Lewis acid–base properties of cellulose acetate phthalate‐polycaprolactonediol blend by inverse gas chromatography

The net retention volumes, V_N, of n‐alkanes and five polar probes are determined on cellulose acetate phthalate–polycaprolactonediol blend column by inverse gas chromatography in the temperature range 323.15–363.15 K. The dispersive surface energy, $\gamma _{\bf S}^{\bf d}$ , of the blend has been calculated using the V_N values of n‐alkanes and the $\gamma _{\bf S}^{\bf d}$ at 333.15 K is 12.6 mJ/m². The $\gamma _{\bf S}^{\bf d}$ values are decreasing linearly with increase of temperature. The V_N values of the five polar solutes are used to calculate the specific component of the enthalpy of adsorption, ${\Delta }{H}_{\bf a}^{\bf S}$ . The Lewis acid–base parameters, K_a and K_b, are derived using ${\bf \Delta }{H}_{\bf a}^{\bf S}$ values and are found to be 0.019 and 0.403, respectively. The K_a and K_b values indicate that the blend surface contain more basic sites and interact strongly with the acidic probes. The acid–base parameters have been used to analyze the preferential interaction of the solid surface with acidic and basic probes. POLYM. ENG. SCI., 2013. © 2013 Society of Plastics Engineers     

Versatility of a succinimidyl‐ester functional alkoxyamine for controlling acrylonitrile copolymerizations

Styrene/acrylonitrile (S/AN) and tert‐butyl methacrylate/acrylonitrile (tBMA/AN) copolymers were synthesized in a controlled manner (low polydispersity $ {{\overline M _w } / {\overline M _n }} $ with linear growth of number average molecular weight $ \overline M _n $ vs. conversion X) by nitroxide mediated polymerization (NMP) with a succinimidyl ester (NHS) terminated form of BlocBuilder unimolecular initiator (NHS‐BlocBuilder) in dioxane solution. No additional free nitroxide (SG1) was required to control the tBMA‐rich copolymerizations with NHS‐BlocBuilder, a feature previously required for methacrylate polymerizations with BlocBuilder initiators. Copolymers from S/AN mixtures (AN molar initial fractions f_AN,0 = 0.13–0.86, T = 115°C) had $ {{\overline M _w } / {\overline M _n }} $ = 1.14–1.26 and linear $ \overline M _n $ versus conversion X up to X ≈ 0.6. tBMA/AN copolymers (f_AN,0 = 0.10–0.81, T = 90°C) possessed slightly broader molecular weight distributions ( $ {{\overline M _w } / {\overline M _n }} $ = 1.23–1.50), particularly as the initial composition became richer in tBMA, but still exhibited linear plots of $ \overline M _n $ versus conversion X up to X ≈ 0.6. A S/AN/tBMA terpolymerization (f_AN,0 = 0.50, f_S,0 = 0.40) was also conducted at 90°C and revealed excellent control with $ \overline M _n $ = 13.6 kg/mol, $ {{\overline M _w } / {\overline M _n }} $ = 1.19, and linear $ \overline M _n $ versus conversion X up to X = 0.54. Incorporation of AN and tBMA in the final copolymer (molar composition F_AN = 0.47, F_tBMA = 0.11) was similar to the initial composition and represents initial designs to make tailored, acid functional AN copolymers by NMP for barrier materials. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Peptide Bioconjugates of Electron‐Poor Metallocenes: Synthesis,Characterization, and Anti‐Proliferative Activity

We report the synthesis of metallocene compounds Cp₂M with two different electron‐withdrawing substituents on both cyclopentadienyl rings (hexafluoroacetone (HFA) and chlorobenzoyl ( 1 – 5 ); HFA and COOH ( 6 and 7 ), M=Fe or Ru). The COOH‐containing derivatives were used to synthesize peptide bioconjugates with enkephalin ( 8 and 9 ) and neurotensin ( 10 and 11 ) as well as fluorescein‐labeled neurotensin ( 12 ). All the molecules were fully characterized, including X‐ray structures for 6 and 7 . The physicochemical properties (lipophilicity and electrochemistry) and cytotoxicity on MCF‐7, HT‐29, and PT‐45 cancer cells were evaluated for selected compounds. Electrochemical investigation by cyclic voltammetry revealed that all bis‐substituted metallocenes are up to 300 mV harder to oxidize compared to the monosubstituted 2‐ferrocenylhexafluoropropan‐2‐ol (FcHFA: Δ${E{{{\rm f}\hfill \atop 0\hfill}}}$ =214 mV; disubstituted derivatives: up to Δ${E{{{\rm f}\hfill \atop 0\hfill}}}$ =512 mV; both vs. FcH^0/+). For the bis‐substituted compounds, log P determinations by RP‐HPLC showed increased lipophilicity in comparison to the monosubstituted FcHFA and RcHFA. Cellular uptake was investigated by fluorescence microcopy, and this revealed endosomal entrapment for 12 .     

Effect of Processing Variables on the Morphology of Electrospun Poly[(lactic acid)‐co‐(glycolic acid)] Nanofibers

A systematic study of the effects of , flow rate, voltage, and composition on the morphology of electrospun PLGA nanofibers is reported. It is shown that changes of voltage and flow rate do not appreciably affect the morphology. However, the of PLGA predominantly determines the formation of bead structures. Uniform electrospun PLGA nanofibers with controllable diameters can be formed through optimization. Further, multi‐walled carbon nanotubes can be incorporated into the PLGA nanofibers, significantly enhancing their tensile strength and elasticity without compromising the uniform morphology. The variable size, porosity, and composition of the nanofibers are essential for their applications in regenerative medicine.

     

Correlations between the Shape of Viscosity Functions and the Molecular Structure of Long‐Chain Branched Polyethylenes

The viscosity functions of long‐chain branched metallocene‐catalyzed ethene homopolymers and copolymers (LCB‐mPE) were described by an extended Carreau‐Yasuda model. The two characteristic relaxation times, λ₁ and λ₂, and the slope of the viscosity function between these two characteristic relaxation times can be correlated to the zero shear‐rate viscosity, η₀, and the molar mass . The characteristic relaxation times, λ₁ and λ₂ (describing the main curvatures of the viscosity function) exhibit a power law dependency on the molar mass, . The parameterization of the viscosity function can be used for a molecular characterization and flow simulations of various kinds.

     

Adsorptive removal of nitrate and phosphate anions from aqueous solutions using functionalised SBA‐15: Effects of the organic functional group

Adsorption of nitrate and monovalent phosphate anions from aqueous solutions on mono, di‐ and tri‐ammonium‐functionalised mesoporous SBA‐15 silica was investigated. The adsorbents were prepared via a post‐synthesis grafting method, using either 3‐aminopropyltrimethoxysilane (N‐silane) or [1‐(2‐aminoethyl)‐3‐aminopropyl]trimethoxysilane (NN‐silane) or 1‐[3‐(trimethoxysilyl)‐propyl]‐diethylenetriamine (NNN‐silane), followed by acidification in HCl solution to convert the attached surface amino groups to positively charged ammonium moieties. The nominal loading of amino moieties on the SBA‐15 surface was varied from 5% to 20% as organoalkoxysilane/silica molar ratio. The adsorption experiments were conducted batchwise at room temperature. Results showed that adsorption capacity increased with increasing the concentration of monoammonium groups on the SBA‐15 adsorbent. Nitrate adsorption capacity increased from 0.34 to 0.66 mmol ${\rm NO}_{3}^{{-} } /{\rm g}$ adsorbent while phosphate adsorption capacity increased from 0.34 to 0.63 mmol ${\rm H}_{2} {\rm PO}_{4}^{{-} } /{\rm g}$ adsorbent when the molar ratio organoalkoxysilane/silica was varied from 5% to 20%, respectively. Also, for the same organoalkoxysilane/silica molar ratio of 10%, the adsorption capacity increased with the increase of the number of protonated amines in the functional groups. Therefore, maximum adsorption capacities of 0.80, 1.16 and 1.38 mmol ${\rm NO}_{3}^{{-} } /{\rm g}$ adsorbent and 0.72, 0.82 and 1.17 mmol ${\rm H}_{2} {\rm PO}_{4}^{{-} } /{\rm g}$ adsorbent were obtained using mono‐, di‐ and triammonium functionalised SBA‐15 adsorbents, respectively. © 2011 Canadian Society for Chemical Engineering     

Determination of crystallinity ratio and some physicochemical properties of poly(4‐methyl‐1‐pentene)

It was determined that the thermal stability of poly(4‐methyl‐1‐pentene) (P4MP) was maintained up to 424°C in an inert atmosphere by thermogravimetric analysis. The retention diagrams of ethyl acetate, tert‐butyl acetate, and benzene on P4MP were plotted at temperatures between 30 and 280°C by inverse gas chromatography (IGC) technique. Melting temperature of the polymer was determined as 230 and 239.5°C by IGC and differential scanning calorimetry (DSC), respectively. The percent crystallinity of P4MP was obtained from the retention diagrams at temperatures below melting point. The percent crystallinity obtained by IGC is in good agreement with the ones obtained by DSC. Then, specific retention volume, V, weight fraction activity coefficient, Ω, Flory‐Huggins polymer‐solvent interaction parameter, χ, equation‐of‐state polymer‐solvent interaction parameter, χ, and effective exchange energy parameter, X_eff of octane, nonane, decane, undecane, dodecane, tridecane, n‐butyl acetate, isobutyl acetate, isoamyl acetate with P4MP, were determined between 240 and 280°C by IGC. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Poly(vinyl pyrrolidone‐co‐vinyl acetate)‐graft‐poly(ε‐caprolactone) as a compatibilizer for cellulose acetate/poly(ε‐caprolactone) blends

Poly(vinyl pyrrolidone‐co‐vinyl acetate)‐graft‐poly(ε‐caprolactone) (PVPVAc‐g‐PCL) was synthesized by radical copolymerization of N‐vinyl‐2‐pyrrolidone (VP)/vinyl acetate (VAc) comonomer and PCL macromonomer containing a reactive 2‐hydroxyethyl methacrylate terminal. The graft copolymer was designed in order to improve the interfacial adhesiveness of an immiscible blend system composed of cellulose acetate/poly(ε‐caprolactone) (CA/PCL). Adequate selections of preparation conditions led to successful acquisition of a series of graft copolymer samples with different values of molecular weight ( ), number of grafts (n), and segmental molecular weight of PVPVAc between adjacent grafts (M_n (between grafts)). Differential scanning calorimetry measurements gave a still immiscible indication for all of the ternary blends of CA/PCL/PVPVAc‐g‐PCL (72 : 18 : 10 in weight) that were prepared by using any of the copolymer samples as a compatibilizer. However, the incorporation enabled the CA/PCL (4 : 1) blend to be easily melt‐molded to give a visually homogeneous film sheet. This compatibilizing effect was found to be drastically enhanced when PVPVAc‐g‐PCLs of higher and M_n (between grafts) and lower n were employed. Scanning electron microscopy revealed that a uniform dispersion of the respective ingredients in the ternary blends was attainable with an assurance of the mixing scale of several hundreds of nanometers. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Molecularly imprinted poly(MAA‐co‐AM) composite membranes for selective recognition of nicosulfuron herbicide

Molecularly imprinted membranes with different ratio of acrylamide (AM) versus methacrylic acid (MAA) were prepared by photocopolymerization on commercial filter paper using nicosulfuron as the template. The structures, the thermal stability, and the morphology of membranes were characterized by infrared spectroscopy (IR), thermogravimetric analysis (TGA), and scanning electron microscopy (SEM), respectively. Static equilibrium binding and competitive recognition properties of the membranes to nicosulfuron and its analogs (pyrazosulfuron ethyl and bensulfuron methyl) were tested. The results showed that nicosulfuron‐imprinted membranes had the best recognition capacity to nicosulfuron compared with its analogs. The biggest selectivity factors of ${\rm \alpha }_{{\rm N}_{\rm 1} /{\rm P}_{\rm 2} }$ and ${\rm \alpha }_{{\rm N}_{\rm 1} /{\rm B}_{\rm 3} }$ were 1.28 and 1.83 and the imprinted factor reached to 2.34. The results of this study implied that the molecularly imprinted composite membranes could be used as separation membranes for nicosulfuron enrichment. The Scatchard plot revealed that one class of binding sites was mainly produced in the imprinted composite membrane in the studied concentration range of nicosulfuron. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Tailoring the Degree of Polymerization of Low Molecular Weight Cellulose

The degradation of cellulose to lmw samples with $\overline {DP} _{{\rm w}} $ varying from 15 to 130 is investigated. Cellulose samples prepared from the hydrolysis of regenerated cellulose fibers in dilute HCl possess $\overline {DP} _{{\rm w}} $ = 50. Applying homogenous degradation of microcrystalline cellulose in H₃PO₄ at RT for 3 weeks, samples with $\overline {DP} _{{\rm w}} $ = 35 and a PDI of 1.58 are obtained. Decreasing the hydrolysis temperature to 8 °C results in lmw cellulose with $\overline {DP} _{{\rm w}} $ > 70. Fractionation in DMA/LiCl provides samples with $\overline {DP} _{{\rm w}} $ = 12 to 130, together with a narrow molecular weight distribution. Detailed structural analysis by 2D NMR spectroscopy reveals that the prepared lmw celluloses are suitable as mimics for cellulose.

     

Water‐soluble/dispersible carbazole‐containing random and block copolymers by nitroxide‐mediated radical polymerisation

A series of carbazole‐containing water‐dispersible poly(acrylic acid)‐b‐(9‐(4‐vinylbenzyl)‐9H‐carbazole) block copolymers (poly(AA)‐b‐poly(VBK)) and water‐soluble poly(methacrylic acid‐ran‐(9‐(4‐vinylbenzyl)‐9H‐carbazole)) (poly(MAA‐ran‐VBK)) random copolymers were synthesised in a controlled manner (i.e. low polydispersities $(\overline {M_{{\rm w}} } /\overline {M_{n} } < 1.3)$ by nitroxide‐mediated polymerisation (NMP) using an SG1‐based alkoxyamine initiator, BlocBuilder. Poly(AA)‐b‐poly(VBK) block copolymers were most easily accessed by using poly(AA) in its protected form as the macroinitiator for the 9‐(4‐vinylbenzyl)‐9H‐carbazole (VBK) block. Controlled polymerisation of MAA was accomplished using an excess of 10 mol.% SG1 relative to BlocBuilder with VBK as controlling co‐monomer (initial molar feed content f_VBK,0 = 0.03–0.20) in dimethylformamide at 80°C. Poly(MAA‐ran‐VBK) copolymers with a final VBK molar composition of F_VBK < 0.30 resulted in water‐soluble copolymers. In addition, as macroinitiators, poly(MAA‐ran‐VBK)s were sufficiently pseudo‐living to reinitiate a second batch of monomer (90 mol.% methyl methacrylate with styrene) in organic solvent and by ab initio, surfactant‐free emulsion polymerisation. In both cases, low polydispersity, amphiphilic block copolymers resulted $(\overline {M_{{\rm w}} } /\overline {M_{{\rm n}} } < 1.3)$ . © 2012 Canadian Society for Chemical Engineering     

CLA TAG rich in cis‐9,trans‐11‐CLA is stable beyond 2 years of proper storage

We analyzed a triacylgylcerol esterified CLA preparation characteristically rich in c9,t11‐CLA and free of t10,c12‐CLA three times within a period of 2${1 \over 2}$ years by GC and silver ion‐HPLC. For the first time, we present data on the long‐term stability of this preparation with regard to the fatty acid profile and the isomeric composition of CLA under certain storage conditions, providing useful information for the planning of long‐term trials.     

Poly[ethylene‐co‐(vinyl alcohol)]‐graft‐poly(ε‐caprolactone) Synthesis by Reactive Extrusion, 1 ‐ Structural and Kinetic Study

Chemical modification of EVOH in the molten state at 185 °C by a grafting from process of poly(ε‐caprolactone) in batch was studied. ¹H NMR was used to characterize the structure evolutions of PCL grafts. In addition to grafting reactions, dynamic covalent transesterification reactions between EVOH residual alcohols and the polyester grafts led to a redistribution of the PCL grafts length. up to 27 and SR up to 80% were obtained. Experiments made in a corotating mini twin‐screw extruder also confirmed these results. The effect of the alcohol to caprolactone ratio and catalyst concentration (SnOct₂) on kinetic evolution showed that few minutes were necessary to complete the polymerization. A kinetic model was proposed and adequate conditions for the synthesis by reactive extrusion were defined.

     

Structural development of poly(ethylene terephthalate) during uniaxial stretching above the glass‐transition temperature: Study of the statistical influence of the stretching variables

In this article, we present an investigation of the structural development of poly(ethylene terephthalate) (PET) during uniaxial stretching above the glass‐transition temperature; this followed a statistical design of experiment approach to determine the influence of the stretching variables on the structural development. Amorphous PET was submitted to a stretching program with variations in the stretching temperature (T_st), stretching rate ( $\dot {\varepsilon}_{st}$ ), and stretching ratio (λ_st). Stretched samples were rapidly quenched and characterized by wide‐angle X‐ray scattering, optical birefringence, and differential scanning calorimetry. The relevance and influence of the stretching variables on the obtained parameters (phase fraction, phase orientation, and thermal parameters) were analyzed. The strain‐induced crystallinity was controlled by T_st, λ_st, and the interactions between them. Mesophase development was not dependant on T_st but on the interactions between $\dot {\varepsilon}_{st}$ and λ_st. The molecular orientation was proportionally dependent on T_st, λ_st, and their interactions. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Preparation and characterization of polystyrene modified single‐walled carbon nanotube

A halogen atom terminated Polystyrene (PSt) was prepared by means of atom transfer radical polymerization. Then, the halogen atom was converted into ‐N₃ group and a ‐N₃ terminated PSt was obtained. Finally PSt was grafted onto the surface of single walled carbon nanotube (SWNT) by the reaction of azide group with SWNT. Comparison of X‐ray photoelectron spectrometer of N1s electron belonging to ‐N₃ and the surface of SWNT demonstrated that three‐membered rings were formed by releasing N₂ from ‐N₃ during the reaction. The structure of PSt modified SWNT was characterized by FTIR, UV, Raman spectrum, and TEM. The experimental results showed that the PSt was connected assuredly to SWNT by the covalent bond. TGA data showed that the amount of PSt on the surface of SWNT firstly increased with growing of PSt and then decrease when continues to grow. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Solvent effects in the hydrodechlorination of 2,4‐dichlorophenol over Pd/Al2O3

Solvent effects in the liquid phase (0.1 MPa; 303 K) hydrodechlorination (HDC) of 2,4‐dichlorophenol have been established over Pd/Al₂O₃. In the absence of secondary reactions, catalyst deactivation, and transport limitations, a stepwise HDC yields 2‐chlorophenol and phenol, where product selectivity was insensitive to the nature of the solvent. In contrast, the initial HDC rates exhibited a marked dependence on the reaction medium and increased in the order: benzene < THF < n‐hexane < cyclohexane < alcohols < water. Higher rates result from the concomitant effect of an increase in the dielectric constant (ε) and a decrease in the molar volume ( $\overline {\nu}$ ) of the solvent, where the major (ca. 80%) contribution is due to ε. We attribute this response to the increased solvent capacity to stabilize the arenium intermediate at higher/lower ε/$\overline {\nu}$ , an effect that extends to reaction in water + organic combinations. We provide, for the first time, a reliable quantification of solvent effects that can be potentially applied to other catalytic hydrogenolysis systems. © 2009 American Institute of Chemical Engineers AIChE J, 2010     

Shape memory properties of polycaprolactone‐based polyurethanes prepared by reactive extrusion

The shape memory properties of polycaprolactone‐based polyurethanes (PCLUs) synthesized via a novel route of reactive extrusion were investigated in terms of the deformation amplitude, temperature, and rate by differential scanning calorimetry (DSC), dynamic mechanical analyzer, and polarized optical microscopy (POM). DSC analysis shows that the crystalline melting temperature and crystallinity of PCLU increased monotonically with increasing the average polymerization degree $ ( \overline {DPn}) $ of poly(ε‐caprolactone) (PCL) block. The retract force increased with increasing the temperature and reached the maximum (6–7 MPa) within 45–55°C. Furthermore, a modified model with two recovery stages was postulated to elucidate the shape memory process, which is visually presented by POM analysis. The two stages of tensile and compressive recovery are distinguished by the inflexion temperature, within 43–48°C and 64–66°C, respectively. The shape fixity is about 60–70% and can be improved to 100% by choosing proper deformation temperature. The tensile deformation recovery ratio was 80–98% due to the water absorption, whereas the compressive deformation recovery ratio was almost 100%. Besides, recovery tests show that the lowest recovery temperature ranged from 24 to 47°C was influenced by the deformation temperature, rate and the PCL block $ ( \overline {DPn}) $ . Thus, the shape memory properties can be adjusted according to different purposes. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Diffusion of semi‐flexible polyelectrolyte through nanochannels

The diffusion of sodium polystyrene sulfonate through polycarbonate nanochanels was studied in salt‐free dilute aqueous solution. A stronger molecular weight dependence of diffusion was observed compared to free diffusion in dilute solution. Scaling exponentials relating polymer size to diffusivity were between Flory's theory (D_eff ∝ N^?0.6) and Rouse's model (D_eff ∝ N^?1), revealing a crossover regime from 3‐D diffusion to 1‐D diffusion. Diffusion was less hindered for the polyelectrolyte (D_eff/D₀), than for a rigid sphere, when the polymer/channel size ratio exceeded 0.2. This is attributed to elongated chains with reduced frictional hindrance. Simulation of the confined diffusion based on an elongated cigar model gave D ∝ N^?1 ${R_{\rm t}^{2/3}}$ while the experimental results agree with D ∝ N^?0.94${R_{\rm t}^{ 2/3}}$ . For charged polyelectrolytes, the transition to 1‐D diffusion therefore begins before the polymer radius of gyration exceeds the channel size contrary to model assumptions. We attribute this to the charged nature of the polyelectrolytes causing extended chain conformations. © 2009 American Institute of Chemical Engineers AIChE J, 2010     

Transfer RNA Misidentification Scrambles Sense Codon Recoding

Sense codon recoding is the basis for genetic code expansion with more than two different noncanonical amino acids. It requires an unused (or rarely used) codon, and an orthogonal tRNA synthetase:tRNA pair with the complementary anticodon. The Mycoplasma capricolum genome contains just six CGG arginine codons, without a dedicated tRNA^Arg. We wanted to reassign this codon to pyrrolysine by providing M. capricolum with pyrrolysyl‐tRNA synthetase, a synthetic tRNA with a CCG anticodon (${{\rm tRNA}{{{\rm Pyl}\hfill \atop {\rm CCG}\hfill}}}$ ), and the genes for pyrrolysine biosynthesis. Here we show that ${{\rm tRNA}{{{\rm Pyl}\hfill \atop {\rm CCG}\hfill}}}$ is efficiently recognized by the endogenous arginyl‐tRNA synthetase, presumably at the anticodon. Mass spectrometry revealed that in the presence of ${{\rm tRNA}{{{\rm Pyl}\hfill \atop {\rm CCG}\hfill}}}$ , CGG codons are translated as arginine. This result is not unexpected as most tRNA synthetases use the anticodon as a recognition element. The data suggest that tRNA misidentification by endogenous aminoacyl‐tRNA synthetases needs to be overcome for sense codon recoding.