Degree Of Branching Research Articles

The characteristics of solid-phase substrate during the co-fermentation of lignite and straw.

Co-fermentation of lignite and biomass has been considered as a new approach in achieving clean energy. Moreover, the study of the characteristics of solid phase in the synergistic degradation process is of great significance in revealing their synergistic relationship. Accordingly, in order to produce biogas, lignite, straw, and the mixture of the two were used as the substrates, the solid phase characteristics of which were analyzed before and after fermentation using modern analytical methods. The results revealed that the mixed fermentation of lignite and straw promoted the production of biomethane. Moreover, the ratios of C/O and C/H were found to be complementary in the co-fermentation process. Furthermore, while the relative content of C-C/C-H bonds was observed to be significantly decreased, the aromatics degree of lignite was weakened. Also, while the degree of branching increased, there found to be an increase in the content of cellulose amorphous zone, which, consequently, led to an increase in the crystallinity index of the wheat straw. Hence, the results provide a theoretical guidance for the efficient utilization of straw and lignite.

High-Accuracy Heats of Formation for Alkane Oxidation: From Small to Large via the Automated CBH-ANL Method.

It is generally challenging to obtain high-accuracy predictions for the heat of formation for species with more than a handful of heavy atoms, such as those of importance in standard combustion mechanisms. To this end, we construct the CBH-ANL approach and illustrate that, for a set of 194 alkane oxidation species, it can be used to produce ΔHf(0 K) values with 2σ uncertainties of 0.2-0.5 kcal mol-1. This set includes the alkanes, hydroperoxides, and alkyl, peroxy, and hydroperoxyalkyl radicals for 17 representative hydrocarbon fuels containing up to 10 heavy atoms with various degrees of branching in the alkane backbone. The CBH-ANL approach, automated in the QTC and AutoMech software suites, builds balanced chemical equations for the calculation of ΔHf(0 K), in which the reference species may be up to five heavy atoms. The high-level ANL0 and ANL1 reference ΔHf(0 K) values are further refined for even the largest of these reference species with a novel laddering approach. We perform a comprehensive quantification of the uncertainties for both the individual reference species (the largest of which is 0.15 kcal mol-1) and the propagation of those uncertainties when used in the calculation of ΔHf(0 K) for the 194 target species. We examine the sensitivity of the predicted ΔHf(0 K) values to (i) electronic energies from various methods, including ωB97X-D/cc-pVTZ, B2PLYP-D3/cc-pVTZ, CCSD(T)-F12b/cc-pVDZ-F12//B2PLYP-D3/cc-pVTZ, and CCSD(T)-F12b/cc-pVTZ-F12//B2PLYP-D3/cc-pVTZ; (ii) the zero-point vibrational energies (ZPVEs), where we consider harmonic ZPVEs as well as two scaling-based estimates of the anharmonic ZPVEs, all implemented for both ωB97X-D/cc-pVTZ and B2PLYP-D3/cc-pVTZ calculations; (iii) the particular CBH-ANL scheme employed; and (iv) the procedure for choosing the reference conformer for the analyses. The discussion concludes with a summary of the estimated overall uncertainty in the predictions and a validation of the predictions for the alkane subset.

Effect of branching in zwitterionic polymer brushes grafted from PES UF membrane surfaces via AGET-ATR(c)P

This research explored the relationship between the antifouling behavior of porous ultrafiltration (UF) membranes and linear or branched brushes adorning their surfaces. Polyethersulfone UF membranes were functionalized via one-pot lithiation/acylation to enable surface-initiated activators generated by electron transfer for atom transfer radical (co)polymerization of sulfobetaine methacrylate (SBMA) and N,N′-methylenebisacrylamide (MBAm). Changing the SBMA/MBAm ratio and polymerization time grafted brushes at different branching and thicknesses. Surface analyses verified differences in brush architecture and that the degree of grafting increased with grafting time – it was higher for linear brushes than branched ones. Colloidal probe lateral force atomic force microscopy (LFM) showed ideal hydration–lubrication propensity of the lower branching degree poly(SBMA-co-MBAm) over pristine, linear poly(SBMA), and higher branching poly(SBMA-co-MBAm)-grafted membranes. Sharp-tip LFM predicted a critical size of <15 nm for penetrating the branched brush layers. Fouling experiments with bovine serum albumin (∼10 nm) and dextran (∼18 nm) revealed that linear and branched modifications had significantly less fouling than the pristine membrane. An optimal degree of branching can limit foulant adsorption, but fouling could be enhanced if the polymers' hydration capacity was diminished relative to a less dense network. Fouling experiments with soluble microbial products further demonstrated the branched membrane's high antifouling activity.

The relationship between starch structure and digestibility by time-course digestion of amylopectin-only and amylose-only barley starches

The multi-scale structural dynamics of amylopectin-only barley starch (APBS), normal barley starch (NBS), and amylose-only barley starch (AMBS) digested with amylolytic enzymes for 120 min were investigated in this study. For all starches, 0–20 min was identified as a rapid digestion stage, followed by a 20–120 min slow digestion. For APBS and NBS, the content of short chains (DP ≤ 12) and the thickness of crystalline and amorphous nano-lamellae increased, whereas the crystallinity decreased, and pores were generated on the granular surface during the rapid digestion stage. At the following slow digestion stage, the branching degree and relative amount of double helices increased, the crystalline and lamellar structures were lost, and the hydrolyzed starch segments aggregated. For AMBS, the rapid digestion stage was characterized by an increased content of short chains (DP ≤ 8) and B-type crystals and decreased amounts of V-type crystals. Furthermore, the lamellar and granular structures were lost, and digestion residues aggregated during the first stage of AMBS, which were formed in the second digestion stage of APBS and NBS. The second slow digestion stage of AMBS was characterized by an increased branching degree and a decreased relative content of single helices. It is suggested that the aggregated digestion residues at the initial digestion stage are the main reason for the overall low digestibility of AMBS.

On Trees with Given Independence Numbers with Maximum Gourava Indices

In mathematical chemistry, molecular descriptors serve an important role, primarily in quantitative structure–property relationship (QSPR) and quantitative structure–activity relationship (QSAR) studies. A topological index of a molecular graph is a real number that is invariant under graph isomorphism conditions and provides information about its size, symmetry, degree of branching, and cyclicity. For any graph N, the first and second Gourava indices are defined as GO1(N)=∑u′v′∈E(N)(d(u′)+d(v′)+d(u′)d(v′)) and GO2(N)=∑u′v′∈E(N)(d(u′)+d(v′))d(u′)d(v′), respectively.The independence number of a graph N, being the cardinality of its maximal independent set, plays a vital role in reading the energies of chemical trees. In this research paper, it is shown that among the family of trees of order δ and independence number ξ, the spur tree denoted as Υδ,ξ maximizes both 1st and 2nd Gourava indices, and with these characterizations this graph is unique.

Pectin-based aerogel particles for drug delivery: Effect of pectin composition on aerogel structure and release properties

In this work, nanostructured pectin aerogels were prepared via a sol-gel process and subsequent drying under supercritical conditions. To this end, three commercially available citrus pectins and an in-house produced and enzymatically modified watermelon rind pectin (WRP) were compared. Then, the effect of pectin's structure and composition on the aerogel properties were analysed and its potential application as a delivery system was explored by impregnating them with vanillin. Results showed that the molecular weight, degree of esterification and branching degree of the pectin samples played a main role in the production of hydrogels and subsequent aerogels. The developed aerogel particles showed high specific surface areas (468–584 m2/g) and low bulk density (0.025–0.10 g/cm3). The shrinkage effect during aerogel formation was significantly affected by the pectin concentration and structure, while vanillin loading in aerogels and its release profile was also seen to be influenced by the affinity between pectin and vanillin. Furthermore, the results highlight the interest of WRP as a carrier of active compounds which might have potential application in food and biomedical areas, among others.

On modification of eutectic cast iron graphite

It has been shown that elementary crystalline cells of graphite and basic products of iron modification do not correspond to the principle of structural and dimensional correspondence of Dankov –Konobeevsky. Modifying elements Al, Ca, Mg, Ba, Ce increase the phase tension melt‑graphite by binding surface‑active oxygen and sulfur. Modifying cast iron eutectic graphite is a nanostructured process in which modifying elements refine elemental graphite nanocrystals from adsorbed oxygen and sulfur atoms. This contributes to an increase in the concentration of graphite nuclei upon solidification of the cast iron melt. The modification reduces the concentration of dissolved hydrogen, which increases the effectiveness of the modifying effect. Reduced concentrations of demodifying surface‑active elements, melt degassing, increased heat removal contribute to increasing the degree of branching and compactness of graphite dendrites during iron crystallization. The strongest modifying element of eutectic cast iron graphite is magnesium.

Sulfonated branched poly(arylene ether ketone sulfone) proton exchange membranes: Effects of degree of branching and ion exchange capacity

Sulfonated branched polymers exhibit substantial potential for application as proton exchange membranes (PEMs). Most studies develop branched polymer PEMs by regulating the degree of branching (DB), without considering another important factor, i.e., the ion exchange capacity (IEC). Herein, we report on a systematical comparison regarding the effects of DB and IEC on the branched polymer PEMs and a solution to advance the properties of PEMs. To accomplish this, two series of branched poly(arylene ether ketone sulfone)s containing densely sulfonated tetraarylmethane units were synthesized. The DB and IEC were controlled in the range of 5–10 % and 1.41–1.94 meq g−1, respectively. It was found that both increasing DB and IEC of membranes promoted water absorption, proton conductivity, single-cell performance, denser distribution of microscopic hydrophilic phase, and also reduced the mechanical property. Furthermore, the strengthening via increased DB maintained dimensional stability and improved oxidative stability, while the impact of IEC was the opposite. Ultimately, a polymer membrane bearing optimal DB (7.5 %) and IEC (1.94 meq g−1) exhibited the highest proton conductivity (134.5 mS cm−1) and maximum power density (426.8 mW cm−2), satisfactory dimensional change (18.8 % in-plane, 27.2 % through-plane, and 79.5 % volume) at 80 ℃, and sufficient thermal, oxidative, and mechanical stability. This work is expected to serve as a guide for designing and synthesizing the DB and IEC of sulfonated branched polymer PEMs.

Systematically derived thermodynamic properties for alkane oxidation

Key combustion properties, such as ignition delay time, show strong sensitivity to the thermochemistry of the main species in the standard radical oxidation pathway at low temperatures (600–1000 K). Significant uncertainties persist in current estimates of thermodynamic properties, particularly for the larger species of relevance to common practical fuels. In this article, we use advanced computational schemes to evaluate thermodynamic properties for the fuel, fuel radical, peroxy, hydroperoxy-alkyl radical, and hydroperoxide species for a set of 17 fuels containing up to 9 carbon atoms, and with various degrees of branching in the alkane backbone. The procedure, termed STAR-1D, combines conformer sampling to find the minimum geometry, B2PLYP-D3/cc-pVTZ harmonic frequency evaluations, and ωB97X-D/cc-pVTZ one-dimensional torsional mapping. It includes two physically-based scaling routines: a frequency-dependent scaling to B2PLYP-D3/cc-pVTZ anharmonic frequencies and a scaling of one-dimensional ωB97X-D/cc-pVTZ torsional profiles to reproduce the product of the B2PLYP-D3/cc-pVTZ frequencies in the harmonic limit. Substantive comparisons with existing experimental databases, together with careful examinations of key theoretical assumptions, are used to explore the accuracy of the predictions. These computationally intensive explorations of 195 species were facilitated by automated thermochemistry software. High accuracy 0 K heats of formation from a separate study are used with the STAR-1D computations to generate NASA polynomial representations. In addition to their intrinsic value, the present results also provide a reliable database for the optimization of group additivity or machine learning schemes for scaling to larger combustion systems. Towards this end a complementary extensive conformational analysis is carried out for the medium sized species and the thermodynamic properties of the lowest energy hydrogen-bonded and non-hydrogen bonded conformers are contrasted for larger hydroperoxy-alkyl radical species.

Controlled Synthesis of Dendrite-like Polyglycerols Using Aluminum Complex for Biomedical Applications.

This work describes a one-pot synthesis of dendrite-like hyperbranched polyglycerols (HPGs) via a ring-opening multibranching polymerization (ROMBP) process using a bis(5,7-dichloro-2-methyl-8-quinolinolato)methyl aluminum complex (1) as a catalyst and 1,1,1-tris(hydroxymethyl)propane/trimethylol propane (TMP) as an initiator. Single-crystal X-ray diffraction (XRD) analysis was used to elucidate the molecular structure of complex 1. Inverse-gated (IG)13C NMR analysis of HPGs showed degree of branching between 0.50 and 0.57. Gel permeation chromatography (GPC) analysis of the HPG polymers provided low, medium, and high-molecular weight (M n) polymers ranging from 14 to 73 kDa and molecular weight distributions (M w/M n) between 1.16 and 1.35. The obtained HPGs exhibited high wettability with water contact angle between 18 and 21° and T g ranging between -39 and -55 °C. Notably, ancillary ligand-supported aluminum complexes as catalysts for HPG polymerization reactions have not been reported to date. The obtained HPG polymers in the presence of the aluminum complex (1) can be used for various biomedical applications. Here, nanocomposite electrospun fibers were fabricated with synthesized HPG polymer. The nanofibers were subjected to cell culture experiments to evaluate cytocompatibility behavior with L929 and MG63 cells. The cytocompatibility studies of HPG polymer and nanocomposite scaffold showed high cell viability and spreading. The study results concluded, synthesized HPG polymers and composite nanofibers can be used for various biomedical applications.

Influence of physicochemical properties of depressor additives on their performance in diesel fuels

The work investigates the influence of the physicochemical properties of depressor additives on their performance in diesel fuels of various chemical and fractional compositions. Heavy, summer and marine diesel fuels were used. The following physicochemical properties of fuels were determined: cloud point, freezing point, density, viscosity, fraction composition and hydrocarbon content that formed a complex with carbamide. The content and molar mass distribution of individual n-alkanes in diesel fuels were determined. The following foreign depressant-dispersing additives were used: Dodiflow with codes 4971, 5416, 5817 and 7118, Keroflux with codes 3501, 5696a and Ofi-8863. Their active agents were isolated from the commercial additives by dialysis using semi-permeable rubber membranes. The dropping point of the active agents, their intrinsic viscosity in kerosene and the refractive index at 100 °C were identified. The content of vinyl acetate components and the degree of branching of aliphatic radicals of depressor additives were determined using infrared spectroscopy of the active agents. The relationship between the physicochemical properties of depressor-dispersing additives and their performance in diesel fuels was established. Additives characterised by a relatively high melting point, an average intrinsic viscosity and low branching of aliphatic compounds in the polymer structure exhibit the best performance in fuels. The consumption of additives to achieve the maximum depression of freezing point decreases with the transition from summer to marine fuel and further to heavy diesel fuel. A complex tкп / СВА value, comprising the ratio of the dropping points tкп and the content of vinyl acetate components in the additives, was proposed as a means of predicting the efficiency of depressant additives СВА. In the range of tкп / СВА values of 3.02–4.00 the additives have universal depressant properties. A correlation was established between the refractive index nD100 of additives and the complex value tкп / СВА (R2 = 0.975).

Quasilinear polyglycidols by triethyborane-controlled anionic polymerization of unprotected glycidol.

In this study, quasilinear polyglycidols (PG)s with ultralow degree of branching (DB) could be synthesized through anionic polymerization of glycidol carried out in the presence of triethylborane (TEB). PGs with DB ≤ 0.10, and molar masses up to 40 kg mol-1 could be indeed obtained using mono- or trifunctional ammonium carboxylates as initiator and under slow monomer addition conditions. The synthesis of degradable PGs through ester linkages obtained by copolymerization of glycidol with anhydride is also described. PG-based amphiphilic di- and triblock quasilinear copolymers were also derived. The role played by TEB is discussed and a polymerization mechanism is proposed.

Recent Developments in Molecular Characterization, Bioactivity, and Application of Arabinoxylans from Different Sources

Arabinoxylan (AX) is a polysaccharide composed of arabinose, xylose, and a small number of other carbohydrates. AX comes from a wide range of sources, and its physicochemical properties and physiological functions are closely related to its molecular characterization, such as branched chains, relative molecular masses, and substituents. In addition, AX also has antioxidant, hypoglycemic, antitumor, and proliferative abilities for intestinal probiotic flora, among other biological activities. AXs of various origins have different molecular characterizations in terms of molecular weight, degree of branching, and structure, with varying structures leading to diverse effects of the biological activity of AX. Therefore, this report describes the physical properties, biological activities, and applications of AX in diverse plants, aiming to provide a theoretical basis for future research on AX as well as provide more options for crop breeding.

Effects of thermal aging atmospheres on oxidation activity, element composition and microstructure of diesel soot particles.

As an emission control device for diesel engines, DPF plays an important role in reducing particulate matter emissions. The research work on soot thermal aging will help optimize DPF regeneration strategies, improve regeneration efficiency, and promote the progress of engine emission control technology. In order to explore the influence of thermal aging under different atmospheres on particle physicochemical characteristics from diesel engines, the oxidation activity of soot particles after different thermal aging were evaluated by thermogravimetric analysis (TGA) and pyrolysis kinetics calculation, and the distribution of functional groups and elemental composition on the soot surface were investigated by FT-IR and XPS analysis. Additionally, the microstructure and graphitization degree of basic carbon with O2/NO2 aging were analyzed by HRTEM technology. The results show that the ignition temperature and activation energy of soot significantly increase after thermal aging, and their lowest values are 569 °C and 165.29 kJ mol-1 in O2/NO2/N2 atmosphere, respectively. The branching degree and content of hydrocarbon functional groups on the soot surface decrease after thermal aging, and the relative content of hydrocarbon functional groups with NO2 participating in thermal aging is the highest. The content of O element on the soot surface decreases after thermal aging, and the maximum O/C molar ratio of soot particles after thermal aging in O2/NO2/N2 atmosphere is 0.15. After thermal aging, the hybridization degree of carbon atoms and the content of -C-OH and -C[double bond, length as m-dash]O functional groups on the soot surface decrease. The content of -C-OH functional group decreases to 0.21% and 0.53% respectively after the addition of O2 and NO2 in the thermal aging atmosphere, while the content of -C[double bond, length as m-dash]O functional group increases to 4.98% and 5.98% respectively. In addition, the layer spacing and microcrystalline curvature of basic carbon particles decrease after thermal aging, however, the microcrystalline size and the graphitization degree increase.

Synthesis and self-assembly of hyperbranched multiarm copolymer peptide conjugates based on light-induced metal-free ATRP

Light-induced metal-free ATRP was applied in the preparation of the hyperbranched multiarm copolymer peptide conjugates, which can self-assemble into monolayer or bilayer vesicles depending on the degree of branching of the hyperbranched copolymer.

Novel lignin polymerization pathway leading to branching in the structure.

The chemical structure of lignin has been shrouded in controversies, with a particularly prevalent issue pertaining to the degree of branching in it. The present work computationally demonstrates that the predominant β-O-4 linkage comprising lignin can act as a branching point via an α-O-γ lignin linkage, altering how the community thinks of the lignin structure from a fundamental and valorization perspective.

Effects of solvent conditions on the self-assembly of heterotrimeric collagen-like peptide (CLP) triple helices: a coarse-grained simulation study.

We perform coarse-grained (CG) molecular dynamics (MD) simulations to investigate the self-assembly of collagen-like peptide (CLP) triple helices into fibrillar structures and percolated networks as a function of solvent quality. The focus of this study is on CLP triple helices whose strands are different lengths (i.e., heterotrimers), leading to dangling 'sticky ends'. These 'sticky ends' are segments of the CLP strands that have unbonded hydrogen-bonding donor/acceptor sites that drive heterotrimeric CLP triple helices to physically associate with one another, leading to assembly into higher-order structures. We use a validated CG model for CLP in implicit solvent and capture varying solvent quality through changing strength of attraction between CG beads representing the amino acids in the CLP strands. Our CG MD simulations show that, at lower CLP concentrations, CLP heterotrimers assemble into fibrils and, at higher CLP concentrations, into percolated networks. At higher concentrations, decreasing solvent quality causes (i) the formation of heterogeneous network structures with a lower degree of branching at network junctions and (ii) increases in the diameter of network strands and pore sizes. We also observe a nonmonotonic effect of solvent quality on distances between network junctions due to the balance between heterotrimer end-end associations driven by hydrogen bonding and side-side associations driven by worsening solvent quality. Below the percolation threshold, we observe that decreasing solvent quality leads to the formation of fibrils composed of multiple aligned CLP triple helices, while the number of 'sticky ends' governs the spatial extent (radius of gyration) of the assembled fibrils.

Cu(triNHC)-catalyzed polymerization of glycidol to produce ultralow-branched polyglycerol.

We have successfully synthesized a novel form of polyglycerol with an unprecedentedly low degree of branching (DB = 0.08-0.18), eliminating the need for glycidol protection. Leveraging the remarkable efficiency and selectivity of our Cu(triNHC) catalyst, comprising copper(i) ions and NHC ligands, we achieved a highly selective polymerization process. The proposed Cu-coordination mechanisms presented the formation of linear L1,3 units while effectively suppressing dendritic units. Consequently, our pioneering approach yielded polyglycerol with an ultralow DB and exceptional yields. To comprehensively assess the physical properties and topology of the synthesized polyglycerol, we employed 1H diffusion-ordered spectroscopy, size-exclusion chromatography, and matrix-assisted laser desorption/ionization-time of flight spectrometry. Remarkably, the ultralow-branched cyclic polyglycerol (DB = 0.08) synthesized at 0 °C showcased extraordinary characteristics, exhibiting the lowest diffusion coefficient and the highest molecular weight. This achievement establishes the significant potential of our polyglycerol with a low degree of branching, revolutionizing the field of biocompatible polymers.

Anisotropic short-range attractions precisely model branched erythrocyte aggregates.

Homogeneous suspensions of red blood cells (RBCs or erythrocytes) in blood plasma are unstable in the absence of driving forces and form elongated stacks, called rouleaux. These erythrocyte aggregates are often branched porous networks - a feature that existing red blood cell aggregation models and simulations fail to predict exactly. Here we establish that alignment-dependent attractive forces in a system of dimers can precisely generate branched structures similar to RBC aggregates observed under a microscope. Our simulations consistently predict that the growth rate of typical mean rouleau size remains sub-linear - a hallmark from past studies - which we also confirm by deriving a reaction kernel taking into account appropriate collision cross-section, approach velocities, and an area-dependent sticking probability. The system exhibits unique features such as the existence of percolated and/or single giant cluster states, multiple coexisting mass-size scalings, and transition to a branched phase upon fine-tuning of model parameters. Upon decreasing the depletion thickness we find that the percolation threshold increases but the morphology of the structures opens up towards an increased degree of branching. Remarkably the system self-organizes to produce a universal power-law size distribution scaling irrespective of the model parameters.

Starch/PVOH aqueous solutions: a chemical-physical characterization.

This work investigates the relationship between the structure and physicochemical properties of three different starches in starch/polyvinyl alcohol aqueous solutions. For this purpose, accurate nuclear magnetic resonance (NMR) analyses were performed to determine the role that the starch structure plays in the formation of binder solutions. Moreover, a dynamic shear rheometer (DSR) was used to investigate the mechanical properties of the solutions and correlate them with the structure of each starch. Complete characterization of the analysed starches and the starch/PVOH solutions was also carried out through light scattering measurements. Furthermore, by crossing the data coming from NMR and light scattering with those coming from rheology, the best solution was identified. Finally, to confirm the interaction mechanism between starch and PVOH, thermogravimetric analysis and an NMR study, using 1H and 13C NMR spectra, were carried out on the film obtained from the best solution. The analyses carried out showed that PVOH has a stabilizing effect on starch/PVOH solutions, and the starch with the greatest branching degree is the one that forms a more structured network.