Degree Of Branching Research Articles

Preparation of organosilicon and organofluorine synergistically modified amphiphilic branched polyurethanes and their application in diisocyanate emulsifiers

AbstractIsocyanate‐based monomers and polymers have found widespread industrial application; however, the realization of green water‐based products via the preparation of stable isocyanate aqueous emulsions remains challenging. Herein, a series of organosilicon and organofluorine synergistically modified amphiphilic branched polyurethanes (HBWPU), synthesized by grafting perfluorohexyl ethanol semi‐terminated isophorone diisocyanate (IPDI) onto a hydrophilic polyurethane prepolymer, is presented. Subsequently, using a physical mixing method, stable diisocyanate emulsions are fabricated by preparing diisocyanate latex particles with IPDI as the core and hyperbranched water‐based polyurethanes (HBWPU) as the shell. Structural investigations showed that the branching degree and fluorine content of the HBWPU significantly affects the stability of the diisocyanate emulsions. Increasing the degree of branching from 0.34 to 0.86 causes the amount of residual isocyanate (NCO) groups to decrease from 20.1% to 16.7%. In contrast, an increase in the fluorine content from 0% to 17.8% increases the amount of residual NCO groups from 11.5% to 24.6%. Thus, HBWPU can be used as an emulsifier to prepare waterborne diisocyanate cross‐linking agents. Such polyurethane‐coated isocyanate aqueous emulsions can increase the hardness and significantly improve the acetone resistance of hydroxyl polyacrylate resins.

Synthesis and structure–property relationship of coal-based isomeric alkylbenzene sulfonate surfactants

Using coal resources to synthesize high-value surfactants is effective for clean coal utilization and low-carbon conversion, attracting more attention from academia and industry. Herein, three coal-based isomeric alkylbenzene sulfonate surfactants were successfully synthesized via sulfonation with gas phase SO3 utilizing isomeric alkylbenzenes, derived from the alkylation of benzene and Fischer–Tropsch synthesized α-olefins, as raw materials in a microchannel reactor. Moreover, their surfactant properties were systematically investigated to reveal the structure–property relationship. The results indicated that the equilibrium surface tension (γCMC) for the synthesized surfactants was reduced with the increase of the degree of hydrophobic tails branching, and the order of γCMC was: sodium dodecylbenzene sulfonate (35.67 mN·m−1) > sodium C6 olefin dimer alkylbenzene sulfonate (34.18 mN·m−1) > sodium dihexylalkylbenzene sulfonate (29.94 mN·m−1). Sodium dihexylalkylbenzene sulfonate with the lower γCMC exhibited superior wettability (the contact angle of 50.2 ° at 30 s) and excellent emulsifying capacity (emulsification time of 1337 s) at the corresponding critical micelle concentration. This study provides new insights into rational design of hydrophobic tail architectures of surfactant molecules to meet specific needs in various fields.

Rheology of polyborazanes with various molecular structures and dynamic transformation process

AbstractThe molecular structure of polymer precursors significantly affects their rheological properties, thermal stability, and ceramic conversion rates. For the first time, we revealed the effects of polyborazane molecular structure on rheology and molecular configuration dynamic transformation process. The systems studied are polyborazane precursors with rigid six‐membered ring structures. We synthesized precursors with different molecular structures, including polyborazanes with varying degrees of branching and molecular chain flexibility, and investigated how molecular structure affects viscosity under different conditions of temperature, time, and shear rates. The results indicate that decreasing the branching degree enhances thermal stability and reduces both zero‐shear viscosity and infinite‐shear viscosity. Increasing the flexibility of molecular chains notably reduces infinite‐shear viscosity, while having minimal impact on zero‐shear viscosity and thermal stability. In conclusion, the ideal molecular structure should aim to increase the flexibility of the molecular chains while maintaining a certain degree of branching, such as a dendritic molecular configuration. By correlating viscosity data with molecular structure, we constructed a dynamic transition process of molecular chain entanglement, disentanglement, and crosslinking. This research is essential for understanding polymer rheology and its applications in industry, particularly in designing and synthesizing precursor structures for producing various ceramic fibers through Polymer‐Derived Ceramics.

Synthesis and end-group control of soluble, high-molecular-weight hyperbranched poly(phenylene thienylene)s by non-stoichiometric A2 + B3 Suzuki-Miyaura polycondensation without gelation

Non-stoichiometric Suzuki-Miyaura polycondensation of tribromo monomer 1, containing a thienylene group, with diboronic acid (ester) monomer 7 in the presence of tBuPPd catalyst, which has a propensity for intramolecular catalyst transfer on a π-electron face, was investigated. We anticipated that the presence of thienylene groups in the obtained hyperbranched polymer would increase the detection sensitivity in matrix-assisted laser desorption/ionization time-of-flight (MALDI-TOF) mass spectrometry and enable the analysis of the polymer end groups up to the high-molecular-weight region. We first conducted Suzuki-Miyaura reaction of several kinds of 1 with phenylboronic acid 2 in the presence of tBuPPd precatalyst 3. The reaction of tris(5-bromo-4-hexylthien-2-yl)benzene 1c with 2 afforded exclusively tri-substituted product 4c, indicating that the tBuPPd catalyst undergoes intramolecular catalyst transfer on 1c after the first and second substitutions of 1c with 2. The polycondensation of equimolar 1c and pinacol phenylenediboronate 7a (reaction site ratio of Br:BPin = 1.5:1.0 (BPin = pinacol boronate)) was then carried out in the presence of 3 for 3 h, affording hyperbranched polymer with Mn = 37500 without gelation. The product was purified by precipitation. The degree of polymerization (DP) was calculated from the absolute molecular weight, determined by multi-angle light scattering (MALLS) analysis, to be 200, which is a far higher than would be predicted from the Flory-Stockmayer theory at the critical gel point (DP = 6.6). Furthermore, the MALDI-TOF mass spectra showed two series of peaks due to polymer with boronate ends and boronate ends along with one cyclic unit up to m/z of about 7500, as we had expected. The absence of peaks due to polymer with Br ends indicates that the degree of branching (DB) of this hyperbranched polymer is 100 %.

Sustainable improvement in the polylactic acid properties of 3D printing filaments: The role of bamboo fiber and epoxidized soybean oil‐branched cardanol ether compatibilizer

AbstractPolylactic acid (PLA) is the prevailing raw material for fused deposition modeling (FDM) 3D printing filaments, offering benefits such as a low printing temperature, minimal shrinkage, and biodegradability. However, this material has challenges such as poor toughness, low heat deflection temperature, susceptibility to moisture‐induced thermal degradation, and high costs. This study addressed these concerns by incorporating natural bamboo fiber (BF) into PLA, elevating heat the deflection temperature and lowering the material costs. Additionally, a synthesized branched structure compatibilizer, in the form of epoxidized soybean oil‐branched cardanol ether (ESOn‐ECD), enhanced the toughness of PLA, the bonding strength between PLA and the BF surface, and the flowability of high‐fiber composites during processing and printing. The mechanical, thermal, and rheological properties were assessed, demonstrating the promising processing performance of PLA/BF/ESO3‐ECD. The fully biobased composite exhibits strength, toughness, good processability, excellent 3D printability, and durability, implying substantial potential in FDM 3D filament production.Highlights Bio‐based PLA/bamboo fiber/ESO3‐ECD FDM 3D printing filaments were developed. The excellent nucleation ability of the bamboo fibers enhances the crystallization rate and crystallinity of PLA. The epoxy values and branching degree of ESOn‐ECD are crucial for its effective modification.

Modeling the influence of carbon branching structure on secondary organic aerosol formation via multiphase reactions of alkanes

Abstract. Branched alkanes represent a significant proportion of hydrocarbons emitted in urban environments. To accurately predict the secondary organic aerosol (SOA) budgets in urban environments, these branched alkanes should be considered as SOA precursors. However, the potential to form SOA from diverse branched alkanes under varying environmental conditions is currently not well understood. In this study, the Unified Partitioning Aerosol Phase Reaction (UNIPAR) model is extended to predict SOA formation via the multiphase reactions of various branched alkanes. Simulations with the UNIPAR model, which processes multiphase partitioning and aerosol-phase reactions to form SOA, require a product distribution predicted from an explicit gas kinetic mechanism, whose oxygenated products are applied to create a volatility- and reactivity-based αi species array. Due to a lack of practically applicable explicit gas mechanisms, the prediction of the product distributions of various branched alkanes was approached with an innovative method that considers carbon lengths and branching structures. The αi array of each branched alkane was primarily constructed using an existing αi array of the linear alkane with the nearest vapor pressure. Generally, the vapor pressures of branched alkanes and their oxidation products are lower than those of linear alkanes with the same carbon number. In addition, increasing the number of alkyl branches can also decrease the ability of alkanes to undergo autoxidation reactions that tend to form low-volatility products and significantly contribute to alkane SOA formation. To account for this, an autoxidation reduction factor, as a function of the degree and position of branching, was applied to the lumped groups that contain autoxidation products. The resulting product distributions were then applied to the UNIPAR model for predicting branched-alkane SOA formation. The simulated SOA mass was compared to SOA data generated under varying experimental conditions (i.e., NOx levels, seed conditions, and humidity) in an outdoor photochemical smog chamber. Branched-alkane SOA yields were significantly impacted by NOx levels but insignificantly impacted by seed conditions or humidity. The SOA formation from branched and linear alkanes in diesel fuel was simulated to understand the relative importance of branched and linear alkanes with a wide range of carbon numbers. Overall, branched alkanes accounted for a higher proportion of SOA mass than linear alkanes due to their higher contribution to diesel fuel.

Relationship between Chalkiness and the Structural and Physicochemical Properties of Rice Starch at Different Nighttime Temperatures during the Early Grain-Filling Stage.

The chalkiness, starch fine structure, and physiochemical properties of rice starch were analyzed and their correlations were investigated under different nighttime temperatures during the early grain-filling stage. Compared to MT, medium temperature (MT) and low (LNT) and high (HNT) nighttime temperatures resulted in an increased chalky grain rate (CGR) and chalkiness degree (CD). LNT mainly affected the chalkiness by increasing peak1 (short branch chains of amylopectin), the branching degree, and the proportion of small starch granules but decreasing peak2 (long branch chains of amylopectin) and peak3 (amylose branches). This altered the pasting properties, such as by increasing the peak viscosity and final viscosity. However, HNT mainly affected the chalkiness by increasing peak2 and the crystallinity degree but decreasing peak1 and peak3. Regarding the thermal properties, HNT also elevated peak and conclusion temperatures. The CGR and CD were significantly and positively correlated with the proportions of small and medium starch granules, peak1, branching degree, gelatinization enthalpy, setback viscosity, and pasting time but markedly and negatively correlated with the proportion of large starch granules, amylose content, peak3, peak viscosity, and breakdown viscosity. These findings suggest that LNT and HNT disrupted the starch structure, resulting in increased chalkiness. However, their mechanisms of action differ.

Enhancing the nonlinear rheological property and digestibility of mung bean flour gels using controlled microwave treatments: Effect of starch debranching and protein denaturation

In this study, we examined the possibility of using industrial microwave processing to enhance the gelling properties and reduce the starch digestibility of mung bean flour (MBF). MBF (12.6 % moisture) was microwaved at a power of 6 W/g to different final temperatures (100–130 °C), and then its structural and functional properties were characterized. The microwave treatment had little impact on the crystalline structure or amylose content of the starch, but it roughened the starch granule surfaces and decreased the short-range ordered structure and degree of branching. In addition, the extent of mung bean protein denaturation caused by the microwave treatment depended on the final temperature. Slightly denaturing the proteins (100 °C) did not affect the nature of the gels (protein phase dispersed in a starch phase) but the gel network became more compact. Moderately denaturing the proteins (110–120 °C) led to more compact and homogeneous starch-protein double network gels. Excessive protein denaturation (130 °C) caused the gel structure to become more heterogeneous. As a result, the facilitated tangles between starch chains by more linear starch molecules after debranching, and the protein network produced by moderate protein denaturation led to the formation of stronger gel and the improvement of plasticity during large deformation (large amplitude oscillatory shear-LAOS). Starch recrystallization, lipid complexion, and protein network retard starch digestion in the MBF gels. In conclusion, an industrial microwave treatment improved the gelling and digestive properties of MBF, and Lissajous curve has good adaptability in characterizing the viscoelasticity of gels under large deformations.

A unified kinetic analysis for the hyperbranched polymerization with ABg type monomers

The unified analytical expressions of the size distribution function and the degree of branching for the hyperbranched polymerization with ABg type monomers are developed by kinetic theory of polymerization, based on the ABg + ABh + Bf model. The effect of the reactant parameters, the monomers branching degree g and h, the monomers feed ratio r, the functionality f and feed ratio α of the core molecule Bf, on the molecular parameters of the products formed was investigated. Compared with the general polycondensation of ABg monomer or copolycondensation of ABg and AB monomer without core molecule, the presence of multifunctional core molecules makes the polydispersity index of the products go down fast when the reaction approaches completion. At the end of the reaction, the polydispersity index increases with increasing g, and decreases with increasing α and f. For the ABg + AB + B3 polycondensation system, within the range of the feed ratio of ABg monomer less than 0.3, the average chain segment length significantly decreases with the increasing r, and then the change becomes moderate with its further increase. For g > 2, the average chain segment length shows a shallow minimum with increasing r. The degree of branching, fractions of terminal and branching units also show maximum value with the change of monomer feed ratio r. The information obtained in this work can help people understand the structure of ABg type hyperbranched polymers and carry out molecular design.

Controlled Enzymatic Synthesis of Polyesters Based on a Cellulose-Derived Triol Monomer: A Design of Experiment Approach.

Regioselective enzymatic polycondensation of the bio-based cellulose derived polyol, Triol-citro, and dimethyl adipate using Candida antarctica Lipase B (CaLB) was investigated. A Design of Experiment approach with MODDE® Pro 13 was used to determine important factors in the branching behavior of this polymer, and reactant ratio, temperature, reaction time and enzyme wt % were the studied factors. Multifunctional polyesters with pendant hydroxy groups were synthesized and fully characterized using 2D NMR techniques to determine degree of branching. Branching was minimal, with a maximum of 16 % observed, and monomer ratio, temperature and reaction time were all determined to be significant factors. In this work, Mn of up to 13 kDa were achieved, while maintaining degree of branching below 15 %, resulting in a linear polyester with the potential to be further functionalized.

Machine learning-based screening of fuel properties for SI and CI engines using a hybrid group extraction method

The design of high-performance fuels is crucial for achieving clean and efficient combustion of engines. In the current study, a framework for machine learning (ML) model-based fuel design is presented to identify compounds with desired properties for internal combustion engine (ICE) applications. Descriptors computed from newly proposed structural and positional-based group extraction method in this study are used as input in ML models due to the simplicity and computational-efficiency. The ML models were trained and validated using publically available experimental data for up to 1135 compounds. The results demonstrated a high level of predictive accuracy, with R2 values generally exceeding 0.99 for 11 physicochemical properties including melting point, boiling point, enthalpy of vaporization, surface tension, dynamic viscosity, low heating value, liquid density, yield sooting index, cetane number, research octane number and motor octane number. Furthermore, by employing the developed ML models to predict new data, a Fuel Property Database containing 1135 fuels with 12 fuel properties is established, enhanced by an interface for a user-friendly Fuel Physicochemical Properties Prediction Tool that facilitates swift property predictions and database expansion. The Pearson correlation coefficient (PCC) approach is subsequently employed to assess the correlation between descriptors and predicted or experimental properties. The strong agreement between the correlations affirms the effective predictive performance of the ML models within the calibrated data range. Additionally, a PCC analysis is conducted to reveal the individual effects of influential factors and their interactions, highlighting significant features like molecular weight size, degree of branching, and functional group content that influence physical and chemical properties, thereby providing valuable insights for fuel design and optimization. Finally, a initial comprehensive data-driven screening was carried out to identify potential fuel candidates that meet the key property limits for combustion applications in both spark-ignition (SI) and compression-ignition (CI) engines.

Spider silk-inspired heterogeneous interphase featuring hybrid interaction for simultaneously improving the interfacial strength and fracture toughness between carbon fiber and epoxy by regulating hydrogen bond density

Designing advanced fiber-reinforced polymer composites through biological inspiration proved to be a crucial strategy for overcoming limitations in simultaneously enhancing the strength and toughness of composites. To achieve simultaneous improvement in the interfacial strength and toughness between carbon fiber (CF) and epoxy, a spider silk-inspired interphase featuring hybrid interaction was constructed by introducing hyperbranched polyamide-amine (HPAA) and graphene oxide (GO) onto the surface of CF. The results suggested that manipulating the feed ratio to adjust the branching degree of HPAA allowed for the attainment of various hydrogen bond densities. The fiber surface with high hydrogen bond density provided more hydrogen bond interaction sites to promote the deposition of GO. Benefitting from the ameliorative interfacial adhesion force, surface energy and interface thickness, impressive improvements of 94.5 % and 110.0 % in respective interfacial strength and fracture toughness over those of untreated CF/EP composites were achieved for functionalized CF/EP composites. The enhancement mechanism of interfacial performance was attributed to the formation of a “nano-fishnet” structure, which improved the stress transformation efficiency and consumption of external energy absorbed by hydrogen bonds. The method of regulating the branching degree of hyperbranched polymers and hydrogen bond density has opened an advanced way for surface modification of high-performance fibers.

A hybrid steric ligand modification strategy promotes propylene (co)polymerization

Recently, a Hybrid Steric Ligand Modification (HSLM) strategy has been shown to significantly increase the polymerization activity and the branching degree of the resulting (co)polymers in the ethylene (co)polymerization via α-diimine catalysts. In this study, the HSLM strategy was employed for propylene (co)polymerization using a group of α-diimine Pd(II) catalysts with bulky hybrid ligands. The HSLM catalysts (Pd1-4) produced polypropylene with high molecular weights (45.4–156.9 kg/mol) and resulted in significantly high levels of activity (105 g mol−1 h−1). Additionally, nearly half of the propylene underwent chain straightening (1,3-enchainment = 43–46 %). Our findings suggest that Pd1-4 catalysts are more effective than the symmetrical catalysts Pd5-6 in producing high molecular weight polypropylene with high activity. Among all the catalysts tested, Pd4 with 4-tert-butylphenyl displayed the highest polymerization activity and molecular weight, although with lowest branching densities. It is suggested that the HSLM may provide a more open spatial configuration around the metal center, which facilitates the coordination and insertion of propylene molecules as well as chain walking. The hybrid Pd(II) catalysts showed moderate activity during the copolymerization of propylene with MA. The copolymers produced had low molecular weights (3.1–11.2 kg/mol), high branching densities (120–211/1000C), and high incorporation ratios (8.82–18.08 mol%). The copolymerization activity was highest with 4-tert-butylphenyl Pd4. The resulting P-MA copolymers had the highest molecular weight, the largest branching degree, and the lowest incorporation ratios.

Simultaneously efficient dissolution and structural modification of chrysanthemum pectin: Targeting at proliferation of Bacteroides

Pectic polysaccharide is a bioactive ingredient in Chrysanthemum morifolium Ramat. ‘Hangbaiju’ (CMH), but the high proportion of HG domain limited its use as a prebiotic. In this study, hot water, cellulase-assisted, medium-temperature alkali, and deep eutectic solvent extraction strategies were firstly used to extract pectin from CMH (CMHP). CMHP obtained by cellulase-assisted extraction had high purity and strong ability to promote the proliferation of Bacteroides and mixed probiotics. However, 4 extraction strategies led to general high proportion of HG domain in CMHPs. To further enhance the dissolution and prebiotic potential of CMHP, pectinase was used alone and combined with cellulase. The key factor for the optimal extraction was enzymolysis by cellulase and pectinase in a mass ratio of 3:1 at 1 % (w/w) dosage. The optimal CMHP had high yield (15.15 %), high content of total sugar, and Bacteroides proliferative activity superior to inulin, which was probably due to the cooperation of complex enzyme on the destruction of cell wall and pectin structural modification for raised RG-I domain (80.30 %) with relatively high degree of branching and moderate HG domain. This study provided a green strategy for extraction of RG-I enriched prebiotic pectin from plants.

Isolation and characterization of exopolysaccharides from kombucha samples of different origins

Kombucha is prepared by fermenting sugared green or black tea with a symbiotic culture of bacteria and yeast (SCOBY). Some of the bacteria within the SCOBY are known to form exopolysaccharides (EPS) from sucrose. However, it is yet unknown whether water-soluble EPS are formed in kombucha, and if so, which specific EPS are present. Therefore, different kombucha samples were prepared by fermentation of green and black tea with SCOBYs from different manufacturers. Subsequently, the EPS were isolated and characterized by using various chromatographic methods, partial enzymatic hydrolyses and NMR spectroscopy. It was demonstrated that levans with a varying degree of branching at position O1 (4.3–7.9 %) are present, while only trace amounts of glucans were detected. Furthermore, levans isolated from kombucha had a comparably low molecular weight and the content of levan within the kombucha samples varied from 33 to 562 mg levan/L kombucha. Therefore, our study demonstrated that levans are the main EPS type in kombucha and that levan amounts and structures varied when different starter cultures and ingredients were used. Furthermore, we provide a comprehensive data set on the structural variability of levans from kombucha.

Characterization, antioxidant activity and in vitro digestion of hawthorn pectin prepared by gradient ethanol precipitation

Four modified hawthorn pectin fractions (MHPs), named MHP-30, MHP-50, MHP-70 and MHP-90, were obtained by ultrasonic-assisted pectin methyl esterase modification and gradient ethanol precipitation. The results indicated that all four MHPs were composed of galacturonic acid, galactose, xylose, arabinose, glucose and mannose in different proportions. With the increase of the ethanol concentration, the molecular weight, esterification degree and galacturonic acid content of MHPs all decreased, whereas the arabinose content and branching degree increased. The structural characterization from XRD, SEM, and FT-IR showed that four MHPs exhibited amorphous structure, similar functional groups, diverse surface morphologies. Besides, in vitro antioxidant assays confirmed that MHP-70 and MHP-90 exhibited stronger total antioxidant activities than MHP-30 and MHP-50. The results of simulated saliva-gastrointestinal digestion showed that the molecular weight of MHP-70 and MHP-90 remained stable, yielded small amounts of reducing sugars, and were resistant to digestion in the human upper digestive tract. Overall, MHP-70 and MHP-90 shown great potential as novel natural antioxidants, which are expected to be good carbon sources for the utilization of intestinal microorganisms.

Hierarchical Principal Components for Data-Driven Multiresolution fMRI Analyses.

Understanding the organization of neural processing is a fundamental goal of neuroscience. Recent work suggests that these systems are organized as a multiscale hierarchy, with increasingly specialized subsystems nested inside general processing systems. Current neuroimaging methods, such as independent component analysis (ICA), cannot fully capture this hierarchy since they are limited to a single spatial scale. In this manuscript, we introduce multiresolution hierarchical principal components analysis (hPCA) and compare it to ICA using simulated fMRI datasets. Furthermore, we describe a parametric statistical filtering method developed to focus analyses on biologically relevant features. Lastly, we apply hPCA to the Human Connectome Project (HCP) to demonstrate its ability to estimate a hierarchy from real fMRI data. hPCA accurately estimated spatial maps and time series from networks with diverse hierarchical structures. Simulated hierarchies varied in the degree of branching, such as two-way or three-way subdivisions, and the total number of levels, with varying equal or unequal subdivision sizes at each branch. In each case, as well as in the HCP, hPCA was able to reconstruct a known hierarchy of networks. Our results suggest that hPCA can facilitate more detailed and comprehensive analyses of the brain's network of networks and the multiscale regional specializations underlying neural processing and cognition.

Relationship between the poly(glycerol adipate) prepolymers chain microstructure and linear viscoelastic properties of the elastomers

This paper investigates the influence of the time of enzymatic polymerization of glycerol and divinyl adipate on the chain microstructure and the thermal and linear viscoelastic properties (LVE) of the poly(glycerol adipate) prepolymer (pPGA). The immobilized Candida antarctica lipase B (CALB) was used as a regioselective catalyst in the polytransesterification reaction. A series of pPGA prepolymers were synthesized at different duration times of 8, 24, 48 and 72 h and the degree of polymerization (DP) and degree of branching (DB) were determined based on a quantitative NMR analysis. Due to lack in the literature of the described relationship between the properties of the pPGA prepolymers and the PGA elastomers, the main goal of the research was to correlate the microstructure of the prepolymers with linear viscoelastic properties of the elastomers obtained by thermal crosslinking of the respective prepolymers. The respective pPGA prepolymers were cured at 110 °C for 5 days to obtain PGA elastomers. The LVE properties of the PGA elastomers were investigated based on the master curves of the storage (G') and loss (G") modulus. The differences in DP and BD for the pPGA prepolymers translated into the PGA elastomer crosslinking densities and the rubbery plateau modulus (G0). It was shown for the first time that the minor differences in the structure of the pPGA prepolymers (DP of 13 and 21, and DB of 8.4% and 9.7% for the pPGA prepolymers synthesized for 8 and 24 h, respectively) translate into significant differences in the LVE of the PGA elastomers (G0 of 116 kPa and 50 kPa for the PGA elastomers derived from pPGA8 and pPGA24 prepolymers, respectively).

Selective sorting of hexane isomers by anion-functionalized metal-organic frameworks with optimal energy regulation

Extensive efforts have been made to improve the separation selectivity of hydrocarbon isomers with nearly distinguishable boiling points; however, how to balance the high regeneration energy consumption remains a daunting challenge. Here we describe the efficient separation of hexane isomers by constructing and exploiting the rotational freedom of organic linkers and inorganic SnF62− anions within adaptive frameworks, and reveal the nature of flexible host-guest interactions to maximize the gas-framework interactions while achieving potential energy storage. This approach enables the discrimination of hexane isomers according to the degree of branching along with high capacity and record mono-/di-branched selectivity (6.97), di-branched isomers selectivity (22.16), and upgrades the gasoline to a maximum RON (Research Octane Number) of 105. Benefitting from the energy regulation of the flexible pore space, the material can be easily regenerated only through a simple vacuum treatment for 15 minutes at 25 °C with no temperature fluctuation, saving almost 45% energy compared to the commercialized zeolite 5 A. This approach could potentially revolutionize the whole scenario of alkane isomer separation processes.

Two-step modification of pullulanase and transglucosidase: A novel way to improve the gel strength and reduce the digestibility of rice starch

The multiscale structure, gel strength and digestibility of rice starch modified by the two-step modification of pullulanase (PUL) pretreatment and transglucosidase (TG) treatment for 6, 12, 18 and 24 h were investigated. The debranching hydrolysis of PUL produced some linear chains, which rearranged to form stable crystalline structures, reducing the digestible starch content, but weakening the gel strength. TG treatment connected some short chains to longer linear chains via α-1,6-glycosidic bonds, generating the structures of linear chain with fewer branches. The short branches promoted the interaction between starch molecules to form a more compact three-dimensional gel network structure, showing higher hardness and springiness. Moreover, these chains could form more stable crystals, reducing the digestible starch content, and the increase of branching degree inhibited digestive enzyme hydrolysis, reducing the digestion rate. The multiscale structure of starch tended to stabilize after TG treatment for 18 h, which could form a gel with stronger strength and lower digestibility than native starch gel. Therefore, the two-step modification of PUL and TG was an effective way to change the structure of rice starch to improve the gel strength and reduce the digestibility.