Sharif Digital Repository

A kinetic model based on a mechanistic approach was developed for thermal hydrocracking of a paraffinic feedstock. The hydrocarbon feed was described as a mixture of representative molecules based on structural group analysis (SGA) where information from elemental analysis, H1, and C13-NMR of the feed were used to obtain the average concentration of various structural groups from which representative molecules were constructed. The behavior of the feedstock under reaction conditions was described in terms of the reaction of the individual molecules. The reaction of each of the representative molecules and the corresponding product distribution was based on free radical mechanisms. The... 

The free radical activity of lespedezacoumestan was investigated toward hydroxyl (˙OH) radical in polar and nonpolar media using density functional theory. Four reaction mechanisms including radical adduct formation, hydrogen atom transfer, sequential single electron-proton transfer (SET-PT), and sequential proton loss electron transfer were considered. The rate constants and branching ratio for all possible sites of reaction were calculated and reported for the first time. According to the obtained results, lespedezacoumestan reacts faster with ˙OH radical in aqueous solution than in nonpolar media. Also, lespedezacoumestan is an excellent ˙OH radical scavenger regardless of the environment... 

Organ ischemia with inadequate oxygen supply followed by reperfusion (which initiates a complex of inflammatory responses and oxidative stress) occurs in different clinical conditions and surgical procedures including stroke, myocardial infarction, limb ischemia, renal failure, organ transplantation, free-tissue-transfer, cardiopulmonary bypass, and vascular surgery. Even though pharmacological treatments protect against experimental ischemia reperfusion (I/R) injury, there has not been enough success in their application for patient benefits. The main hurdles in the treatment of I/R injury are the lack of diagnosis tools for understanding the complicated chains of I/R-induced signaling... 

In this study a novel alginate-g-poly(acrylic acid)/alumina composite was synthesized and characterized. Preparation of the composite hydrogels involved free radical polymerization of a combination of alginate, acrylic acid (AA) and distilled water, in appropriate amounts and N,N-methylene bisacrylamide (MBA) as crosslinking agent. The composite formation was confirmed by Fourier transform infrared spectroscopic (FTIR). The surface morphologies of the synthesized hydrogels were assessed by scanning electron microscopy. Systematically, the different variables of the graft copolymerization were optimized to achieve maximum swelling capacity. The swelling of superabsorbent hydrogels was... 

Herein, poly (acrylic acid) (PAA) microgels were synthesized via alcohol type cross-linked by a free radical precipitation polymerization approach. At the first time, 1,6-hexanediol (1–6 diol), trimethylolpropane (TMP), and pentaerythritol (PEN) were selected as multifunctional cross- linking agent to synthesize cross-linked poly(acrylic acid) microgels. Alcohol type cross-linking agents can connect the PAA chains. The cross-linking reaction takes place due to reaction between hydroxyl groups of various cross-linkers and carboxyl groups of PAA chains. All of the hydroxyl groups do not participate in the reaction with acid groups of polymer chains through the polymerization stage; therefore,... 

Polycarboxylate superplasticizers based on acrylic acid (AA) and maleic anhydride (MAn) were synthesized via free-radical copolymerization with an ethylene glycol monomer and characterized. The copolymerization temperature (ranging from 50 to 90 °C) appeared to be the key operating factor governing the chemical structure of the superplasticizers. The chemical structures of the products were analyzed by gel permeation chromatography, whereas an optimized sample was further analyzed by Fourier transform infrared spectroscopy and 1H-NMR. Superplasticizers of the AA and MAn classes were then incorporated into concrete, and their performances were measured by slump and slump loss tests, where a... 

In this research, polysulfone (PSf) ultrafiltration (UF) membranes were prepared by a phase inversion method. Surface modification of the PSf membranes was carried out via grafting of acrylic acid as a hydrophilic monomer by free radical graft polymerization initiated by redox reaction. A central composite design (CCD) of response surface methodology (RSM) was applied to design the experiments. The process variables were acrylic acid concentration (CAA), redox system contact time (T1), and acrylic acid polymerization time (T2), while the contact angle (CA), pure water flux (PWF), and flux recovery ratio (FRR) were considered as the responses. Analysis of variance (ANOVA) demonstrated that... 

The hydrogen abstraction reaction of the OH radical with CH 2FCH22F (HFC-152) is studied theoretically over the 150-3000 K temperature range. In this study, the two most recently developed hybrid density functional theories, namely, BBlK and MPWBlK, are applied, and their efficiency in reaction dynamics calculation is discussed. The BBlK/6-31+G(d,p) method gives the best result for the potential energy surface (PES) calculations, including barrier heights, reaction path information (the first and second derivatives of PES), geometry of transition state structures, and even weak hydrogen bond orientations. The rate constants were obtained by the dual-level direct dynamics with the... 

In this work, the synthesis, characterization, and kinetic investigation of the free-radical polymerization of 4-acetylaminobenzene propenoic ester (ABPE) and 4-methylbenzene propenoic ester (MBPE) were studied. The kinetic behaviors of ABPE and MBPE in the polymerization initiated by azobisisobutyronitrile in dimethylformamide solutions at temperatures between 50 and 120°C were investigated, and experimental and theoretical conversion-time curves were compared. Both monomers showed a polymerization ceiling temperature (T c ). Tc was calculated with experimental values of k pk1/2 with a constant concentration of 0.7 mol/L for monomers. Tc was about 141 and 131 °C for ABPE and MBPE,... 

Bromophenols are known as antioxidant radical scavengers for some biomolecules such as those in marine red alga. Full understanding of the role played by bromophenols requires detailed knowledge of the radical scavenging activities in probable pathways, a focus of ongoing research. To gain detailed insight into two suggested pathways, H-atom transfer and electron transfer, theoretical studies employing first principle quantum mechanical calculations have been carried out on selected bromophenols. Detailed investigation of the aforementioned routes revealed that upon H-atom abstraction or the electron transfer process, bromophenols cause an increase in radical species in which the unpaired... 

Novel types of highly swelling hydrogels were prepared by grafting crosslinked polyacrylamide-co-poly-2-acrylamido-2-methylpropane sulfonic acid (PAAm-co-PAMPS) chains onto sodium alginate (Na-Alg) through a free radical polymerization method. The superabsorbent formation was confirmed by Fourier transform infrared spectroscopic (FTIR). The controlled release behavior of diclofenac sodium (DS) from superabsorbent polymer was factinvestigated, and shown that the release profiles of DS from superabsorbent polymer were slow in simulated gastric fluid (SGF, pH 1.2) over 3 h, but nearly all of the initial drug content was released in simulated intestinal fluid (SIF, pH 7.4) within 21 h after... 

In this work, the antioxidant ability of fisetin was explored toward hydroxyl (•OH) radical in aqueous and lipid solution using density functional level of theory. Different reaction mechanisms have been studied: hydrogen atom transfer, single electron transfer followed by proton transfer, and radical adduct formation, and sequential proton loss electron transfer. Rate constants for all possible reaction sites have been calculated using conventional transition state theory in conjunction with the Collins-Kimball theory. Branching ratios for the different channels of reaction are reported for the first time. Results show that the reactivity of fisetin toward hydroxyl (•OH) radical takes place... 

A switchable dual light- and temperature-responsive drug carrier using gold nanoparticles (Au NPs)-grafted poly(dimethylacrylamide-co-acrylamide)/poly acrylic acid [P(DMA-co-AAm)/PAAc] hydrogel was prepared by free radical polymerization procedure using N,N-methylenebisacrylamide as cross-linker and ammonium persulfate as initiator. Initial P(DMA-co-AAm) hydrogel and uniformly-distributed stable Au NPs, prepared by reduction of hydrogen tetrachloroaureate (III) hydrate in the presence of trisodium citrate, were synthesized separately. Then, the prepared P(DMA-co-AAm) and Au NPs were added to an acrylic acid solution along with the cross-linker and initiator to prepare PAAc hydrogel within... 

Biodegradable acrylate-terminated polyurethane/acrylate (APUA) filled with 2-hydroxyethyl methacrylate functionalized carbon nanotube (CNT-HEMA) was prepared by in situ free radical crosslinking. CNT-HEMA enhanced crystallinity of soft domain and caused more phase separation between hard and soft domains of APUA. Tensile testing showed a considerable improvement in elastic modulus (∼160%) and tensile strength (∼30%) at 1 wt% loading. Morphological features of APUA induced by nanotubes were found to be dominant on mechanical properties of APUA/CNT-HEMA. CNT-HEMA increased water contact angle of APUA; however, wettability of APUA/CNT-HEMA maintained in acceptable range for biomedical... 

Anticancer character of gold cluster has been indicated through its free radical scavenging properties. This is in contrast to its free radical promoting ability suggested by other workers. Here, we address this controversy by probing the stabilizing effects of Au3 cluster on RO• vs its impacts on RO-H bond dissociation enthalpy, at B3LYP/ LACVP+* level (RH, methyl, ethyl, n-propyl, i-propyl, n-butyl, t-butyl, and phenyl). In the presence of Au3 cluster, bond dissociation enthalpy of O-H bond and the spin density at the RO• oxygen are reduced dramatically. These are clear evidences for both the Au3 facilitation of the RO-H bond breakage and its scavenging of RO• radical. Since O-Au anchoring... 

A superhydrophobic nanocomposite coating was fabricated using a simple procedure. The nanocomposite is composed of an acrylic copolymer and modified silica nanoparticles. The acrylic copolymer was prepared by free radical copolymerization of methyl methacrylate and dodeycl methacrylate monomers. Silica nanoparticles were synthesized and modified with an alkyl silane reagent, hexadecyltrimethoxysilane. A mixture of acrylic copolymer and modified silica nanoparticles, dispersed in dichloromethane, was then sprayed on glass and filter paper surface. Chemical composition and structure of the coatings were investigated by FTIR, FESEM, AFM, 1H-NMR and GPC. The wettability of the prepared coating... 

Anticancer character of gold cluster has been indicated through its free radical scavenging properties. This is in contrast to its free radical promoting ability suggested by other workers. Here, we address this controversy by probing the stabilizing effects of Au3 cluster on RO• vs its impacts on RO–H bond dissociation enthalpy, at B3LYP/ LACVP+* level (R═H, methyl, ethyl, n-propyl, i-propyl, n-butyl, t-butyl, and phenyl). In the presence of Au3 cluster, bond dissociation enthalpy of O–H bond and the spin density at the RO• oxygen are reduced dramatically. These are clear evidences for both the Au3 facilitation of the RO–H bond breakage and its scavenging of RO• radical. Since O–Au...