Synthesis and characterization of side-chain oxazoline–methyl methacrylate copolymers bearing azo-dye

We synthesized new polymeric structures by attaching a side-chain azo-moiety on poly(oxazoline) and poly(oxazoline-co-methyl methacrylate)s. For the polymer analogous transformation, we took advantage of the highly effective ring-opening addition of carboxyl group to the oxazoline cycle. The comonomers feed ratio allowed us to control the composition of the products while the kinetic treatment, employing an integral method, revealed a statistical copolymerization tendency of 2-isopropenyl-2-oxazoline with methyl methacrylate in acetonitrile at 70 °C. The elemental analysis and ¹H NMR spectroscopy provided almost identical composition data for both the substrates and the side-chain copolymers. The UV spectroscopy sustained the quantitative addition of 4-(4-hydroxy-3,5-dimethylphenylazo)benzoic acid to the oxazoline rings. Both the unmodified copolymers and the coloured ones exhibited good thermal stabilities, up to 371 °C and 302 °C, respectively. The glass transition temperatures ranged from 141.5 to 177.5 °C and from 153.8 to 200.9 °C for the substrates and for the modified copolymers, respectively. Preliminary investigations showed fluorescence activity for all copolymers bearing azo-moieties.     

Synthesis and characterization of molecularly imprinted polymers with metallic zinc center for enrofloxacin recognition

A molecularly imprinted polymer with a metallic center (MIPc) was prepared and characterized. The template molecule for MIPc was a complex [Zn(Aza-f)(Enr)]NO₃?H₂O, Com, based on the ligands: enrofloxacin (Enr) and azabis(oxazoline) functionalized with styrene. Com was characterized before preparing MIPc. Moreover, the polymer prepared via non-covalent (MIPe) was prepared using Enr as the template molecule while no template molecules were used to prepare the non-imprinted polymer (NIP).MIPc was characterized using different spectroscopic techniques. In addition, the polymer molecular recognition capacity was studied by using rebinding kinetic studies. The kinetics shows that MIPc reach the equilibrium before the MIPe and NIP and the amount of Enr adsorbed is approximately 5 times higher that MIPe and NIP.Scatchard plots analysis for NIP, MIPe and MIPc shows K_d = 0.4768, 0.020, 0.0067 (mmol L^?1) respectively. In comparison with the MIPe the binding affinity is nearly 100 times higher taking into account the high affinity sites. The selectivity of MIPc for Enr was higher than that for ofloxacin or flumequin, isotherms were fit to the Langmuir–Freundlich model, and the Enr showed a value of K_o = 21.38 mM^?1, while the ofloxacin had a value of 2.2 × 10^?8 mM^?1 and the flumequin of 1.6 × 10^?5 mM^?1.     

Microwave dielectric properties of Mn-doped BaO–(Nd0.7,Sm0.3)2O3–4TiO2 ceramic sintered in a reducing atmosphere

The effect of MnCO₃ doped from 0 to 55 mol% into BaO–(Nd_0.7Sm_0.3)₂O₃–4TiO₂ (BNST) sintered in a reducing atmosphere on the microstructure and electrical properties was studied. Mn³⁺ completely substituted into Ti⁴⁺-sites of BNST to form a solid solution, so there is no second phase until 42 mol% which is the maximum solubility. Mn (<42 mol%)-doped BNST sintered in a reducing atmosphere is in a semi-conducing state because the concentration of free electron is higher than that of the acceptors. On the other hand, when Mn content doped into BNST exceeds a critical value (>43 mol%), the second Mn-rich phase due to excess of Mn³⁺ substituted into Ti⁴⁺-site, corresponding to original BaO–(Nd_0.7Sm_0.3)₂O₃–4TiO₂ (1 1 4) phase, is formed. Mn (>43 mol%)-doped BNST sintered in a reducing atmosphere is in an insulating state because the concentration of the acceptors is higher than that of liberated free electron, so the insulation resistance becomes high and tan δ becomes low. The formation of the second Mn-rich phase affects Q × f factor and temperature coefficient of capacitance (T.C.C.) of BNST significantly.     

Synthesis and photoresponsive behavior of the high-Tg azobenzene polymers via RAFT polymerization

Well-defined photo-responsive alternating copolymers, poly(4-(N-maleimido)azobenzene-alt-styrene)s (PMSts), were successfully synthesized via reversible addition–fragmentation chain transfer (RAFT) polymerization. A divinyl monomer was used in this polymerization to prepare high molecular weight azobenzene polymers. These polymers had good solubility in most organic solvents, formed films well, and had high glass transition temperatures (T_g = 174–250 °C) and were heat resistant (T_d > 320 °C). The photo-induced trans–cis isomerization of the copolymers was examined in chloroform solution. Surface-relief-gratings (SRGs) formed on the polymer films were also investigated using illumination from a linearly polarized Kr⁺ laser beam.     

Microwave-enhanced catalytic degradation of phenol over nickel oxide

A mix-valenced nickel oxide, NiO_x, was prepared from nickel nitrate aqueous solution through a precipitation with sodium hydroxide and an oxidation by sodium hypochlorite. Further, pure nickel oxide was obtained from the NiO_x by calcination at 300, 400 and 500 °C (labeled as C300, C400 and C500, respectively). They were characterized by thermogravimetry (TG), X-ray diffraction (XRD), nitrogen adsorption at −196 °C and temperature-programmed reduction (TPR). Their catalytic activities towards the degradation of phenol were further studied under continuous bubbling of air through the liquid phase. Also, the effects of pH, temperature and kinds of nickel oxide on the efficiency of the microwave-enhance catalytic degradation (MECD) of phenol have been investigated. The results indicated that the relative activity affected significantly with the oxidation state of nickel, surface area and surface acidity of nickel oxide, i.e., NiO_x (>+2 and S_BET = 201 m² g⁻¹) ≫ C300 (+2 and S_BET = 104 m² g⁻¹) > C400 (+2 and S_BET = 52 m² g⁻¹) > C500 (+2 and S_BET = 27 m² g⁻¹). The introduction of microwave irradiation could greatly shorten the time of phenol degradation.     

High transition temperature shape memory polymers (SMPs) by telechelic oligomer approach

This work describes the synthesis and comparative shape memory properties of cross-linked networks derived from epoxy and cyanate ester monomers containing polyether oligomers as reactive shape memory segments. The hydroxy telechelic oligomers viz. polyethyleneglycol (PEG), polypropyleneglycol (PPG), and polytetramethyleneglycol (PTG) are reacted with epoxy–cyanate ester matrix resulting in shape memory polymers with high transition temperatures. The soft oligomer segments act as flexible linker unit which interconnect oxazolidone, isocyanurate and triazine ring structures in the cross-linked polymer. The resultant cyclomatrix SMPs exhibit high transition temperatures 132, 178 and 161 °C respectively for PEG, PPG and PTG integrated SMPs. The E_g/E_r ratios are increased in the order PEG < PTG < PPG. The PTG and PPG based SMPs show shape retention of 99% and shape recovery of >98% with recovery time <100 s. All the SMPs display good thermal stabilities (both inert and oxidative) above 275 °C.     

Extrusion of AlSBA-15 molecular sieves: An industrial point of view

AlSBA-15 in the powder form with different n_Si/n_Al ratios (45, 136 and 215) were synthesized by hydrothermal technique. The powdered materials were made into cylindrical extrudates with the addition of bentonite as a binder. The AlSBA-15 materials were characterized by XRD, N₂ adsorption, AAS and thermogravimetric analysis. The orderly growth of AlSBA-15 is evidenced by its XRD. The surface area of the powder catalyst is around 950 m²/g and that of extrudate is close to 600 m²/g. Vapor phase alkylation of phenol with tert-butanol was carried out over the extrudates of AlSBA-15 as a model reaction. The activity of AlSBA-15 extrudates follows the order: AlSBA-15 Si/Al = 45 > AlSBA-15 Si/Al = 136 > AlSBA-15 Si/Al = 215. The reaction products were found to be 2-TBP, 4-TBP and 2,4-DTBP. The selectivity to para tertiary butylation is higher than other reactions.     

Transesterification of leather tanning waste to biodiesel at supercritical condition: Kinetics and thermodynamics studies

Catalyst-free transesterification of leather tanning waste with high free fatty acid (FFA) content at supercritical condition was reported in this work. The experiments were performed in batch system at various temperatures (250–325 °C) under constant pressure of 12 MPa and methanol/fatty oil molar ratio of 40:1 for reaction time of 2–10 min. Kinetic modeling of formation of fatty acid methyl esters (FAMEs) that incorporate reversible esterification and non-reversible transesterification simultaneously was verified. The proposed semi-empirical model was fitted against kinetic experimental data over temperature range studied. The kinetic parameters (i.e. k′_TE, k′_E, and k_E′) were determined by nonlinear regression fitting. Thermodynamic activation parameters of the reactions were evaluated based on activation complex theory (ACT) and the following results are obtained: ΔG³ > 0, ΔH³ > 0, and ΔS³ < 0. The activation energy (E_a) of transesterification, forward and reverse esterification reactions was 36.01 kJ/mol, 28.38 kJ/mol, and 5.66 kJ/mol, respectively.     

Synthesis and chemosensory properties of terpyridine-containing diblock polycarbazole through RAFT polymerization

This paper describes the synthesis of a terpyridine-containing diblock copolymer, poly(N-vinylcarbazole)-block-poly[4′-((4-vinylphenyl) phenyl)-2,2′:6′,2″- terpyridine] (poly(VK₁₅-b-TPY₄)), using the macro-chain transfer agent VK macro-CTA, and employing two-step reverse addition-fragmentation transfer (RAFT) polymerization. We examined the effect of terpyridine units on sensory characteristics of fluorescent chemosensors. VK macro-CTA and diblock copolymer poly(VK₁₅-b-TPY₄) both exhibited moderate thermal stability, with thermal decomposition temperatures of 5% weight losses at approximately 307 °C and 378 °C, respectively, suggesting that the enhancement of thermal stability was attributed to the incorporation of terpyridine segments into the block copolymer. Poly(VK₁₅-b-TPY₄) exhibited higher sensitivities to Ni^2 + and Mn^2 + ions, with Stern–Volmer constants (K_sv) of 2.58 × 10⁵ M^− 1 and 2.57 × 10⁵ M^− 1, respectively. Adding a Zn^2 + ion not only caused partial fluorescence enhancement (3.2-fold quantum efficiency) but also induced a bathochromic shift of emission peak by approximately 56 nm (from 429 nm to 485 nm), indicating that the Zn^2 +-terpyridine complex reduced the twist and vibration of the C–C polymer backbone and enhanced the charge transfer from donors to acceptors because of the more planar and rigid structure. Our results suggest that poly(VK₁₅-b-TPY₄) is a promising material for chemosensory applications.     

Thermal inactivation of airborne viable Bacillus subtilis spores by short-term exposure in axially heated air flow

In this investigation, an experimental facility was developed for quantifying the inactivation of viable bioaerosol particles in a controlled axially heated air flow. The tests were conducted with Bacillus subtilis var. niger endospores. The thermal inactivation of aerosolized spores was measured based on the loss of their culturability that resulted from a short-term exposure to air temperatures ranging from ～150 to >1000 °C. The cross-sectional and longitudinal temperature profiles in the test chamber were determined for different heating and flow conditions. The characteristic exposure temperature (T_e) was defined using a conservative approach to assessing the spore inactivation. Experimentally determined inactivation factors (IF) were corrected to account for the temperature profiles in the axially heated air flow. The reported IF-values serve as the lower approximation of the actual inactivation. Two data sets obtained at different flow rates, Q=18 and 36 L min^?1, represent different exposure conditions. In both cases, the thermal exposure of aerosolized spores produced no effect or only a moderate inactivation when the T_e remained below ～200 °C for 18 L min^?1 and ～250^oC for 36 L min^?1. The IF-values increased exponentially by about four orders of magnitude as the temperature rose by 150 °C. Depending on the flow rate, IF exceeded ～10⁴ at T_e>320 °C (Q=18 L min^?1) or >360 °C (Q=36 L min^?1). At T_e≈375–400 °C, the spore inactivation obtained at both flow rates reached the limit of quantification established in this study protocol, which translates to approximately 99.999% viability loss. The findings were attributed primarily to the heat-induced damage of DNA and denaturation of essential proteins. Up to a certain level of the thermal exposure, these damages are repairable; however, the self-repair capability diminishes as the heat rises and then the damage becomes totally irreversible. The data generated in this study provide an important reference point for thermal inactivation of stress-resistant spores in various biodefense/counterterrorism and air quality control applications.     

Surface acidity study of Mn+-montmorillonite clay catalysts by FT-IR spectroscopy: Correlation with esterification activity

A simple method for evaluating the surface acidity of different cation-exchanged montmorillonite (mont) clay catalysts, Mⁿ⁺-mont (Mⁿ⁺=Al³⁺, Fe³⁺, Cr³⁺, Zn²⁺, Ni²⁺, Cu²⁺, and H⁺), involving treatment with pyridine is described. After treating with pyridine, the samples were heated at 120 °C and the FT-IR spectra were directly recorded in the region 1650 and 1350 cm⁻¹. The data obtained show the presence of both Lewis and Brønsted acid sites. The activities of the catalysts to bring about Brønsted acid catalysed esterification of succinic acid with iso-butanol to yield di-(iso-butyl) succinate have been studied. The Brønsted acidity data obtained for Mⁿ⁺-mont correlated well with activity in the esterification reaction. The activities of the catalysts were found to decrease in the order of exchange ions Al³⁺ > Fe³⁺ > Cr³⁺ > Zn²⁺ > Ni²⁺ > Cu²⁺ > Na⁺-mont. They also correlated well with the charge to radius ratio of the cations. The catalysts exchanged with trivalent cations showed stronger absorption bands attributed to Brønsted acidity (1540 cm⁻¹) whereas those exchanged with divalent cations showed an increased Lewis acidity (1450 cm⁻¹) and reduced Brønsted acidity along with charge to radius ratio. Zn²⁺-, Cu²⁺- and Ni²⁺-exchanged clays showed an additional peak around 1605 cm⁻¹ which is attributed to the pyridine adsorption on surface sites through its π electrons. The method suggested here to evaluate the acidity is suitable for active sites which are thermally unstable such as water molecules in the hydration shell of a cation in exchanged clay.     

A novel organocatalyst for direct asymmetric Michael additions of cyclohexanone to nitroolefins

A novel catalyst combining pyrrolidinyl and cyclohexanediamine was designed and synthesized. Only 5 mol% of catalyst loading was required for enantioselective Michael additions of cyclohexanone and nitroolefins affording desired γ-nitroketones with > 99% yield, up to 91% ee and up to > 99/1 dr under mild conditions. The enantioselectivity of the product could be further improved to > 99% ee after a single recrystallization in petroleum ether/ethyl acetate.     

Synthesis and optical properties of a series of thermally stable diphenylanthrazolines

A series of diphenylanthrazolines were synthesized by Friedländer condensation of 2,5-dibenzoyl-1,4-phenylenediamine and acetyl-functionalized compounds in the presence of polyphosphoric acid as catalyst, in yields ranging from 61% to 88%. The diphenylanthrazolines are thermally robust with high decomposition temperatures (>380.0 °C) and high melt transitions (317–462 °C). All of them show the lowest energy absorption bands (λ_max^Abs: 394–433 nm) from the π–π¹ transitions by virtue of their large molar extinction coefficients (? ≈ 10⁴ M^?1 cm^?1), revealing low optical band gaps (2.59–2.80 eV). The compounds emit blue fluorescence with λ_max^Em ranging from 430 to 466 nm in dilute toluene solution.     

Thermal degradation of rice straw fibers: Global kinetic modeling with isothermal thermogravimetric analysis

Thermal degradation behavior of rice straw fibers under isothermal heating conditions was studied. The data were modeled by considering the fiber as one pseudo-component using the Málek method. The kinetic model with reaction order n > 1 [i.e., RO(n > 1) = (1 ? α)ⁿ] described the degradation process of rice straw fiber fairly well in a temperature range up to about 265 °C. The kinetic parameters used include activation energy of 116 ± 5 kJ/mol, reaction order of 3.0 ± 0.2, and logarithmic value of pre-exponential factor [ln A] of 18.7 ± 0.1 ln s^?1. The model obtained can be used to aid the development of straw fiber-engineering plastic composites.     

Synthesis and characterization of a cross-linkable nonlinear optical polymer functionalized with a thiophene- and tricyanovinyl-containing chromophore

This paper reports a novel nonlinear optical polymer BP-AVT-TCV functionalized with a thiophene- and tricyanovinyl-substituted chromophore. BP-AVT-TCV was synthesized by the post-tricyanovinylation of an epoxy-based precursor polymer BP-AVT, and had a high molar functionalization degree of chromophore (70 mol.%). It had an enhanced glass transition temperature (T_g = 164 °C) compared with BP-AVT (T_g = 114 °C), and a high decomposition temperature (T_d,5% = 295 °C). BP-AVT-TCV was further cross-linked to achieve the three-dimensional (3D) network of thermosetting polyurethane (PU). The poled PU films revealed an electro-optic (EO) coefficient (γ₃₃) value of 21 pm/V at a wavelength of 1315 nm. The structures of the polymers were confirmed by FT-IR, UV–Vis, and ¹H NMR spectra.     

Electrochromic performance and ion sensitivity of a terthienyl based fluorescent polymer

A novel terthienyl based fluorescent polymer bearing strong electron-withdrawing substituents directly attached to the 3,4-positions of the central thiophene ring was synthesized by electrochemical polymerization of diethyl 2,5-di(3,4-ethylenedioxythiophen-2-yl)thiophene-3,4-dicarboxylate. The corresponding polymer was characterized by cyclic voltammetry, FT-IR and UV–vis spectroscopy. The polymer has a well-defined redox process (E_p,1/2 = 0.74 V) and demonstrates a reversible electrochromic behavior; lilac in the neutral state and transparent sky blue in the oxidized state. Also, the polymer had low band gap (E_g = 1.82 eV) and high redox stability (retaining 94.0% of its electro-activity after 500th switch). Moreover, the sensitivity of both the monomer and its polymer towards metal cations was investigated by monitoring the change in the fluorescence intensity. Among various common ions both the monomer and its polymer were found to be selective towards Cu²⁺ and Cu⁺ ions by quenching the fluorescence efficiency with a Stern–Volmer constant (K_sv) of (1.4–1.6 × 10³ M^?1) and (1.5–1.8 × 10² M^?1) for monomer and polymer solutions, respectively.     

Association phenomena of a chiral perylene derivative in solution and in poly(ethylene) dispersion

In this work, the aggregation behaviour of a chiral perylene derivative, that is, N,N′-bis-(R)-(1′-phenylethyl)-perylene-3,4,9,10-tetracarboxyldiimide (R-Pery), was studied by means of ¹H NMR (including DOSY techniques), circular dichroism, UV–Vis and fluorescence spectroscopies in various conditions. The acquired data demonstrate that R-Pery tends to aggregate in pure solvents at high concentrations (>10^?5 M in DMSO and >10^?3 M in CHCl₃), whereas aggregation occurred at lower concentrations by adding a poor solvent, such as water (to DMSO) or CH₃CN (to chloroform). Interesting results were obtained studying the optical behaviour of R-Pery when dispersed into a linear low-density polyethylene matrix (LLDPE). In particular, the aggregation extent of R-Pery into LLDPE was investigated by means of UV–Vis, fluorescence and CD spectroscopies as a function of dye concentration as well as thermal stimuli. The optical responsiveness of R-Pery (both in absorption and in emission) versus moderate temperature changes (i.e., for T > 35 °C) suggests applications of polymer dispersions as smart and reversible indicators to thermal solicitations.     

High-yield exfoliation of graphite in acrylate polymers: A stable few-layer graphene nanofluid with enhanced thermal conductivity

High-yield exfoliation of pristine graphite in low boiling point alcohols was achieved using a set of acrylate polymers resulting in few-layer graphene concentrations of up to ∼4 mg mL⁻¹. The polymer showed superior dispersing capabilities for graphene compared to the best reported dispersants, including the solvent N-methyl-pyrrolidone, the surfactants sodium cholate and sodium taurodeoxycholate, and the polymer polyvinylpyrrolidone. The dispersions were stable regardless of freezing (−26 °C) or heating (70 °C) for 24 h, or dilution with water up to 80% volume ratio over 160 h. The as-obtained nanofluid exhibited an enhancement in thermal conductivity suggesting a great potential in coolant applications.     

Poly[bis(2-aminophenyloxy)disulfide]: A polyaniline derivative containing disulfide bonds as a cathode material for lithium battery

A new conductive polyaniline derivative containing disulfide bonds, poly[bis(2-aminophenyloxy)disulfide] (PAPOD), has been proposed as a high energy-storage material. PAPOD has been synthesized using a moderate oxidant ferric chloride and characterized by elemental analysis, X-ray photoelectron spectroscopy (XPS), FT-IR, FT-Raman, and UV–vis spectroscopy. The cyclic voltammograms of this polymer show that the intramolecular self-catalysis occurs between the conductive main-chain polyaniline (doping/undoping processes of the π-conjugated system) and side-chain disulfide bonds (scission/reformation processes of the S–S bonds) in PAPOD. Because the redox reaction of conductive main-chain polyaniline occurs in the same potential range as that of the side-chain disulfide bonds of this polymer, the Li/PAPOD test cell displays a charge capacity of 230 mAh g⁻¹-cathode and an energy density of 460 mWh g⁻¹-cathode, which is about 2–3 times higher than those of inorganic intercalation compounds.     

Synthesis and ion responsiveness of optically active polyacetylenes containing salicylidene Schiff-base moieties

Acetylenic monomers containing salicylidene Schiff-base groups (1a and 1b) as well as Schiff-base and hydroxy groups (1c) were synthesized and polymerized with [(nbd)RhCl]₂/Et₃N catalyst to afford the corresponding polymers 2a–c with high molecular weights (M_n = 2.6–7.2 × 10⁵) in high yields (75–97%). Polarimetric, circular dichroism (CD), and UV–vis spectroscopic analyses indicated that the polymers formed helical structures with a predominantly one-handed screw sense. The addition of metal ions to salicylidene Schiff-base-containing polymers 2a and 2b produced insoluble polymer/metal complexes through ionic cross-linking as a result of salicylaldimine–metal ion complexation. Polymers 2b and 2c underwent a helix–coil transition upon the addition of HSO₄⁻, whereas these polymers did not exhibit responsiveness to other anions, such as F⁻, Cl⁻, and Br⁻.