Excess molar volumes,viscosity, refractive index,and Gibbs energy of activation of binary biodiesel + benzene,and biodiesel + toluene mixtures at 298.15 and 303.15 K

Excess molar volumes (V ^E), viscosities, refractive index, and Gibbs energies were evaluated for binary biodiesel + benzene and toluene mixtures at 298.15 and 303.15 K. The excess molar volumes V ^E were determined from density, while the excess Gibbs free energy of activation G*^E was calculated from viscosity deviation Δη. The excess molar volume (V ^E), viscosity deviation (Δη), and excess Gibbs energy of activation (G*^E) were fitted to the Redlich-Kister polynomial equation to derive binary coefficients and estimate the standard deviations between the experimental data and calculation results. All mixtures showed positive V ^E values obviously caused by increased physical interactions between biodiesel and the organic solvents.     

Synthesis of chiral calix[4]arenes bearing aminonaphthol moieties and their use in the enantiomeric recognition of carboxylic acids

Two armed chiral calix[4]arenes 8-16 functionalized at the lower rim with chiral aminonaphthol units have been prepared and the structures of these receptors characterized by FTIR, (1)H, and (13)C, DEPT and COSY NMR spectroscopy and elemental analysis. The enantioselective recognition of these receptors with various carboxylic acids has been studied by (1)H NMR and UV/Vis spectroscopy. The receptors exhibited different chiral recognition abilities towards the enantiomers of racemic materials and formed 2 : 1 or 1 : 1 complexes between host and guest. It was also demonstrated that chiral calix[4]arenes 9 and 16 could be used as chiral NMR solvating agents to determine the enantiomeric purity of mandelic acid.     

Block‐brush copolymers via ROMP and sequential double click reaction strategy

We report an efficient way, sequential double click reactions, for the preparation of brush copolymers with AB block‐brush architectures containing polyoxanorbornene (poly (ONB)) backbone and poly(ε‐caprolactone) (PCL), poly(methyl methacrylate) (PMMA) or poly(tert‐butyl acrylate) (PtBA) side chains: poly(ONB‐g‐PMMA)‐b‐poly(ONB‐g‐PCL) and poly(ONB‐g‐PtBA)‐b‐poly(ONB‐g‐PCL). The living ROMP of ONB affords the synthesis of well‐defined poly(ONB‐anthracene)₂₀‐b‐poly (ONB‐azide)₅ block copolymer with anthryl and azide pendant groups. Subsequently, well‐defined linear alkyne end‐functionalized PCL (PCL‐alkyne), maleimide end‐functionalized PMMA (PMMA‐MI) and PtBA‐MI were introduced onto the block copolymer via sequential azide‐alkyne and Diels‐Alder click reactions, thus yielding block‐brush copolymers. The molecular weight of block‐brush copolymers was measured via triple detection GPC (TD‐GPC) introducing the experimentally calculated dn/dc values to the software. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Study on Post-Polymerization Modification of Ring-Opening Metathesis Polymers Involving Pendant Thiolactone Units

Two different oxanorbornene monomers were prepared and copolymerized with butyl-functionalized oxanorbornene monomer through the ring-opening metathesis polymerization. The resulting polymers were then subjected to the aminolysis reactions with propylamine (PA) in the presence of methyl acrylate (MA) to capture, in situ, the latent thiol. It was found that the polymer, in which the thiolactone unit is close to the polymer backbone, did not undergo an efficient aminolysis reaction even an excess amount of PA was utilized, while the other polymer, in which the thiolactone unit away from the polymer backbone, did efficiently undergo aminolysis reaction even PA was used in low amounts. Besides, a variety of primary amine compounds along with MA were reacted with the polymer, in which the thiolactone group away from the polymer backbone, to test their reactivity toward the aminolysis reactions. All modified polymers were characterized by using conventional instruments such as gel permeation chromatography, nuclear magnetic resonance, and differential scanning calorimetry. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 2145–2153     

Screening of Carbonic Anhydrase,Acetylcholinesterase, Butyrylcholinesterase,and α-Glycosidase Enzyme Inhibition Effects and Antioxidant Activity of Coumestrol

Coumestrol (3,9-dihydroxy-6-benzofuran [3,2-c] chromenone) as a phytoestrogen and polyphenolic compound is a member of the Coumestans family and is quite common in plants. In this study, antiglaucoma, antidiabetic, anticholinergic, and antioxidant effects of Coumestrol were evaluated and compared with standards. To determine the antioxidant activity of coumestrol, several methods—namely N,N-dimethyl-p-phenylenediamine dihydrochloride radical (DMPD^•+)-scavenging activity, 2,2′-azinobis-(3-ethylbenzothiazoline-6-sulphonate) radical (ABTS^•+)-scavenging activity, 1,1-diphenyl-2-picrylhydrazyl radical (DPPH^•)-scavenging activity, potassium ferric cyanide reduction ability, and cupric ion (Cu²⁺)-reducing activity—were performed. Butylated hydroxyanisole (BHA), Trolox, α-Tocopherol, and butylated hydroxytoluene (BHT) were used as the reference antioxidants for comparison. Coumestrol scavenged the DPPH radical with an IC₅₀ value of 25.95 μg/mL (r²: 0.9005) while BHA, BHT, Trolox, and α-Tocopherol demonstrated IC₅₀ values of 10.10, 25.95, 7.059, and 11.31 μg/mL, respectively. When these results evaluated, Coumestrol had similar DPPH^•-scavenging effect to BHT and lower better than Trolox, BHA and α-tocopherol. In addition, the inhibition effects of Coumestrol were tested against the metabolic enzymes acetylcholinesterase (AChE), butyrylcholinesterase (BChE), carbonic anhydrase II (CA II), and α-glycosidase, which are associated with some global diseases such as Alzheimer’s disease (AD), glaucoma, and diabetes. Coumestrol exhibited K_i values of 10.25 ± 1.94, 5.99 ± 1.79, 25.41 ± 1.10, and 30.56 ± 3.36 nM towards these enzymes, respectively.     

Chemically Orthogonal Three‐Patch Microparticles

Compared to two‐dimensional substrates, only a few methodologies exist for the spatially controlled decoration of three‐dimensional objects, such as microparticles. Combining electrohydrodynamic co‐jetting with synthetic polymer chemistry, we were able to create two‐ and three‐patch microparticles displaying chemically orthogonal anchor groups on three distinct surface patches of the same particle. This approach takes advantage of a combination of novel chemically orthogonal polylactide‐based polymers and their processing by electrohydrodynamic co‐jetting to yield unprecedented multifunctional microparticles. Several micropatterned particles were fabricated displaying orthogonal click functionalities. Specifically, we demonstrate novel two‐ and three‐patch particles. Multi‐patch particles are highly sought after for their potential to present multiple distinct ligands in a directional manner. This work clearly establishes a viable route towards orthogonal reaction strategies on multivalent micropatterned particles.     

Sequential double polymer click reactions for the preparation of regular graft copolymers

In this study, graft copolymers with regular graft points containing polystyrene (PS) backbone and poly(methyl methacrylate) (PMMA), poly(tert‐butyl acrylate) (PtBA), or poly (ethylene glycol) (PEG) side chains were simply achieved by a sequential double polymer click reactions. The linear α‐alkyne‐ω‐azide PS with an anthracene pendant unit per chain was produced via atom transfer radical polymerization of styrene initiated by anthracen‐9‐ylmethyl 2‐((2‐bromo‐2‐methylpropanoyloxy)methyl)‐2‐methyl‐3‐oxo‐3‐(prop‐2‐ynyloxy) propyl succinate. Subsequently, the azide–alkyne click coupling of this PS to create the linear multiblock PS chain with pendant anthracene sites per PS block, followed by Diels–Alder click reaction with maleimide end‐functionalized PMMA, PtBA, or PEG yielded final PS‐g‐PMMA, PS‐g‐PtBA or PS‐g‐PEG copolymers with regular grafts, respectively. Well‐defined polymers were characterized by ¹H NMR, gel permeation chromatography (GPC) and triple detection GPC. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Linear tetrablock quaterpolymers via triple click reactions,azide‐alkyne,diels–alder,and nitroxide radical coupling in a one‐pot fashion

Azide‐alkyne and Diels–Alder click reactions together with a click‐like nitroxide radical coupling reaction were used in a one‐pot fashion to generate tetrablock quaterpolymer. The various living polymerization generated linear polymers with orthogonal end‐functionalities, maleimide‐terminated poly(ethylene glycol) (PEG‐MI), anthracene‐ and azide‐terminated polystyrene, alkyne‐ and bromide‐terminated poly(tert‐butyl acrylate) or alkyne‐poly(n‐butyl acrylate), and tetramethylpiperidine‐1‐oxyl (TEMPO)‐terminated poly(ε‐caprolactone) (PCL‐TEMPO) were clicked together in a one‐pot fashion to generate PEG‐b‐PS‐b‐PtBA‐b‐PCL or PEG‐b‐PS‐b‐PnBA‐b‐PCL quaterpolymer using Cu(0), CuBr, and N,N,N′,N″,N″‐pentamethyldiethylenetriamine as catalyst in dimethyl formamide at 80 °C for 36 h. Linear precursors and target quaterpolymers were analyzed via ¹H NMR and gel permeation chromatography. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Heteroarm H‐shaped terpolymers through click reaction

Heteroarm H‐shaped terpolymers, (polystyrene)(poly(methyl methacrylate))‐ poly(tert‐butyl acrylate)‐(polystyrene)(poly(methyl methacrylate)), (PS)(PMMA)‐PtBA‐(PMMA)(PS), and, (PS)(PMMA)‐poly(ethylene glycol)(PEG)‐(PMMA)(PS), through click reaction strategy between PS‐PMMA copolymer (as side chains) with an alkyne functional group at the junction point and diazide end‐functionalized PtBA or PEG (as a main chain). PS‐PMMA with alkyne functional group was prepared by sequential living radical polymerizations such as the nitroxide mediated (NMP) and the metal mediated‐living radical polymerization (ATRP) routes. The obtained H‐shaped polymers were characterized by using ¹H‐NMR, GPC, DSC, and AFM measurements. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 1055–1065, 2007     

Post‐functionalization of perfluorophenyl ester‐functional acyclic diene metathesis polymer

The acyclic diene metathesis (ADMET) polymerization was utilized for the design of the ADMET polymer (M_n = 21,200 g/mol, M_w/M_n = 1.74) with pendant perfluorophenyl ester functionality using Grubbs first generation catalysis overnight in bulk at 80 °C. Next, a wide variety of functional groups, like benzyl, octyl, propargyl, allyl, and furfuryl was quantitatively incorporated to the ADMET polymer backbone through various amines using activated ester substitution reaction. The ADMET polymers studied in this work were characterized using ¹H, ¹³C, and ¹⁹F NMR, GPC and DSC and displayed a monomodal distribution and a rather broad polydispersity index in the range of ?1.33 to 1.90. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 2593–2598