Molecular-level insights into dissolved organic matter and its variations of the full-scale processes in a typical petrochemical wastewater treatment plant.

Petrochemical wastewater (PCWW) treatment poses challenges due to its unique and complex dissolved organic matter (DOM) composition, originating from various industrial processes. Despite the addition of advanced treatment units in PCWW treatment plants to meet discharge standards, the mechanisms of molecular-level sights into DOM reactivity of the upgraded full-scale processes including multiple biological treatments and advanced treatment remain unclear. Herein, we employ water quality indexes, spectra, molecular weight (MW) distribution, and Fourier transform ion cyclotron resonance mass spectrometry to systematically characterize DOM in a typical PCWW treatment plant including influent, micro-oxygen hydrolysis acidification (MOHA), anaerobic/oxic (AO), and micro-flocculation sand filtration-catalytic ozonation (MFSF-CO). Influent DOM is dominated by tryptophan-like and soluble microbial products with MW fractions 〈 1 kDa and 〉 100 kDa, and CHO with lignin and aliphatic/protein structures. MOHA effectively degrades macromolecular CHO (10.86 %) and CHON (5.24 %) compounds via deamination and nitrogen reduction, while AO removes CHOS compounds with MW < 10 kDa by desulfurization, revealing distinct DOM conversion mechanisms. MFSF-CO transforms unsaturated components to less aromatic and more saturated DOM through oxygen addition reactions and shows high CHOS and CHONS reactivity via desulfurization and deamination reactions, respectively. Moreover, the correlation among multiple parameters suggests UV254 combined with AImod as a simple monitoring indicator of DOM to access the chemical composition. The study provides molecular-level insights into DOM for the contribution to the improvement and optimization of the upgraded processes in PCWW.

Molecular weight-dependent differences in spectral properties and metal-binding behaviors of dissolved organic matter from different lakes.

Dissolved organic matter (DOM) plays an important role in governing metal speciation and migration in aquatic systems. In this study, various DOM samples were collected from Lakes Erhai, Kokonor, and Chaka, and size-fractionated into high molecular weight (HMW, 1 kDa-0.7 µm) and low molecular weight (LMW, <1 kDa) fractions for measurements of dissolved organic carbon (DOC), spectral properties, and metal binding behaviors. Our results demonstrated that samples from Lake Chaka exhibited the highest DOC concentration and fluorescence indices but the lowest percentage of carbohydrates. Regardless of sampling locations, the HMW-DOM fractions contained higher abundances of aromatic DOM, carbohydrates and protein-like substances, but lower abundance of fulvic acid-like substances compared to those in the LMW fractions. Metal titration experiments coupled with the excitation-emission matrix (EEM)-parallel factor (PARAFAC) modeling revealed that the quenching of the PARAFAC-derived fluorescent components was more pronounced in the presence of Cu(II) compared to Pb(II). Humic-like components emerged as a superior model, exhibiting higher binding affinities for Cu(II) than protein-like substances, while the opposite trend was observed for Pb(II). In samples obtained from Lakes Erhai and Kokonor, the condition stability constants (Log KM) for the binding of both Cu(II) and Pb(II) with the HMW-DOM fraction were higher than those with the LMW-DOM fraction. Conversely, a contrasting trend was observed for Lake Chaka. This study highlighted the heterogeneity in spectral properties and metal-binding behaviors of natural DOMs, contributing to an improved understanding of the molecular interactions between DOM components and metal ions and their environmental fate in aquatic ecosystems.

Ultrafiltration fractionation of potentially inhibitory substances of hydrothermal liquefaction aqueous phase derived from municipal sludge.

Hydrothermal liquefaction (HTL) is a promising thermo-chemical technology for municipal sludge treatment due to its potential for biocrude oil recovery and minimizing biosolids management costs. However, the process generates a high volume of an aqueous byproduct that needs to be treated due to its high chemical oxygen demand (COD) and various organic and inorganic compounds. Although the aqueous phase is known to contain recalcitrant and potentially inhibitory substances that may affect its biological treatment, their molecular weight distribution (MwD) and its impact on anaerobic biodegradability are poorly understood. Ultrafiltration (UF) was conducted to fractionate HTL aqueous into different molecular weight (Mw) fractions using 300, 100, 10, and 1 kDa membranes. Mesophilic biochemical methane potential (BMP) assays were conducted to assess the anaerobic biodegradability of each fraction, and the first-order model was used to calculate the degradation kinetics of potential inhibitory compounds. The highest percentage of organics (65 %) was found in the Mw<1 kDa range, whereas the 10>Mw>1 kDa had the lowest percentage (8 %). There was no significant difference in the cumulative specific methane produced from various Mw fractions (p>0.05). The Mw<1 kDa fraction had the highest first-order specific methane production rate (0.53 day-1), whereas the unfiltered HTL had the lowest (0.38 day-1). Although UF fractionation increased the rate of anaerobic degradation of HTL aqueous for the Mw<1 kDa fraction, the observed methane potential was only 55 % of the theoretical value. This implies that 45 % of COD remains undegraded even after permeation through the lowest Mw cut-off membrane. Therefore, further characterization of HTL aqueous is needed for compounds with molecular weights below 1 kDa to fully understand the nature of inhibitory organics and their impact on anaerobic digestion. Furthermore, pretreatments utilizing techniques such as adsorption and advanced oxidation may be necessary to enhance the specific methane yields from various HTL aqueous fractions, thereby bringing them closer to the theoretical yield.

Revealing the Effect of the Molecular Weight Distribution on the Chain Diffusion and Crystallization Process under a Branched Trimodal Polyethylene System.

With the increasing demand for high-end materials, trimodal polyethylene (PE) has become a research hotspot in recent years due to its superior performance compared with bimodal PE. By means of molecular dynamics (MD) simulations, we aim to expound the effect of the molecular weight distribution (MWD) on the mechanism of nucleation and crystallization of trimodal PE. The crystallization rate is faster when short-chain branching is distributed on a single backbone compared to that on two backbones. In addition, as the content of high molecular weight backbone decreases, the time required for nucleation decreases, but the crystallization rate slows down. This is because low molecular weight backbones undergo intra-chain nucleation and crystallize earlier due to the high diffusion capacity, which leads to entanglement that prevents the movement of medium or high molecular weight backbones. Furthermore, crystallized short backbones hinder the movement and crystallization of other backbones. What is more, a small increase in the high molecular weight branched backbone of trimodal PE can make the crystallinity greater than that of bimodal PE, but when the content of high molecular weight backbone is too high, the crystallinity decreases instead, because the contribution of short and medium backbones to high crystallinity is greater than that of long backbones.

4D-Printable Photocrosslinkable Polyurethane-Based Inks for Tissue Scaffold and Actuator Applications.

4D printing recently emerges as an exciting evolution of conventional 3D printing, where a printed construct can quickly transform in response to a specific stimulus to switch between a temporary variable state and an original state. In this work, a photocrosslinkable polyethylene-glycol polyurethane ink is synthesized for light-assisted 4D printing of smart materials. The molecular weight distribution of the ink monomers is tunable by adjusting the copolymerization reaction time. Digital light processing (DLP) technique is used to program a differential swelling response in the printed constructs after humidity variation. Bioactive microparticles are embedded into the ink and the improvement of biocompatibility of the printed constructs is demonstrated for tissue engineering applications. Cell studies reveal above 90% viability in 1 week and ≈50% biodegradability after 4 weeks. Self-folding capillary scaffolds, dynamic grippers, and film actuators are made and activated in a humid environment. The approach offers a versatile platform for the fabrication of complex constructs. The ink can be used in tissue engineering and actuator applications, making the ink a promising avenue for future research.

An exact and vigorous kinetic Monte Carlo simulation to determine the properties of bimodal HDPE synthesized with a dual-site metallocene catalyst.

A vigorous and progressed Monte Carlo strategy was developed to precisely simulate the ethylene and 1-butene copolymerization within the presence of hydrogen by dual-site metallocene catalyst. The results showed up that the ethylene and 1-butene consumption rates at the second catalyst site were approximately 5 times higher than at the first site, and hydrogen transfer rates at the first catalyst site were over 3 times more rapid than at the second site. It was found that the most elevated molar percentage of 1-butene inside the copolymers synthesized from the second site was around 12% and within the copolymers gotten from the first site was around 2%. At a steady hydrogen concentration, with 8 times increase in the 1-butene concentration within the initial feed, the overall weight average molecular weight (M‾w) and an overall number average molecular weight (M‾n) extended by approximately 50% and 40%, respectively. Besides, at a consistent 1-butene concentration, with 8 times increase in the concentration of hydrogen, M‾w and M‾n diminished by approximately 18% and 22%, separately. Due to the synthesis of two groups of chains with distinct molecular weights, the overall dispersity (D) was slightly higher than the dispersity resulting from each catalyst site (1.5-2.1). With increasing 1-butene concentrations, the overall bimodal molecular weight distribution (MWD) widened, and the peak sizes grew smaller and moved towards higher molecular weights. As hydrogen concentration increased, peaks became taller and move toward shorter chain lengths. It was observed that the first site created chain lengths between 102 and 103 while the second site generated chain lengths between 102 and 106. As the concentration of 1-butene was increased in the initial feed, the number of short chain branching per 1000 carbon atoms (SCB/1000C) increased from 10 to 50. Compared to the first site, there were 5 times as many SCBs at the chains produced from the second site. By diminishing the ratio of ethylene to 1-butene, the melt index (MI) tended towards smaller numbers (0.2≤MI≤2). With an increase in the ratio of ethylene to 1-butene and ethylene to hydrogen, the weight fraction of crystals raised from 67.4 to 69.5% and diminished from 71 to 69.5%, respectively. At last, increasing the temperature led to a diminish in molecular weight, a narrowing of the bimodal MWD, an increment within the thickness and weight fraction of crystals, and an increment within the density of HDPE.

Heterogeneity of Active Sites in the Polymer Chain Transfer Reactions at Olefin Polymerization over Multisite Supported Ziegler-Natta Catalysts.

In this review, we summarize and discuss our experimental data published in a number of papers on the transfer reactions of polymer chains in the polymerization of ethylene, propylene, and hexene-1, and the copolymerization of ethylene with α-olefins over multisite supported titanium-magnesium catalysts (TMC). Three groups of transfer reactions are discussed in the review: (1) transfer reactions with AlEt3 cocatalyst, (2) transfer reactions with hydrogen, and (3) transfer reactions with participation of α-olefins in the case of ethylene copolymerization with α-olefins. We have found polymerization conditions where it is possible to observe heterogeneity of active sites of TMC for all three groups of the indicated reactions. It is shown that (1) the transfer reaction with AlEt3 proceeds with higher reactivity on the active sites that produce polymers with low molecular weight; (2) the transfer reaction with hydrogen, in the case of α-olefin polymerization and copolymerization of ethylene with α-olefins, proceeds with higher reactivity on the active sites which produce polymers with high molecular weight; (3) the transfer reaction with α-olefins proceed with higher reactivity on the active sites that produce high molecular weight polymers.

The Effects of Enzymes, Species, and Storage of Raw Material on Physicochemical Properties of Protein Hydrolysates from Whitefish Heads.

The rest raw materials of whitefish have great potential for increased utilisation and value creation. Whitefish heads have a high protein content and should be considered a healthy protein source for the growing population's demands for sustainable protein. In this study, the heads of four different species of whitefish were processed via enzymatic hydrolysis, namely cod (Gadus morhua), cusk (Brosme bromse), haddock (Melanogrammus aeglefinus), and saithe (Pollachius virens), using three commercially available enzymes. Trials were conducted after 0, 3, and 6 months of the frozen storage of heads. A proximate analysis, molecular weight distribution, and protein solubility were evaluated for each of the products. The results show that, although the enzymatic hydrolysis of rest raw materials from different species of whitefish yielded products of slightly different characteristics, this process is viable for the production of high-quality protein from cod, cusk, haddock, and saithe heads. Six months of frozen storage of heads had a minimal effect on the yield and proximate composition of hydrolysates.

Visible Light Photoiniferter Polymerization for Dispersity Control in High Molecular Weight Polymers.

The synthesis of polymers with high molecular weights, controlled sequence, and tunable dispersities remains a challenge. A simple and effective visible-light controlled photoiniferter reversible addition-fragmentation chain transfer (RAFT) polymerization is reported here to realize this goal. Key to this strategy is the use of switchable RAFT agents (SRAs) to tune polymerization activities coupled with the inherent highly living nature of photoiniferter RAFT polymerization. The polymerization activities of SRAs were in situ adjusted by the addition of acid. In addition to a switchable chain-transfer coefficient, photolysis and polymerization kinetic studies revealed that neutral and protonated SRAs showed different photolysis and polymerization rates, which is unique to photoiniferter RAFT polymerization in terms of dispersity control. This strategy features no catalyst, no exogenous radical source, temporal regulation by visible light, and tunable dispersities in the unprecedented high molecular weight regime (up to 500 kg mol-1 ). Pentablock copolymers with three different dispersity combinations were also synthesized, highlighting that the highly living nature was maintained even for blocks with large dispersities. Tg was lowered for high-dispersity polymers of similar MWs due to the existence of more low-MW polymers. This strategy holds great potential for the synthesis of advanced materials with controlled molecular weight, dispersity and sequence.

Influence of Hydrothermal Treatment of Brewer's Spent Grain on the Concentration and Molecular Weight Distribution of 1,3-1,4-ß-D-Glucan and Arabinoxylan.

Brewer's spent grain (BSG) is the most abundant residual in the brewing process. Non-starch polysaccharides such as 1,3-1,4-ß-D-glucan (ß-glucan) and arabinoxylan (AX) with proven beneficial effects on human health remain in this by-product in high amounts. Incorporating the valuable dietary fiber into the food industry could contribute to a healthy diet. However, a major challenge is extracting these dietary fibers (i.e., ß-glucan and AX) from the solid residue. In this study, hydrothermal treatment (HT) was applied to dissolve the remaining water-insoluble carbohydrates from BSG with the aim to extract high amounts of ß-glucan and AX. Particular focus was placed on the molecular weight (MW) range above 50 kDa and 20 kDa, respectively, as these are considered to have health-promoting effects. Different treatment temperatures, reaction times, and internal reactor pressures were tested to determine the best process settings to achieve high yields of ß-glucan and AX and to examine the influence on their molecular weight distribution (MWD). Overall, 85.1% ß-glucan and 77.3% AX were extracted corresponding to 6.3 g per kg BSG at 160 °C and 178.3 g kg-1 at 170 °C, respectively. However, less than 20% of both fiber substances were in the desirable MW range above 50 kDa and 20 kDa, respectively. When lower temperatures of 140 and 150 °C were applied, yields of only 3.0 g kg-1 ß-glucan and 128.8 g kg-1 AX were obtained, whereby the proportion of desirable fiber fractions increased up to 45%. Further investigations focused on the heat-induced degradation of monosaccharides and the formation of undesirable by-products (i.e., HMF and furfural) that might pose a health risk.

Antioxidant Activities of Konjac Glucomannan Hydrolysates of Different Molecular Weights at Different Values of pH.

Konjac glucomannan (KGM) is a high-molecular-weight polysaccharide that was originally extracted from the corms (underground storage organs) of Amorphophallus konjac. KGM and its oligomers have been reported as dietary fibers that exhibit an array of health benefits. The depolymerization of KGM via enzymatic hydrolysis at different conditions gives products of low viscosity and can be used for coating materials in microencapsulation. In the present study, konjac glucomannan hydrolysates (KGMHs) were produced by enzymatic hydrolysis using commercial mannanase at pH 4.5 at 70 °C for 5-120 min, then KGMHs' molecular weight (Mw), Degree of Polymerization (DP) and their bioactivities were determined. A longer hydrolysis time resulted in KGMH of a lower DP. Oligoglucomannans (Mw < 10,000) could be obtained after hydrolysis for 20 min. The DP of KGMH rapidly decreased during an early stage of the hydrolysis (first 40 min); DP reached around 7 at the end of the hydrolysis. Antioxidant activities were determined by the DPPH radical scavenging and FRAP assays of KGMHs prepared at pH 4.5 and evaluated at pH 2.0-8.0 depending on pH. KGMH having lower Mw exhibited higher antioxidant activities. KGMHs having the smallest molecular weight (Mw = 419) exhibited the highest DPPH radical scavenging activity. Mw and pH have a greater impact on KGMHs' bioactivities which can be useful information for KGMHs as functional ingredients.

Dimethylformamide Impurities as Propylene Polymerization Inhibitor.

This research study examined how the use of dimethylformamide (DMF) as an inhibitor affects the propylene polymerization process when using a Ziegler-Natta catalyst. Several experiments were carried out using TiCl4/MgCl2 as a catalyst, aluminum trialkyl as a cocatalyst, and different amounts of DMF. Then, we analyzed how DMF influences other aspects of the process, such as catalyst activity, molecular weight, and the number of branches in the polymer chains obtained, using experimental and computational methods. The results revealed that as the DMF/Ti ratio increases, the catalyst activity decreases. From a concentration of 5.11 ppm of DMF, a decrease in catalyst activity was observed, ranging from 45 TM/Kg to 44 TM/Kg. When the DMF concentration was increased to 40.23 ppm, the catalyst activity decreased to 43 TM/Kg, and with 75.32 ppm, it dropped even further to 39 TM/Kg. The highest concentration of DMF evaluated, 89.92 ppm, resulted in a catalyst productivity of 36.5 TM/Kg and lost productivity of 22%. In addition, significant changes in the polymer's melt flow index (MFI) were noted as the DMF concentration increased. When 89.92 ppm of DMF was added, the MFI loss was 75%, indicating a higher flowability of the polymer. In this study, it was found that dimethylformamide (DMF) exhibits a strong affinity for the titanium center of a Ziegler-Natta (ZN) catalyst, with an adsorption energy (Ead) of approximately -46.157 kcal/mol, indicating a robust interaction. This affinity is significantly higher compared to propylene, which has an Ead of approximately -5.2 kcal/mol. The study also revealed that the energy gap between the highest occupied molecular orbital (HOMO) of DMF and the lowest unoccupied molecular orbital (SOMO) of the Ziegler-Natta (ZN) catalyst is energetically favorable, with a value of approximately 0.311 eV.

Inhibition of human cervical cancer development through p53-dependent pathways induced by the specified triple helical ß-glucan.

This study demonstrates that the purified ß-glucan (LNT) with a triple helix and relatively narrow molecular weight distribution, extracted and purified from artificially cultured Lentinus edodes, showed a significant cervical cancer inhibition with little cytotoxicity against normal cells in vitro and in vivo. From the in vitro data, the potential mechanism of anti-cervical cancer was preliminarily revealed as follows: LNT was firstly recognized by the human cervical cancer cell line of Hela and induced cell proliferation inhibition through p21 and apoptosis via a mitochondrion-dependent pathway by targeting the tumor suppressor of p53, indicated by an increase in reactive oxygen species (ROS) generation and a loss of mitochondrial membrane potential (Δψm), in a significant dosage-dependent manner. Meanwhile, LNT repressed tumor growth with an inhibition ratio of 61.2 % and induced tumor cell apoptosis through endogenous MDM2/p53/Bax/mitochondrion signal pathway by up-regulating the expression of p53, Bax, Cyt. c, caspase 9, and caspase 3, as well as down-regulating Bcl-2, MDM2, and PARP1 levels in Hela cells-transplanted BALB/c nude mice. This study provides a scientific basis for the clinical treatment of cervical cancer with LNT as a potential drug candidate characterized by the triple helix and specified molecular weight with a relatively narrow distribution.

Type of intrinsic resistant starch type 3 determines in vitro fermentation by pooled adult faecal inoculum.

Resistant starch (RS) results in relatively high health-beneficial butyrate levels upon fermentation by gut microbiota. We studied how physico-chemical characteristics of RS-3 influenced butyrate production during fermentation. Six highly resistant RS-3 substrates (intrinsic RS-3, 80-95 % RS) differing in chain length (DPn 16-76), Mw distribution (PI) and crystal type (A/B) were fermented in vitro by pooled adult faecal inoculum. All intrinsic RS-3 substrates were fermented to relatively high butyrate levels (acetate/butyrate ≤ 2.5), and especially fermentation of A-type RS-3 prepared from polydisperse α-1,4 glucans resulted in the highest relative butyrate amount produced (acetate/butyrate: 1). Analysis of the microbiota composition after fermentation revealed that intrinsic RS-3 stimulated primarily Lachnospiraceae, Bifidobacterium and Ruminococcus, but the relative abundances of these taxa differed slightly depending on the RS-3 physico-chemical characteristics. Especially intrinsic RS-3 of narrow disperse Mw distribution stimulated relatively more Ruminococcus. Selected RS fractions (polydisperse Mw distribution) obtained after pre-digestion were fermented to acetate and butyrate (ratio ≤ 1.8) and stimulated Lachnospiraceae and Bifidobacterium. This study indicates that especially the α-1,4 glucan Mw distribution dependent microstructure of RS-3 influences butyrate production and microbiota composition during RS-3 fermentation.

Long-Term Aging Behavior of Plastic/Styrene Butadiene Rubber (SBR) Composite Modified Bitumen.

The reuse of recycled waste plastics has long been attempted in pavement engineering as bitumen modifier. It was revealed that waste plastics can significantly enhance the high-temperature performance of bitumen and bitumen mixtures. Even so, the application of waste plastics as a bitumen modifier is still not widespread. This is attributable to the generally poor low-temperature performance of plastic-modified bitumen, which often fails to meet specification requirements. For this purpose, styrene butadiene rubber (SBR) was selected to improve the low-temperature performance of plastic-modified bitumen. However, due to the long-term aging process, the composite and structure of the modified bitumen will change, which negatively impacts its performance. The objective of this study is to investigate the long-term aging behavior of plastic/SBR composite-modified bitumen. For this purpose, waste polyethylene was used as a plastic modifier and was mixed with base bitumen and 3% SBR at ratios 4.5%, 6% and 7.5%. The rheological properties and molecular weight distribution of base bitumen, plastic and plastic/SBR-modified bitumen before and after long-term aging were measured. Results show that the incorporation of plastic can improve the complex modulus, rutting factor and percent recovery of bitumen and reduce the non-recoverable creep compliance of the bitumen, indicating the modification process enhances the high-temperature performance of bitumen. The enhancement effect is more pronounced with the increase of plastic content. For modified bitumen with 7.5% plastic modifier, the complex modulus of modified bitumen is increased by 1127.55% compared to base bitumen. The addition of 3% SBR modifier can further improve the high-temperature performance of the modified bitumen. In addition, the modification process also increases the large molecule size percentage (LMSP) and weight average molecular weight of bitumen. Compared with weight average molecular weight, the LMSP correlates well with the rheological properties of modified bitumen. In accordance with the complex modulus, using the LMSP and weight average molecular weight of bitumen before and after aging, the corresponding aging index was calculated. The quantitative results showed that the addition of plastic modifier can improve the aging resistance of bitumen, but the enhancement effect is not as obvious as that of SBR modifier.

Multi-Scale Structural Insights into Enzymatically Hydrolyzed Lentil Starch Concentrates Prepared by In Vitro Method Using Different Types of Enzymes.

This study was undertaken to investigate the enzymatic hydrolysis of lentil starch concentrates from conventional cooked seeds (CCLSC) by the action of different types of enzymes, including pancreatin (PC-EHSC), heat-stable α-amylase (HS-EHSC), ß-amylase (ßA-EHSC), amyloglucosidase (AMG-EHSC), and multi-enzymes (ßA-HS-AMG-EHSC); their multi-scale structural characteristics of the enzymatic hydrolysis products of lentil starch concentrates were compared. The morphological features distinguished among different samples. The Fourier-transform infrared spectroscopy and solid-state 13C CP/MAS NMR spectral features indicated the possible formation of a binary and ternary complex among amylose, protein and lipids. The X-ray diffraction results revealed that the V-type characteristic diffraction peaks were more obvious for samples including PC-EHSC and ßA-EHSC, which was in line with their lowest polydispersity index (DPn). PC-EHSC and ßA-EHSC also showed an increased peak intensity of the scattering maximum on the small-angle X-ray scattering spectra, whereas CCLSC exhibited an overall lower peak intensity within the studied q range of scattering. The highest XRD crystallinity and the lowest DPn value obtained for PC-EHSC indicated that the starch polymers modified by pancreatin could produce glucan chains with a comparatively homogenous Mw distribution that are readily recrystallized by hydrogen bonding through chain aggregation. Comparatively, the lowest relative crystallinity for HS-EHSC obtained from XRD suggested that thermostable α-amylolysis was unfavorable for the formation of starch structure with a higher degree of molecular order. This study could provide useful information for the needed research to obtain a deeper understanding of the impact of different amylolysis actions on the structural organization of starch hydrolysates and to provide a theoretical foundation for the development of fermentable enzymatically hydrolyzed starch with well-tailored physiological properties.

Ketyl Radical Anion Mediated Radical Polymerization and Anionic Ring-Opening Polymerization to Give Polymers with Low Molecular Weight Distribution.

The development of novel polymerization capable of yielding polymers with low molecular weight distribution (D) is essential and significant in polymer chemistry, where monofunctional initiator contains only one initiation site in these polymerizations generally. Here, ketyl radical anion species is introduced to develop a novel Ketyl Mediated Polymerization (KMP), which enables radical polymerization at carbon radical site and anionic ring-opening polymerization at oxygen anion site, respectively. Meanwhile, polymerization and corresponding organic synthesis generally couldn't be performed simultaneously in one pot. Through KMP, organic synthesis and polymerization are achieved in one pot, where small molecules (cyclopentane derivates) and polymers with low D are successfully prepared under mild condition simultaneously. At the initiation step, both organic synthesis and polymerization are initiated by single electron transfer reaction with ketyl radical anion formation. Cyclopentane derivates are synthesized through 3-3 coupling reaction and cyclization. Polystyrene and polycaprolactone with low D and a full monomer conversion are prepared by KMP via radical polymerization and anionic ring-opening polymerization, respectively. This work therefore enables both organic synthesis and two different polymerizations from same initiation system, which saves time, labour, resource and energy and expands the reaction mode and method libraries of organic chemistry and polymer chemistry.

Molecular Weight Distribution of Branched Polymers: Comparison between Monte Carlo Simulation and Flory-Stockmayer Theory.

It is challenging to predict the molecular weight distribution (MWD) for a polymer with a branched architecture, though such information will significantly benefit the design and development of branched polymers with desired properties and functions. A Monte Carlo (MC) simulation method based on the Gillespie algorithm is developed to quickly compute the MWD of branched polymers formed through step-growth polymerization, with a branched polyetherimide from two backbone monomers (4,4'-bisphenol A dianhydride and m-phenylenediamine), a chain terminator (phthalic anhydride), and a branching agent (tris[4-(4-aminophenoxy)phenyl] ethane) as an example. This polymerization involves four reactions that can be all reduced to a condensation reaction between an amine group and a carboxylic anhydride group. A comparison between the MC simulation results and the predictions of the Flory-Stockmayer theory on MWD shows that the rates of the reactions are determined by the concentrations of the functional groups on the monomers involved in each reaction. It further shows that the Flory-Stockmayer theory predicts MWD well for systems below the gel point but starts to fail for systems around or above the gel point. However, for all the systems, the MC method can be used to reliably predict MWD no matter if they are below or above the gel point. Even for a macroscopic system, a converging distribution can be quickly obtained through MC simulations on a system of only a few hundred to a few thousand monomers that have the same molar ratios as in the macroscopic system.

Effects of glutenin and gliadin on the surface tackiness of frozen cooked noodles.

The mechanism of glutenin and gliadin on the surface tackiness of recooked frozen cooked noodles (FCNs) is unclear. In this study, the effects of glutenin and gliadin addition on the surface tackiness of FCNs were investigated. The addition of glutenin and gliadin reduced the surface tackiness (3.60 and 3.50 N) of recooked FCNs stored for 0 min. The addition of glutenin increased the rigidity of the gluten network and the compactness of FCNs and made the FCNs have a moisture-distribution with multilayers. The addition of gliadin increased the tensile distance of FCNs, restricted water migration during frozen storage, and increased the membranous structure of the gluten network to wrap starch particles. Glutenin had a stronger effect on reducing the surface tackiness of FCNs than gliadin. In the future, the synergistic effects of different proportions of glutenin and gliadin on the gluten network of FCNs could be further studied.

Seasonal Changes in Qualitative and Quantitative Characteristics of Humic Substances in Waters of Different Genesis: Membrane Technologies and Equilibrium Processes.

Membrane filtration methods were applied in this study to research natural waters specification (and speciation). Lysimetric waters (soil waters) of background territories in different seasons are considered. Features of the change in molecular weights, elemental composition, and zeta potential of organic matter during fractionation from 8 µm to 100 kDa were found. The number of labile and non-labile speciation of some elements obtained by membrane filtration and ion-exchange separation methods were found and compared. The highest molecular weights of organic substances were found in summer samples of lysimetric waters (more than 100 kDa) with a predominance of the aromatic component in the IR spectra of the samples. Several maxima were also found in the molecular weight distribution, including the increase in autochthonous organic substances. The most stable negative zeta potential, as a stabilized colloid matter, are represented in summer (near -26 mV) and in autumn (near -22 mV) lysimetric water. A slight increase in metal ions bound into organic complexes is typical for summer and autumn samples.