Molecular Weight Distribution (molecular + weight_distribution)

Distribution by Scientific Domains

Kinds of Molecular Weight Distribution

  • bimodal molecular weight distribution
  • broad molecular weight distribution
  • full molecular weight distribution
  • narrow molecular weight distribution
  • narrower molecular weight distribution

  • Selected Abstracts


    ABSTRACT Our previous study showed that in vitro pepsin digestibility of Chinese tartary buckwheat protein was relatively low compared to those of other edible seeds. In vitro pepsin digestibilities of four protein fractions of tartary buckwheat, microstructure and molecular weight (MW) distributions of hydrolysates were investigated. In vitro pepsin digestion assay showed that the digestibilities of tartary buckwheat protein fractions were albumin (81.20%), globulin (79.56%), prolamin (66.99%) and glutelin (58.09%). Scanning electron microscopy showed that albumin and globulin fractions were digested by pitting from the outer surface to the inner part and were more digestible, while prolamin and glutelin fractions resisted digestion because only the outer surfaces of their protein bodies were digested and the interior was protected. MW distribution of the hydrolysates from the four protein fractions was determined by high-performance liquid chromatography. The hydrolysates of albumin mainly consisted of polypeptides with lower MW. The hydrolysates of glutelin had larger polypeptides together with small and medium-sized peptide fractions. [source]

    High-Pressure Polymerization of Ethylene in Tubular Reactors: A Rigorous Dynamic Model Able to Predict the Full Molecular Weight Distribution

    Mariano Asteasuain
    Abstract A rigorous dynamic model of the high-pressure polymerization of ethylene in tubular reactors is presented. The model is capable of predicting the full molecular weight distribution (MWD), average branching indexes, monomer conversion and average molecular weights as function of time and reactor length. The probability generating function method is applied to model the MWD. This technique allows easy and efficient calculation of the MWD, in spite of the complex mathematical description of the process. The reactor model is used to analyze the dynamic responses of MWD and other process variables under different transition policies, as well as to predict the effects of process perturbations. The influence of the material recycle on the process dynamics is also shown. [source]

    Fundamental Molecular Weight Distribution of RAFT Polymers

    Hidetaka Tobita
    Abstract The molecular weight distribution formed in an ideal reversible addition-fragmentation chain transfer (RAFT)-mediated radical polymerization is considered theoretically. In this polymerization, the addition to the RAFT agent is reversible, and the active period on the same chain could be repeated, via the two-armed intermediate, with probability 1/2. This possible repetition is accounted for by introducing a new concept, the overall active/dormant periods. With this method, the apparent functional form of the molecular weight distribution (MWD) reduces to that proposed for the ideal living radical polymers (Tobita, Macromol. Theory Simul. 2006, 15, 12). The repetition results in a broader MWD than without the repetition. The formulae for the average molecular weights formed in batch and a continuous stirred tank reactor are also presented. [source]

    RAFT Miniemulsion Polymerization Kinetics, 2 , Molecular Weight Distribution,

    Hidetaka Tobita
    Abstract The molecular weight distribution formed in a RAFT polymerization conducted inside submicron particles (Dp,<,300 nm) is considered. For small particles, the MWD at low to middle conversion might be rather broad because of the large differences in MWDs formed in different polymer particles. Such a broad MWD can be made narrower by increasing the radical entry frequency. On the other hand, larger frequencies of radical entry result in a broader MWD at the final conversion levels. The number of dead polymer chains increases with time, and the dead polymer peak could be observed in the MWD at a prolonged aging time. According to this theoretical investigation, smaller particles are advantageous in implementing a faster polymerization rate, a narrower MWD, and a smaller number of dead polymer molecules. [source]

    Theoretical Derivation of the Molecular Weight Distribution of End-Capped Linear Condensation Polymers

    Henk Knoester
    Abstract End-capped, low molecular weight polymers have found numerous practical applications. By providing the end-capper molecules with specific chemical functionality, the polymer material can be equipped with a desired chemical behavior for product application or polymer processing. Using probabilistic methods, formulas are derived for calculating the target molecular weight distribution and its averages for the case of linear condensation polymerization. The formulas are generally applicable, allowing for arbitrary amounts of monofunctional monomers or end-capper molecules affecting either one or both functional groups involved in the polymerization process. [source]

    Control of the Molecular Weight Distribution of Petroleum Pitches via Dense-Gas Extraction

    E. G. Cervo
    Abstract Dense-gas extraction (DGE) was used to fractionate an isotropic petroleum pitch (number-average molecular weight Mn,=,516) into oligomeric cuts. A countercurrent-flow packed column was used to effect the separation, with supercritical toluene being used as the dense-gas solvent and commercially available M-50 or A-240 pitch being used as the feed. Isothermal operation at 330, 350, and 380,C was investigated, as well as operation with a linear positive temperature gradient (+,T), with the bottom of the column at 330 and the top at 380,C. For isothermal operation, the molecular weight distribution of the bottom products consisted primarily of dimer (Mn,=,508) and trimer (Mn,=,759) species, with pressure changes of as little as 5 bar producing significant changes in their relative distribution, as observed by MALDI mass spectrometry. On the other hand, by operating with a +,T, we could produce a bottom product consisting primarily of trimers and tetramers (Mn,=,997). [source]

    Effect of Comonomer Ethylene on Plateau Modulus of Crystal-line Ethylene-propylene Random Copolymer with Broad Molecular Weight Distribution

    Ding Jian
    Abstract Ethylene-propylene random copolymer with ultra-high molecular weight (UHPPR) and broad molecular weight distribution (MWD) was prepared with Ziegler-Natta catalyst. The viscoelastic behavior of UHPPR has been investigated by means of oscillatory rheometer at 180, 200 and 220 C. The loss modulus (G, curves of 180 and 200 C present a pronounced maximum at 38.10 and 84.70 r/s, respectively. For the first time, this makes it possible to directly determine the plateau modulus () of crystalline ethylene-propylene random copolymer with broad MWD in a certain experimental temperature G,(,) curve. The plateau modulus of UHPPR is 4.51105 and 3.67105 Pa at 180 and 200 C respectively, increasing with random incorporation of comonomer ethylene into the molecular chains and being independent of molecular weight. [source]

    "Living" Radical Polymerization in Tubular Reactors, 2 , Process Optimization for Tailor-Made Molecular Weight Distributions

    Mariano Asteasuain
    Abstract "Living" radical polymerization is a relatively new polymerization process that can be used to prepare resins with controlled structures. In this work, a mathematical model developed previously to describe nitroxide-mediated "living" radical polymerizations performed in tubular reactors is used for the optimization of the process and obtainment of tailor-made MWDs. Operating conditions and design variables are determined with the help of optimization procedures in order to produce polymers with specified MWDs. It is shown that bimodal and trimodal MWDs, with given peak locations, can be obtained through proper manipulation of the operating conditions. This indicates that the technique discussed in this work is suitable for detailed design of the MWD of the final polymer. [source]

    A Simplified Model for Prediction of Molecular Weight Distributions in Ethylene-Hexene Copolymerization Using Ziegler-Natta Catalysts

    Duncan E. Thompson
    Abstract A simplified steady-state model has been developed to predict molecular weight distributions and average compositions of ethylene-hexene copolymers produced using heterogeneous Ziegler-Natta catalysts in gas-phase reactors. The model uses a simplified reaction scheme to limit the number of parameters that must be estimated. The number of parameters is further reduced by assuming that different types of active sites share common rate constants for some reactions. Estimates of kinetic parameters are obtained using deconvolution analysis of industrial copolymer samples produced using a variety of isothermal steady-state operating conditions. The parameter estimates should prove useful as initial guesses for future parameter estimation in a non-isothermal model. [source]

    Free Radical Bulk Polymerization of Styrene: Simulation of Molecular Weight Distributions to High Conversion Using Experimentally Obtained Rate Coefficients

    Per B. Zetterlund
    Abstract Previously obtained experimental conversion-dependences of the propagation rate coefficient (kp), the termination rate coefficient (kt) and the initiator efficiency (f) for the free-radical bulk polymerization of styrene at 70,C have been used to simulate the full molecular weight distributions (MWD) to high conversion using the software package PREDICI, providing a robust test of the kinetic model adopted. Satisfactory agreement with the experimental MWD's (GPC) was obtained up to approximately 70% conversion. Beyond 70% conversion, the high MW shoulder that appears was correctly predicted, although the amount of such polymer was somewhat underestimated. This discrepancy is believed to probably have its origin in experimental error in the conversion-dependences of kp, kt and f, in particular kt, that were employed in the simulations, rather than indicate a more fundamental short-coming of the model employed. [source]

    Water Vapor Permeability of Mammalian and Fish Gelatin Films

    R.J. Avena-Bustillos
    ABSTRACT:, Water vapor permeability of cold- and warm-water fish skin gelatins films was evaluated and compared with different types of mammalian gelatins. Alaskan pollock and salmon gelatins were extracted from frozen skins, others were obtained from commercial sources. Water vapor permeability of gelatin films was determined considering differences on percent relative humidity (%RH) at the film underside. Molecular weight distribution, amino acid composition, gel strength, viscoelastic properties, pH, and clarity were also determined for each gelatin. Water vapor permeability of cold-water fish gelatin films (0.93 gmm/m2hkPa) was significantly lower than warm-water fish and mammalian gelatin films (1.31 and 1.88 gmm/m2hkPa, respectively) at 25 C, 0/80 %RH through 0.05-mm thickness films. This was related to increased hydrophobicity due to reduced amounts of proline and hydroxyproline in cold-water fish gelatins. As expected, gel strength and gel setting temperatures were lower for cold-water fish gelatin than either warm-water fish gelatins or mammalian gelatins. This study demonstrated significant differences in physical, chemical, and rheological properties between mammalian and fish gelatins. Lower water vapor permeability of fish gelatin films can be useful particularly for applications related to reducing water loss from encapsulated drugs and refrigerated or frozen food systems. [source]

    On the determination of molecular weight distributions of asphaltenes and their aggregates in laser desorption ionization experiments

    Ana R. Hortal
    Abstract Molecular weight distributions (MWD) of asphaltenes and their aggregates have been investigated in laser desorption ionization (LDI) mass spectrometric experiments. A systematic investigation of the dependence of the measured MWD on the asphaltene sample density and on the laser pulse energy allows the assignment of most probable molecular weights within 300,500 amu and average molecular weights of 800,1000 amu for the monomeric asphaltenes, as well as for the estimation of the contribution from asphaltene clusters in typical LDI measurements. The results serve to reconcile the existing controversy between earlier mass spectrometric characterizations of asphaltenes based on laser desorption techniques by different groups. Furthermore, the MWD measurements performed on particularly dense samples yield an additional differentiated broad band peaking around 9000,10 000 amu and extending over 20 000 amu, not observed previously in LDI experiments, thereby revealing a strong propensity of the asphaltenes to form clusters with specific aggregation numbers, which is in qualitative agreement with previous theoretical predictions and with the interpretation of measurements performed with other techniques. Copyright 2006 John Wiley & Sons, Ltd. [source]

    Towards a one-pot synthesis of a polystyrene,PMMA block copolymer via atom-transfer radical polymerization

    Claire Keary
    Abstract The solution atom-transfer radical copolymerization of styrene and methyl methacrylate in butyl acetate at 110,C in the presence of Cu(II) bromide and 2,2,-bipyride was investigated. Polystyrene was polymerized by atom-transfer radical polymerization using benzyl bromide as initiator and MMA was then added to the system. Block copolymers were formed when MMA was added at ,90% styrene conversion. Molecular weight distributions (Mw/Mn) of the block copolymers were ,1.5. The possibility of end-capping the polystyrene precursor as a means of improving its initiating efficiency towards MMA was also investigated but did not improve the system. 2002 Society of Chemical Industry [source]

    The morphology and characterization of starch from Pueraria lobata (Willd.) Ohwi

    Xian-Feng Du
    Pueraria lobata (Willd.) Ohwi starch and its components were characterized. Scanning electron microscopy of the starch granules showed they were oval and polygonal in shape. Centric birefringence was clearly observed when viewed under polarized light. The gelatinization temperature range was 61,64,70.5 C. The iodine affinity value (4.12%) indicated an amylose content of 21.68%. Brabender amylograms showed a fairly high maximum viscosity and very low breakdown, indicating high hot stability of the viscosity. The starch underwent a single-stage swelling power pattern over one temperature range, and the solubility pattern paralleled the swelling power. The X-ray diffraction pattern of the starch showed a Ca-type crystallite. The gel chromatogram of the starch demonstrated the polydispersity of its molecular weight distribution. [source]

    Hybrid titanium catalyst supported on core-shell silica/poly(styrene- co -acrylic acid) carrier

    Lijun Du
    Abstract Hybrid titanium catalysts supported on silica/poly(styrene- co -acrylic acid) (SiO2/PSA) core-shell carrier were prepared and studied. The resulting catalysts were characterized by Fourier transform infrared (FTIR) spectroscopy, laser scattering particle analyzer and scanning electronic microscope (SEM). The hybrid catalyst (TiCl3/MgCl2/THF/SiO2TiCl4/MgCl2/PSA) showed core-shell structure and the thickness of the PSA layer in the two different hybrid catalysts was 2.0 ,m and 5.0 ,m, respectively. The activities of the hybrid catalysts were comparable to the conventional titanium-based Ziegler-Natta catalyst (TiCl3/MgCl2/THF/SiO2). The hybrid catalysts showed lower initial polymerization rate and longer polymerization life time compared with TiCl3/MgCl2/THF/SiO2. The activities of the hybrid catalysts were enhanced firstly and then decreased with increasing P/P. Higher molecular weight and broader molecular weight distribution (MWD) of polyethylene produced by the core-shell hybrid catalysts were obtained. Particularly, the hybrid catalyst with a PSA layer of 5.0 ,m obtained the longest polymerization life time with the highest activity (2071 kg PE mol,1 Ti h,1) and the resulting polyethylene had the broadest MWD (polydispersity index = 11.5) under our experimental conditions. The morphology of the polyethylene particles produced by the hybrid catalysts was spherical, but with irregular subparticles due to the influence of PSA layer. 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010 [source]

    Study on bulk polymerization of methyl methacrylate initiated by low intensity ultrasonic irradiation

    Sude Ma
    Abstract Methyl methacrylate (MMA) was polymerized in bulk solutions using low intensity ultrasonic radiation of 0.25 W/cm2. The polymerization occurred after 1 h of irradiation time was applied. The polymerization rate was greatly accelerated either by increasing the amount of poly (methyl methacrylate) (PMMA) granular added into the system or by elongating the irradiation time. However, it was found that the reaction rate increased with the decreasing of the ultrasonic frequencies when the exposure time of the polymerization under the irradiation was less than 3 h. Experimental results verified that the polymerization was initiated by free radicals, which were mainly generated from the degradation of PMMA macromolecular chains, the friction between the polymer macromolecular chains and the solvent monomer. These findings were obviously different from those obtained when high intensity ultrasonic irradiation was used. The polymers fabricated in this study by using ultrasound irradiation have a narrower molecular weight distribution compared to those obtained from the polymerizations induced by the conventional initiators. 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010 [source]

    Dispersion polymerization of methyl methacrylate: Effect of stabilizer concentration

    Sheng Jiang
    Abstract In dispersion polymerizations of methyl methacrylate (MMA), little difference was found in the polymerization kinetics with varying stabilizer (PVP K-30) concentration, indicating that in contrast to emulsion polymerization, the kinetics of these dispersion polymerizations are independent of the number of particles. Comparing MMA precipitation and dispersion polymerizations revealed that nuclei formation in the latter results from precipitation polymerization occurring in the continuous phase, which can contribute significantly to the kinetics, and especially to the molecular weight distributions. No change was found in the molecular weight distribution of the PVP during a dispersion polymerization, nor was there any measurable difference between using fresh and recycled stabilizer. 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008 [source]

    Dimethylsilylbis(1-indenyl) zirconium dichloride/methylaluminoxane catalyst supported on nanosized silica for propylene polymerization

    Kuo-Tseng Li
    Abstract A dimethylsilylene-bridged metallocene complex, (CH3)2Si(Ind)2ZrCl2, was supported on a nanosized silica particle, whose surface area was mostly external. The resulting catalyst was used to catalyze the polymerization of propylene to polypropylene. Under identical reaction conditions, a nanosized catalyst exhibited much better polymerization activity than a microsized catalyst. At the optimum polymerization temperature of 55C, the former had 80% higher activity than the latter. In addition, the nanosized catalyst produced a polymer with a greater molecular weight, a narrower molecular weight distribution, and a higher melting point in comparison with the microsized catalyst. The nanosized catalyst's superiority was ascribed to the higher monomer concentration at its external active sites (which were free from internal diffusion resistance) and was also attributed to its much larger surface area. Electron microscopy results showed that the nanosized catalyst produced polymer particles of similar sizes and shapes, indicating that each nanosized catalyst particle had uniform polymerization activity. 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008 [source]

    The synthesis of poly(3-hydroxybutyrate)- g -poly(methylmethacrylate) brush type graft copolymers by atom transfer radical polymerization method

    Hlya Arslan
    Abstract Brush type of poly (3-hydroxy butyrate), PHB, copolymer synthesis has been reported. Natural PHB was chlorinated by passing chlorine gas through PHB solution in CHCl3/CCl4 mixture (75/25 v/v) to prepare chlorinated PHB, PHB-Cl, with the chlorine contents varying between 2.18 and 39.8 wt %. Toluene solution of PHB-Cl was used in the atom transfer radical polymerization (ATRP) of methyl methacrylate, MMA, in the presence of cuprous bromide (CuBr)/2,2,-bipyridine complex as catalyst, at 90C. This "grafting from" technique led to obtain poly (3-hydroxybutyrate)-g-poly(methylmethacrylate) (PHB- g -PMMA) brush type graft copolymers (cylindrical brush). The polymer brushes were fractionated by fractional precipitation methods and the , values calculated from the ratio of the volume of nonsolvent to volume of solvent of brushes were ranged between 2.8 and 9.5 depending on the molecular weight, grafting density, and side chain length of the brushes, while the , values of PHB, PHB-Cl, and homo-PMMA were 2.7,3.8, 0.3,2.4, and 3.0,3.9, respectively. The fractionated brushes were characterized by gel permeation chromatography, 1H-NMR spectrometry, thermogravimetric analysis (TGA), and differential scanning calorimetry techniques. PHB- g -PMMA brush type graft copolymers showed narrower molecular weight distribution (mostly in range between 1.3 and 2.2) than the PHB-Cl macroinitiator (1.6,3.5). PHB contents in the brushes were calculated from their TGA thermograms and found to be in range between 22 and 42 mol %. The morphologies of PHB- g -PMMA brushes were also studied by scanning electron microscopy. 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007 [source]

    Copolymerization of carbon dioxide and propylene oxide with zinc glutarate as catalyst in the presence of compounds containing active hydrogen

    L. J. Gao
    Abstract To enhance the catalytic copolymerization of CO2 and propylene oxide catalyzed by zinc glutarate, the influence of trace of water, ethanol, and propanal on the catalytic activity, the resulted copolymer structure, and the molecular weight and molecular weight distribution of the copolymer were investigated extensively. The experimental results showed that the catalytic activity decreased remarkably in the presence of either trace of ethanol or water, but increased in the presence of trace of propanal. Both 1H-NMR and 13C-NMR spectra suggested that the content of carbonate linkages of resulted copolymer was not effected obviously in the presence of above-mentioned impurities, giving completely alternating poly(propylene carbonate) (PPC). GPC results indicated that these impurities reduced the molecular weights but broadened the molecular weight distributions of resulted copolymers. Finally, the byproduct contents including both propylene carbonate determined by GC and polyether increased with the increase of three impurity concentrations. 2006 Wiley Periodicals, Inc. J Appl Polym Sci 2007 [source]

    Hydrothermal processing of rice husks: effects of severity on product distribution

    Rodolfo Vegas
    Abstract BACKGROUND: Treatment in aqueous media (hydrothermal or autohydrolysis reactions) is an environmentally friendly technology for fractionating lignocellulosic materials. Rice husks were subjected to hydrothermal processing under a variety of operational conditions to cause the selective breakdown of xylan chains, in order to assess the effects of reaction severity on the distribution of reaction products. RESULTS: The effects of severity (measured by the severity factor, R0) on the concentrations of the major autohydrolysis products (monosaccharides, xylo- and glucooligosaccharides, xylooligosaccharide substituents, acetic acid, acid-soluble lignin and elemental nitrogen) were assessed. The interrelationship between the severity of treatment and molecular weight distribution was established by high-performance size-exclusion chromatography. Selected samples were subjected to refining treatments as ethyl acetate extraction and ion exchange for refining purposes, and the concentrates were assayed by high-performance anion-exchange chromatography and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry. CONCLUSIONS The protein equivalent of the products present in liquors accounted for 43 to 51% of the protein present in the raw rice husks. The concentrations of glucose (derived from starchy material) and arabinose (split from the xylan backbone) were fairly constant with severity. Even in treatments at low severity, high molecular weight compounds derived from xylan accounted for a limited part of the stoichiometric amount. Operating under harsh conditions, about 50% of the total xylan-derived compounds corresponded to fractions with a degree of polymerization (DP) < 9. After refining, saccharides accounted for more than 90% of the non-volatile components of the sample. The refined products showed a series of xylose oligomers up to about DP 13, and a series of acetylated xylose oligomers up to about DP 15. Copyright 2008 Society of Chemical Industry [source]

    Effects of supplementation of succinic acid on the production and molecular weight distribution of exopolysaccharides by Antrodia camphorata in batch cultures

    Chin-Hang Shu
    Abstract The effects of organic acid supplementation on both yields and molecular weight distributions of exopolysaccharide (EPS) of Antrodia camphorata were investigated in shaker flasks and air-lift bioreactors. In the shaker flask study, five out of six organic acid-supplemented cultures showed negative effects on cell growth, the exception being pyruvic acid-supplemented culture; lower number average molecular weights (Mn) of EPS were obtained in all the supplemented cultures. EPS production was enhanced by 31% due to the addition of succinic acid. Optimum product yield was obtained between 2.0 and 3.0 g dm,3 succinic acid; however, the specific production of EPS increased monotonically as succinic acid concentration was increased from 0 to 5 g dm,3. Enhancement of EPS yield by 28% and a higher Mn of EPS (around 310 kDa) due to the addition of succinic acid were also demonstrated in an air-lift bioreactor. In addition, a novel fermentation process resistant to EPS degradation is proposed, based on the inhibition of ,-glucanase activity by the supplementation with succinic acid. Copyright 2004 Society of Chemical Industry [source]


    ABSTRACT Chitin oligosaccharides (NA-COS) with low molecular weight distribution of 229.21,593.12 Da were produced from crab chitin by acid hydrolysis. They showed reducing power and scavenging effect on 1,1-diphenyl-2-picrylhydrazyl (DPPH) (Sigma Chemical Co., St. Louis, MO), hydroxyl and alkyl radicals. It was observed that the radical-scavenging activity of NA-COS increased in a dose-dependent manner. Their IC50 values for DPPH, hydroxyl and alkyl radicals were 0.8, 1.75 and 1.14 mg/mL, respectively. Furthermore, NA-COS exhibited the inhibitory effect on the oxidative damage of DNA from human lymphoma U937 (American Type Culture Collection, Manassas, VA) and the direct radical-scavenging effect in human fibrosarcoma cells (HT1080) (American Type Culture Collection) in 2,,7,-dichlorofluorescin diacetate (DCFH-DA) assay (Molecular Probes Inc., Eugene, OR). The results suggest that NA-COS can exert antioxidant effect in live cells and have the potential to be applied to food supplements or nutraceuticals. PRACTICAL APPLICATIONS Chitin oligosaccharides (NA-COS) are the hydrolyzed products of chitin (KEUMHO chemical products Co. Ltd., Gyeongbuk, Korea) of which derivatives have shown antioxidant, antimicrobial, anticancer, anti-inflammatory and immunostimulant effects. According to previous studies, NA-COS have beneficial biological activities similar to those of chitin. Furthermore, they are easily soluble in water because of their shorter chain length. Therefore, NA-COS are potentially applicable to improve food quality and human health. [source]

    Determination of Total Protein Content in Gelatin Solutions with the Lowry or Biuret Assay

    P. Zhou
    ABSTRACT:, Gelatins can be obtained from different sources and prepared using different processes, and the end product gelatin may vary in amino acid composition and molecular weight distribution. In the present study, the variation in "protein color" development among gelatins in colorimetric total protein content measurements was investigated at 540 nm using the Biuret assay and at 650 nm using the Lowry assay, with bovine serum albumin as the reference protein. In both the Biuret and Lowry assays, the color response varied significantly among gelatins. The difference in imino acid content was the major factor responsible for this variation, which probably influenced the gelatin helix , coil phase transition and resulted in the difference in gelatin associate state. Based on their "protein color" development abilities in both Biuret and Lowry, gelatins were classified into 2 major groups with the hierarchical cluster analysis: 1 group included all cold water fish gelatins, while the other included gelatins from warm water fish, avian, and mammalian species. [source]

    Cationic polymerization in rotating packed bed reactor: Experimental and modeling

    AICHE JOURNAL, Issue 4 2010
    Jian-Feng Chen
    Abstract On the basis of analysis of key engineering factors predominating in cationic polymerization, butyl rubber (IIR) as an example was synthesized by cationic polymerization in the high-gravity environment generated by a rotating packed bed (RPB) reactor. The influence of the rotating speed, packing thickness, and polymerization temperature on the number average molecular weight (Mn) of IIR was studied. The optimum experimental conditions were determined as rotating speed of 1200 r min,1, packing thickness of 40 mm and polymerization temperature of 173 K, where IIR with Mn of 289,000 and unimodal molecular weight distribution of 1.99 was obtained. According to the experimental results and elementary reactions, a model for the prediction of Mn was developed, and the validity of the model was confirmed by the fact that most of the predicted Mns agreed well with the experimental data with a deviation within 10%. 2009 American Institute of Chemical Engineers AIChE J, 2010 [source]

    Laser desorption/ionization techniques in the characterization of high-molecular-weight oil fractions,Part 2: de-asphalted oils

    Andrea Rizzi
    Abstract The composition of the de-asphalted oil fraction obtained from two different Italian fields was studied by laser desorption/ionization mass spectrometry. These fractions were treated with different solvent mixtures, and subfractions containing saturates, aromatic and polar compounds were obtained and analyzed by the same instrumental approach. The investigation showed clear differences between the samples coming from the two oils. The instrumental approach did not lead to an accurate description of the different components in terms of elemental composition and structures; however, valid information could be obtained on the molecular weight distribution of the components of the different fractions. Copyright 2007 John Wiley & Sons, Ltd. [source]

    Laser desorption/ionization techniques in the characterization of high molecular weight oil fractions.

    Part 1: asphaltenes
    Abstract The molecular weight distribution of the asphaltene fractions of two types of crude oils from two different Italian fields (samples 1 and 2) was investigated. The analytical tools used to perform these analyses were matrix assisted laser desorption ionization (MALDI) and laser desorption ionization (LDI) mass spectrometry. After observing that the use of the matrix (as well as the addition of Ag+) did not improve the quality of the data compared to that obtained in LDI conditions, all further measurements were performed with the latter technique. Operating under usual conditions of laser power and delay time, a very low resolution was observed, showing only macroscopic differences between the two samples in the molecular weight distribution of the different components. An accurate study on the possible reasons of this undesirable behavior indicates that it can originate from space charge phenomena occurring either in the ion source region or during the flight. A valid parameterization of the delay time and the laser power allowed higher quality spectra to be obtained. Surface-enhanced laser desorption ionization (SELDI) measurements were also performed using normal phase (silica) as the sample holder surface. Under these conditions, better results are obtained, proving that the sample,surface interaction is important to achieve, by means of laser irradiation, a homogeneous set of product ions. Both asphaltene samples were fractionated in five subfractions by gel-permeation chromatography (GPC) to obtain a better separation of the molecular weight distributions; the related spectra confirmed these findings. By using different approaches, relevant and reproducible differences between the asphaltene fractions of the two oil samples were observed. Copyright 2006 John Wiley & Sons, Ltd. [source]

    Dynamic optimization of the methylmethacrylate cell-cast process for plastic sheet production

    AICHE JOURNAL, Issue 6 2009
    Martn Rivera-Toledo
    Abstract Traditionally, the methylmethacrylate (MMA) polymerization reaction process for plastic sheet production has been carried out using warming baths. However, it has been observed that the manufactured polymer tends to feature poor homogeneity characteristics measured in terms of properties like molecular weight distribution. Nonhomogeneous polymer properties should be avoided because they give rise to a product with undesired wide quality characteristics. To improve homogeneity properties force-circulated warm air reactors have been proposed, such reactors are normally operated under isothermal air temperature conditions. However, we demonstrate that dynamic optimal warming temperature profiles lead to a polymer sheet with better homogeneity characteristics, especially when compared against simple isothermal operating policies. In this work, the dynamic optimization of a heating and polymerization reaction process for plastic sheet production in a force-circulated warm air reactor is addressed. The optimization formulation is based on the dynamic representation of the two-directional heating and reaction process taking place within the system, and includes kinetic equations for the bulk free radical polymerization reactions of MMA. The mathematical model is cast as a time dependent partial differential equation (PDE) system, the optimal heating profile calculation turns out to be a dynamic optimization problem embedded in a distributed parameter system. A simultaneous optimization approach is selected to solve the dynamic optimization problem. Trough full discretization of all decision variables, a nonlinear programming (NLP) model is obtained and solved by using the IPOPT optimization solver. The results are presented about the dynamic optimization for two plastic sheets of different thickness and compared them against simple operating policies. 2009 American Institute of Chemical Engineers AIChE J, 2009 [source]

    New strategies for polymer development in pharmaceutical science , a short review

    A. Godwin
    We are developing synthetic polymers for pharmaceutical and medical applications. These applications can be broadly grouped on how the polymer will be utilized e.g. material, excipient or molecule. Our focus is to develop polymers with more defined structures that are based on biological, physicochemical and/or materials criteria. Strategies are being developed to more efficiently optimize structure,property correlations during preclinical development. We describe two examples of our research on pharmaceutical polymer development: narrow molecular weight distribution (MWD) homopolymeric precursors which can be functionalized to give families of narrow MWD homo- and co-polymers, and hydrolytically degradable polymers. [source]

    Preparation of high cis -1,4 polyisoprene with narrow molecular weight distribution via coordinative chain transfer polymerization

    Changliang Fan
    Abstract High cis -1,4 polyisoprene with narrow molecular weight distribution has been prepared via coordinative chain transfer polymerization (CCTP) using a homogeneous rare earth catalyst composed of neodymium versatate (Nd(vers)3), dimethyldichlorosilane (Me2SiCl2), and diisobutylaluminum hydride (Al(i -Bu)2H) which has strong chain transfer affinity is used as both cocatalyst and chain transfer agent (CTA). Differentiating from the typical chain shuttling polymerization where dual-catalysts/CSA system has been used, one catalyst/CTA system is used in this work, and the growing chain swapping between the identical active sites leads to the formation of high cis -1,4 polyisoprene with narrowly distributed molecular weight. Sequential polymerization proves that irreversible chain termination reactions are negligible. Much smaller molecular weight of polymer obtained than that of stoichiometrically calculated illuminates that, differentiating from the typical living polymerization, several polymer chains can be produced by one neodymium atom. The effectiveness of Al(i -Bu)2H as a CTA is further testified by much broad molecular weight distribution of polymer when triisobutylaluminum (Al(i -Bu)3), a much weaker chain transfer agent, is used as cocatalyst instead of Al(i -Bu)2H. Finally, CCTP polymerization mechanism is validated by continuously decreased Mw/Mn value of polymer when increasing concentration of Al(i -Bu)2H extra added in the Nd(ver)3/Me2SiCl2/Al(i -Bu)3 catalyst system. 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010 [source]