosion inhibition of three new synthesized cationic surfactants, N‐(2‐(((Z)‐4‐(pyridin‐4‐yl)but‐3‐en‐1‐yl)amino)ethyl)‐N‐(2‐((E)‐(pyridin‐4‐ylmethylene)amino)ethyl)dodecan‐1‐aminium bromide I(4N), N¹,N²‐didodecyl‐N¹‐((Z)‐4‐(pyridin‐4‐yl)but‐3‐en‐1‐yl)‐N²‐(2‐((E)‐(pyridin‐4‐ylmethylene)amino)ethyl)ethane‐1,2‐diaminium bromide II(4N) and 1‐dodecyl‐4‐((E)‐((2‐(dodecyl(2‐(dodecyl((Z)‐4‐(1‐dodecylpyridin‐1‐ium‐4‐yl)but‐3‐en‐1‐yl)ammonio)ethyl)ammonio)ethyl)imino)methyl)pyridin‐1‐ium bromide IV(4N) on carbon steel was investigated by weight loss, electrochemical impedance spectroscopy and polarization measurements. Results show that the synthesized cationic surfactants inhibit corrosion of carbon steel in 1 M HCl. The inhibitive action occurs by virtue of adsorption on the metal surface following a Langmuir adsorption isotherm model. Polarization curves reveal that the investigated cationic surfactants can be classified as mixed inhibitor types. The variations in the corrosion inhibition efficiency between three cationic surfactants are correlated with their chemical structures, with more hydrophobic surfactants yielding higher inhibition efficiency.     

Asymmetric Vinylogous Michael Addition/Cyclization Cascade Reaction for the Construction of Diversely Structured Spiro‐ Oxindole Skeletons

We present the first organocatalytic asymmetric vinylogous Michael/cyclization reaction of α,α‐dicyanoalkenes with 3‐alkylideneoxindoles. A series of diversely structured spiro‐oxindole skeletons was smoothly delivered with excellent yields and stereoselectivity control (94–99% yields, >20:1 dr and 91 to >99% ee).

     

Crystallography and Structure–Property Relationships of 2,2″,4,4′,4″,6,6′,6″‐Octanitro‐1,1′ : 3′,1″‐Terphenyl (ONT)

An X‐ray crystallographic study of 2,2″,4,4′,4″,6,6′,6″‐octanitro‐1,1′ : 3′,1″‐terphenyl (ONT) has been carried out. The dihedral angles between benzene rings vary from 84.9° to 89.4°. Nonbinding interatomic distances of oxygen atoms inside all the nitro groups are shorter than the intermolecular contact radii for oxygen. On the basis of the DFT B3LYP/6‐31(d, p) method it was found that the difference between the X‐ray structure in the solid phase and DFT result for the gas phase is 98 kJ mol⁻¹, and the bearer of the highest initiation reactivity of the ONT molecule in the solid phase should be the nitro group at 4″‐position, in contrast to those at 4′‐ or 6′‐position that play this role in the isolated molecule. It has been stated that the nitro groups at the reaction centers of the ONT molecule are relatively well specified by their ¹⁵N NMR chemical shifts.     

Near white light emission of Ce3+‐, Ho3+‐, and Sm3+‐doped oxyfluoride silicate glasses

The Ce³⁺‐, Ho³⁺‐, and Sm³⁺‐ single and co‐doped oxyfluoride silicate glasses for light emitting diodes are studied. These glasses were prepared by melt quenching method and their optical and structural properties were investigated by absorption spectra, photoluminescence spectra, Commission International de I'Eclairage chromaticity coordinates, X‐ray diffraction, and Fourier transform infrared spectra. It is found that the introduction of Al₂O₃ in glass composition can improve the emissions of Ho³⁺ and Sm³⁺. While the presence of B₂O₃ has the adverse effect and can suppress the emissions of Ho³⁺ and Sm³⁺. With substituting Na₂O for CaO in the glass compositions, CaF₂ crystals can be formed during the melt quenching process. We find the formation of CaF₂ crystals can change the emission behavior of Ho³⁺ and Sm³⁺ ions. White light emissions can be achieved in the glasses and the luminescence colors can be tuned by varying the concentrations of the doped rare‐earth ions and the composition of glass matrix. The Ce³⁺‐, Ho³⁺‐, and Sm³⁺‐doped oxyfluoride silicate glasses presented here demonstrate promising applications in the fields of light emitting diodes.     

Preparation of quadruple responsive polymeric micelles combining temperature‐, pH‐, redox‐, and UV‐responsive behaviors and its application in controlled release system

A novel series of quadruple responsive copolymers, poly(ethylene glycol)‐ss‐[poly(dimethylaminoethyl methacrylate)‐co‐poly(2‐nitrobenzyl methacrylate)] [PEG‐ss‐(PDMAEMA‐co‐PNBM)], were synthesized via atom transfer radical polymerization mediated by home‐made PEG‐based macro‐initiator labeled with disulfides. The obtained copolymers could self‐assemble in aqueous solution forming micelles with the disulfide bridge linking the hydrophilic coronas (PEG) and the hydrophobic cores (PDMAEMA‐co‐PNBM). Investigation on the resulted micelles indicated that the micelles could respond to various stimuli, that is, temperature, pH, the presence of dithiothreitol (DTT), and UV irradiation. Moreover, the responsive behavior of the micelles depends on the type of stimuli, that is, temperature change causes size change of the micelles, while UV irradiation leads to dissolution of the self‐assembled structures. Such stimulus‐dependent responsive behavior could be applied in smart materials that deal with multi‐tasks or in the construction of complex logic gate. The potential application of the multi‐responsive micelles in cargo release system was also evaluated using Nile Red (NR) as model molecule. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46675.     

Synthesis and Antiviral Evaluation of TriPPPro‐AbacavirTP,TriPPPro‐CarbovirTP,and Their 1′,2′‐cis‐Disubstituted Analogues

Herein we describe the synthesis of lipophilic triphosphate prodrugs of abacavir, carbovir, and their 1′,2′‐cis‐substituted carbocyclic analogues. The 1′,2′‐cis‐carbocyclic nucleosides were prepared by starting from enantiomerically pure (1R,2S)‐2‐((benzyloxy)methyl)cyclopent‐3‐en‐1‐ol by a microwave‐assisted Mitsunobu‐type reaction with 2‐amino‐6‐chloropurine. All four nucleoside analogues were prepared from their 2‐amino‐6‐chloropurine precursors. The nucleosides were converted into their corresponding nucleoside triphosphate prodrugs (TriPPPro approach) by application of the H‐phosphonate route. The TriPPPro compounds were hydrolyzed in different media, in which the formation of nucleoside triphosphates was proven. While the TriPPPro compounds of abacavir and carbovir showed increased antiviral activity over their parent nucleoside, the TriPPPro compounds of the 1′,2′‐cis‐substituted analogues as well as their parent nucleosides proved to be inactive against HIV.     

Crystallography and Structure–Property Relationships in 2,2′,2″,2′′′,4,4′,4″,4′′′,6,6′,6″,6′′′‐Dodecanitro‐1,1′ : 3′1″ : 3″,1′′′‐ Quaterphenyl (DODECA)

X‐ray crystallographic study of 2,2′,2″,2′′′,4,4′,4″,4′′′,6,6′,6″,6′′′‐dodecanitro‐1,1′ : 3′1″ : 3″,1′′′‐quaterphenyl (DODECA) has been carried out. Nonbonding interatomic distances of oxygen atoms inside of all the nitro groups are shorter than those corresponding to the intermolecular contact radii for oxygen. By means of the DFT B3LYP/6‐31(d, p) method a difference of 136 kJ mol⁻¹ between the X‐ray and DFT structures of DODECA was found. The bearer of the highest initiation reactivity in its molecule in solid phase should be the nitro group at 4′′′‐position, in contrast to those at 2′‐ or 2″‐positions in its isolated molecule. The most reactive nitro group in the DODECA molecule can be well specified by the relationship between net charges on nitro groups and charges on their nitrogen atoms, both of them for the X‐ray structure. The ¹⁵N chemical shift, corresponding to this nitro group for the initiation by impact and shock, correlates very well with these shifts of the reaction centers of the other six “genuine” polynitro arenes.     

Investigating the acoustical properties of carbon fiber‐, glass fiber‐, and hemp fiber‐reinforced polyester composites

Wood is one of the main materials used for making musical instruments due to its outstanding acoustical properties. Despite such unique properties, its inferior mechanical properties, moisture sensitivity, and time‐ and cost‐consuming procedure for making instruments in comparison with other materials (e.g., composites) are always considered as its disadvantages in making musical instruments. In this study, the acoustic parameters of three different polyester composites separately reinforced by carbon fiber, glass fiber, and hemp fiber are investigated and are also compared with those obtained for three different types of wood specimens called poplar, walnut, and beech wood, which have been extensively used in making Iranian traditional musical instruments. The acoustical properties such as acoustic coefficient, sound quality factor, and acoustic conversion factor were examined using some non‐destructive tests based on longitudinal and flexural free vibration and also forced vibration methods. Furthermore, the water absorption of these polymeric composites was compared with that of the wood samples. The results reveal that the glass fiber‐reinforced composites could be used as a suitable alternative for some types of wood in musical applications while the carbon fiber‐reinforced composites are high performance materials to be substituted with wood in making musical instruments showing exceptional acoustical properties. POLYM. COMPOS., 35:2103–2111, 2014. © 2014 Society of Plastics Engineers     

Surface Analysis of Cr2O3‐, CoO‐, and Al2O3‐Doped Iron–Phosphate Glasses at High Temperature

Surface structures of iron–phosphate glasses were examined using X‐ray photoelectron spectroscopy (XPS). Cr₂O₃, CoO, and Al₂O₃ were introduced to the glass by the replacement of a part of Fe₂O₃, and the simulated fission products are also added. The obtained glasses showed high chemical durabilities by MCC‐1 test. In situ high‐temperature and room‐temperature XPS measurements were conducted on the polished sample surfaces and also those after 1‐week chemical durability test. Unique trends were observed in XPS spectra on heating and after the chemical durability test, respectively. Nature of the glass surface of iron–phosphate glasses was explained from the point of view of surface energy, and the origin of high chemical durability and the effect of chromium ions were discussed based on the changes on surface composition and valence states of transition‐metal ions.     

Pyridin‐, Quinolin‐ and Acridinylidene Palladium Carbene Complexes as Highly Efficient C–C Coupling Catalysts

A series of four new complexes bearing N‐heterocyclic carbene ligands (NHCs) as well as four compounds bearing N‐heterocyclic carbene ligands with remote heteroatoms (rNHCs) of the general types [(NHC)(PPh₃)₂PdCl]⁺BF₄⁻ and [(rNHC)(PPh₃)₂PdCl]⁺BF₄⁻, respectively, have been prepared in high yields. Crystal and molecular structures have been determined for four representative examples. These compounds proved to be efficient catalysts for aryl coupling reactions of the Heck and Suzuki types (reaching TONs of as high as 6,200,000). Both aryl bromides and aryl chlorides can be used as substrates. Like the well known mixed, standard (NHC)(phosphine) compounds, the new six‐numbered, one‐N‐heterocyclic carbene complexes (and in particular certain rNHC‐containing ones) also combine the advantageous stability of bis(carbene) and the high activity of bis(phosphine) complexes. Furthermore, their good catalytic performance and, especially, their easy synthesis based on cheap and commercially available starting materials, make them by far superior when compared to the mixed (NHC)(phosphine) catalysts known thus far.     

Preparation of aldehyde‐, amino‐, and hydrazide‐functionalized polymer particles for direct immobilization of the sugars

The reaction of poly(vinyl alcohol) with glutaraldehyde (GA) at different molar ratio was systematically studied. By this reaction, white particles functionalized with aldehyde groups were obtained and their diameters were found to be between 50 and 150 nm. The amount of free ? CHO groups on the surface of the particles reached more than 1.6 mmol/g by adjusting the ratio of n(GA)/n(? OH). The free ? CHO groups were then converted into alkyl amino, aromatic amino, and hydrazide groups by coupling with hexamethylene diamine, m‐phenylene diamine, and adipic dihydrazide, respectively, and the length of the spacer was also prolonged. Finally, a series of sugar‐particle conjugates were prepared by directly coating the functionalized particles with maltose, D ‐(+)‐glucosamine, and heparin. The anticoagulant experiments show that the heparin immobilized on the aldehyde‐ and hydrazide‐functionalized particles is still biologically active. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009