Carprofen-imprinted monolith prepared by reversible addition–fragmentation chain transfer polymerization in room temperature ionic liquids

To obtain fast separation, ionic liquids were used as porogens first in combination with reversible addition–fragmentation chain transfer (RAFT) polymerization to prepare a new type of molecularly imprinted polymer (MIP) monolith. The imprinted monolithic column was synthesized using a mixture of carprofen (template), 4-vinylpyridine, ethylene glycol dimethacrylate, [BMIM]BF₄, and chain transfer agent (CTA). Some polymerization factors, such as template-monomer molar ratio, the degree of crosslinking, the composition of the porogen, and the content of CTA, on the column efficiency and imprinting effect of the resulting MIP monolith were systematically investigated. Affinity screening of structurally similar compounds with the template can be achieved in 200 s on the MIP monolith due to high column efficiency (up to 12,070 plates/m) and good column permeability. Recognition mechanism of the imprinted monolith was also investigated.     

Polyacrylonitrile molecular weight effect on the structural and magnetic properties of metal–carbon nanomaterial

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The effect of activated fillers on the properties of styrene–acrylic adhesives

Results of kaolin modification by thermal activation, sonication and 3% solution of acetic acid are considered. It is shown that the introduction of thermally activated kaolin to compositions based on styrene–acrylic filming agents increases the adhesion characteristics by 1.25–1.4 times (for steel and cement–sand surfaces) and cohesive strength by 1.5–2 times.     

Polymethacrylamide—An underrated and easily accessible upper critical solution temperature polymer: Green synthesis via photoiniferter reversible addition–fragmentation chain transfer polymerization and analysis of solution behavior in water/ethanol mixtures

Within the group of stimuli-responsive, “smart” materials, upper critical solution temperature (UCST) polymers remain sparsely investigated. Thus, this work focusses on a vastly ignored UCST polymer: polymethacrylamide (PMAAm). A cost-efficient photoiniferter reversible addition–fragmentation chain transfer (RAFT) polymerization yielding narrowly dispersed (Đ < 1.1) PMAAm is presented. This PMAAm exhibits highly thermoreversible UCST-type phase transitions (PT) in water/ethanol mixtures (ethanol content: 17–35 wt%) which are investigated via temperature dependent dynamic light scattering (DLS). Apart from the ethanol content, the PT temperature is affected by polymer mass fraction and chain length and varies between 10–80 °C depending on the three mentioned parameters. Lastly, PMAAm's propensity towards amide hydrolysis and concomitant PT-suppression is investigated. Below temperatures of 40 °C, PMAAm solutions show no sign of amide hydrolysis for at least three days, however, if heated to 70 °C, the thermoresponsiveness gradually degrades within hours.     

Stabilization effect of potential antioxidants on the thermooxidative stability of styrene–butadiene rubber

Effects of several heterocyclic compounds containing nitrogen, trisubstituted amines and diamines and molecules based on N,N,N′,N′,N′′,N′′-substituted-[1,3,5]triazine-2,4,6-triamine in preventing thermooxidative degradation of styrene–butadiene rubber (SBR) have been studied using non-isothermal DSC measurements. The aim of this study was to determine and compare the stabilizing effect of individual compounds and to select the structures with the best antioxidative properties. In order to compare the stabilizing effect of the compounds, induction periods and protection factors have been calculated. The treatment of the experimental data was carried out using a method based on a non-Arrhenian temperature function. The results show that better antioxidative properties can be assigned to heterocyclic compounds. On the other hand, molecules containing triazine structures exhibited only negligible stabilizing effect on SBR at lower temperatures and even destabilizing effect at higher temperatures.     

Molecularly imprinted polymer coated solid-phase microextraction fiber prepared by surface reversible addition–fragmentation chain transfer polymerization for monitoring of Sudan dyes in chilli tomato sauce and chilli pepper samples

Surface reversible addition-fragmentation chain transfer (RAFT) polymerization method was firstly applied to the preparation of molecularly imprinted polymer (MIP) coated silicon solid-phase microextraction (SPME) fibers. With Sudan I as template, an ultra-thin MIP coating with about 0.55-μm thickness was obtained with homogeneous structure and controlled composition, due to the controllable radical growing and chain propagation in surface RAFT polymerization. The MIP-coated fibers were found with enhanced selectivity coefficients (3.0–6.5) to Sudan I–IV dyes in contrast with those reported in our previous work. Furthermore, the ultra-thin thickness of MIP coating was helpful to the effective elution of template and fast adsorption/desorption kinetics, so only about 18 min was needed for MIP-coated SPME operation. The detection limits of 21–55 ng L⁻¹ were achieved for four Sudan dyes, when MIP-coated SPME was coupled with liquid chromatography (LC) and mass spectrometry (MS) detection. The MIP-coated SPME–LC–MS/MS method was tested for the monitoring of ultra trace Sudan dyes in spiked chilli tomato sauce and chilli pepper samples, and high enrichment effect, remarkable matrix peaks-removing capability, and consequent high sensitivities were achieved to four Sudan dyes.     

A critical analysis of the effect of crosslinking on the linear viscoelastic behavior of styrene–butadiene rubber and other elastomers

The linear viscoelastic behavior in dynamic shear and tensile creep at temperatures from −30 to 70 °C is measured for an styrene–butadiene rubber (SBR) elastomer cured with dicumyl peroxide to crosslinking densities between 0 and 23.5 × 10⁻⁵ mol/cm³. The G′, G″, and tan δ isotherms are analyzed by time–temperature superposition (TTS), where the tan δ master curves are consistent with those of Mancke and Ferry. However, to achieve the TTS in the lightly crosslinked SBR systems, an anomalous vertical shift is required in the narrow temperature region from 10 to 30 °C. The vertical shift factor in this temperature region is not the standard from rubber elasticity. No anomalous behavior is detected in the equilibrium modulus, which is a linear function of temperature in accordance with the classical theory of rubber elasticity. In contrast to SBR, standard vertical shifts are required to effect TTS for uncrosslinked polybutadiene and an ethylene propylene diene monomer elastomer. © 2013 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2013     

Synthesis of hybrid polymeric fibers of different functionalized alkoxysilane coupling agents obtained via sol–gel and electrospinning technique: effect on the morphology by addition of PVA

Journal of Sol-Gel Science and Technology - Hybrid functionalized alkoxysilane/PDMS-OH and alkoxysilane/PDMS-OH/PVA polymers were synthesized through acid catalysis sol–gel technique and...     

The effect of chlorosulphonated polyethylene on thermal properties and combustibility of butadiene–styrene rubber

This article describes the test results of thermal properties and flammability of the unconventionally cross-linked blends of chlorosulfonated polyethylene (CSM) and butadiene–styrene rubber (SBR) by means of zinc oxide or nano-zinc oxide. The thermal curves have been interpreted from the point of view of the chemical transitions of elastomers and their blends. It has been found that the content of combined chlorine in CSM exerts a significant influence on the cross-linking kinetics of CSM/SBR blends, their thermal properties and flammability.     

Synthesis and characterizations of new negatively charged organic–inorganic hybrid materials: effect of molecular weight of sol–gel precursor

A series of negatively charged hybrid (organic–inorganic) materials were prepared through sol–gel process. The alkoxysilane-containing sol–gel precursors PEO-[Si(OEt)₃]₂SO₃H were obtained by endcapping polyethylene oxide (PEO) of different molecular weights with 2,4-diisocyanate toluene (TDI), followed by a coupling reaction with phenylaminomethyl triethoxysilane (ND-42) and sulfonation afterwards. The negatively charged precursors were then hydrolyzed and condensed to generate hybrid sol–gel materials, which were characterized by IR, TGA, XRD as well as the conventional ion exchange measurements. The results showed that in the hybrid sol–gel precursors PEO-[Si(OEt)₃]₂SO₃H organic PEO component was incorporated with alkoxysilane-containing ND-42 covalently. As the molecular weight of the precursors increased, thermal stability and cation-exchange capacity of the hybrid material decreased. All the hybrid materials were amorphous and those prepared from higher molecular weight precursors were flexible.     

Study on molecular weight cut-off performance of asymmetric aromatic polyimide membrane “Effect of the additive agents”

Asymmetric polyimide membranes were fabricated from casting solution of 18 wt% polyamic acid and 1.3–20 wt% additive agent in dimethylacetamide at 343 K, with 1 min evaporation time, followed by a cyclization process of thermal treatment in a bath of dioctyl sebacate under N₂ in three steps: 1 h at 373 K, 1 h at 473 K, 1 h at 573 K. The effect of additive agents and their quantity on the molecular weight cut-off (MWCO) performance of the asymmetric aromatic polyimide membrane were examined. By changing a sort of additive agents, the MWCO of the fabricated aromatic polyimide asymmetric membranes can be adjusted in the range of 400–650 daltons. By changing amount of additive agents, MWCO of the fabricated aromatic polyimide asymmetric membranes remain almost constant at the value of approximately 400 daltons for pyrene, and increased from 500–650 daltons for polystyrene.     

Electron transfer reaction of 4,4′-bipyridine with triethylamine in acetonitrile: effect of water addition on the reaction dynamics

The photo-induced electron-transfer reaction of 4,4-bipyridine (BPY) with triethylamine (TEA) in acetonitrile is studied by laser flash photolysis. The reaction mechanism and kinetics are found very sensitive to the presence of a small amount of water. At low water concentrations (i.e. <0.003 M), an extremely fast-rising metastable product is detected for the first time. A triplet charge transfer complex (³ECT) is found to be the primary intermediate preceding the electron transfer process. Up to about 0.1 M, water facilitates the electron transfer rate, whereas higher water concentrations retard the rate of electron transfer. The Stern-Volmer plot of the triplet decay rate versus the TEA concentration is consistent with the presence of ³ECT in equilibrium with the free excited triplet state of BPY.     

The bridged effect on the geometric,optoelectronic and charge transfer properties of the triphenylamine–bithiophene-based dyes: a DFT study

Research on Chemical Intermediates - The dye-sensitized solar cells containing a triphenylamine unit as the electron donor connected with a terminal cyanoacrylic acid electron acceptor by...     

Anionic polymerization of ϵ-caprolactam-lix effect of the ratio of reacting components,of the medium and of the ring size on the initial stage of the anionic polymerization of lactams

Effects of the concentrations and ratio of reacting components and of temperature on the kinetics of reaction of N-propionyllactam (I) with potassium salt of lactam (KL) were studied for derivatives of ϵ-caprolactam, 8-octanelactam and 12-dodecanelactam. For ϵ-caprolactam, the initial rates of propagation, acylation of open-chain amide groups and condensation of growth centres were estimated. At the ratio of the starting components [I]₀/[KL]₀ = 0.5-3, the participation of the polymerization reaction is constant, amounting to ca 45% of the overall consumption of 1. The condensation reaction is 14–36% of the total consumption of I; its initial rate passes through a maximum at [I]₀/[KL]₀ = 2. With increasing permittivity of the medium, the total rate of consumption of I increases; in two media with the same bulk permittivity, however, the rates may differ by as much as one order of magnitude.     

Effect of glycerol and its analogs on polyhydroxyalkanoate biosynthesis by recombinant Ralstonia eutropha: A quantitative structure–activity relationship study of chain transfer agents

Triglycerides such as plant and vegetable oils are desirable feedstock for the fermentative production of polyhydroxyalkanoate (PHA) because the weight yield of PHA from triglycerides is higher than that obtained from sugars. However, glycerol, a multi-hydroxy component of triglyceride, is known to function as a chain transfer (CT) agent in PHA polymerization, resulting in the formation of low-molecular-weight PHA. In this study, we evaluated how glycerol alters the molecular weight of PHA using recombinant Ralstonia eutropha as a practical host for PHA production. We demonstrated that glycerol has the ability to reduce molecular weight of PHA, even as a component of triglyceride. Furthermore, various alcohols that are structurally related to glycerol were examined for their reducing abilities to perform a quantitative structure–activity relationship (QSAR) study. It was found that alcohols with higher hydrophobicity (log P) exhibited higher reducing ability for PHA molecular weight. Glycerol, a less hydrophobic alcohol, was able to reduce PHA molecular weight; however, the efficacy was relatively weak among the examined alcohols.     

DFT study of the conductance of molecular wire:The effect of coupling geometry and intermolecular interaction on the transport properties

The density functional theory (DFT) combining with the non-equilibrium Green functions (NEGF) method is applied to the study of the electronic transport properties for a Di-thiol-benzene (DTB) molecule coupled to two Au(111) surfaces. The dependence of the transport properties on the bias, the coupling geometry of the molecule-electrode interface, and the intermolecular interaction are examined in detail. The results show that the existence of the hydrogen atom at the end of the DTB molecule would significantly decrease the transmission coefficients, and then the differential conductance (dI/dV). By changing the position of the DTB molecule located between two electrodes a maximum value of calculated current is observed. It is also found that the intermolecular interaction will strongly influence the transport properties of the system studied.     

Determination of the molecular weight of poly(ethylene glycol) in biological samples by reversed-phase LC–MS with in-source fragmentation

PEGylation has been widely used to improve the biopharmaceutical properties of therapeutic proteins and peptides. Previous studies have used multiple analytical techniques to determine the fate of both the therapeutic molecule and unconjugated poly(ethylene glycol) (PEG) after drug administration. A straightforward strategy utilizing liquid chromatography–mass spectrometry (LC–MS) to characterize high-molecular weight PEG in biologic matrices without a need for complex sample preparation is presented. The method is capable of determining whether high-MW PEG is cleaved in vivo to lower-molecular weight PEG species. Reversed-phase chromatographic separation is used to take advantage of the retention principles of polymeric materials whereby elution order correlates with PEG molecular weight. In-source collision-induced dissociation (CID) combined with selected reaction monitoring (SRM) or selected ion monitoring (SIM) mass spectrometry (MS) is then used to monitor characteristic PEG fragment ions in biological samples. MS provides high sensitivity and specificity for PEG and the observed retention times in reversed-phase LC enable estimation of molecular weight. This method was successfully used to characterize PEG molecular weight in mouse serum samples. No change in molecular weight was observed for 48 h after dosing.

Influence of the synthesis conditions on the structure and composition of the titanium–magnesium nanocatalyst and on its activity in isoprene polymerization

Synthesis of titanium–magnesium nanocatalyst in a high-pressure reactor under the conditions modeling the industrial conditions was studied. A laboratory scale plant including the units for the product synthesis, washing, and filtration was developed. The effect of elevated pressure (10–90 atm) on the process course, on the properties of the catalyst formed, and on the isoprene polymerization was studied for the first time. An increase in pressure leads to an increase in titanium incorporation into the catalyst from 1.52 to 2–2.3 wt % and simultaneously to an increase in the trivalent titanium content to 81 wt %. The titanium–magnesium nanocatalyst with such properties exhibits enhanced performance in isoprene polymerization without deteriorating the polymer microstructure. The development of the catalyst synthesis procedure on the laboratory scale plant will allow pilot-scale modeling of this process in the future.     

Ceramic Micro-Particles Synthesised using Emulsion and Sol–Gel Technology: An Investigation into the Controlled Release of Encapsulants and the Tailoring of Micro-Particle Size

Controlled release technologies have many applications in such diverse fields as the pharmaceutical, agricultural, cosmetic and food industries, where tailored release rates and protection of the active molecule for delivery at a specific site or time are advantageous. Silica microspheres, with controlled diameters of 10–50 m and containing Orange II dye as a model encapsulant, have been synthesised by combining water-in-oil (w/o) emulsion technology with sol–gel chemistry. The average particle size may be controlled by the microemulsion parameters, including the surfactant and solvent concentrations, and by the sol–gel processing parameters, particularly water-to-silicon alkoxide ratio, pH, temperature, ageing and mixing conditions. Physical properties of the SiO₂ microspheres, which modulate the release rates of the encapsulated molecule (including pore size and tortuosity), are also controlled by the sol–gel process parameters.The effect of synthesis parameters, including surfactant concentration, sol–gel solution pH and drying temperature, on the morphology of the SiO₂ microspheres produced will be discussed. The effect of such parameters on the corresponding release rates of the model encapsulants will also be presented.     

The effect of Nb and Ni addition on crystallization behavior of amorphous–nanocrystalline Fe–Cr–B–Si alloys

The crystallization behavior of amorphous Fe–Cr–B–Si alloys in the presence of Ni and Nb elements was the goal of this study. In this regard, four different amorphous–nanocrystalline Fe₄₀Cr₂₀Si₁₅B₁₅M₁₀ (M=Fe, Nb, Ni, Ni_0.5Nb_0.5) alloys were prepared using mechanical alloying technique up to 20 h. Based on the achieved results, in contrast to Fe₅₀Cr₂₀Si₁₅B₁₅ alloy, the amorphous phase can be successfully prepared in the presence of Ni and Nb in composition. Although the crystallization mechanism of prepared amorphous phase in different alloys was the same, the Fe₄₀Cr₂₀Si₁₅B₁₅Nb₁₀ alloy showed higher thermal stability in comparison with other samples. The crystallization activation energy of this amorphous alloy was estimated about 410 kJ mol^?1 which was much higher than Fe₄₀Cr₂₀Si₁₅B₁₅Ni₁₀ (195.5 kJ mol^?1) and Fe₄₀Cr₂₀Si₁₅B₁₅Ni₅Nb₅ (360 kJ mol^?1) samples. The calculated values of Avrami exponent (1.5 < n < 2.2) indicated that the crystallization process in different alloying systems is the same and to be governed by a three-dimensional diffusion-controlled growth.