Chain Depolymerization Research Articles

Introducing Ion Mobility Mass Spectrometry in Brain Glycosaminoglycomics: Application to Chondroitin/Dermatan Sulfate Octasaccharide Domains.

Glycosaminoglycans (GAGs) are sulfated linear O-glycan chains abundantly expressed in the extracellular matrix (ECM). Among GAGs, chondroitin sulfate (CS) and dermatan sulfate (DS) play important roles at the brain level, where the distribution and location of the sulfates within the CS/DS chains are responsible for numerous biological events. The diversity of the neural hybrid CS/DS expressed in the brain and the need to elucidate their structure gave rise to considerable efforts toward the development of analytical methods able to discover novel regularly and irregularly sulfated domains. In this context, we report here the introduction of ion mobility separation (IMS) mass spectrometry (MS) in brain glycosaminoglycomics. Based on IMS MS and tandem MS (MS/MS) by collision-induced dissociation (CID), we have developed a powerful approach for the screening and structural analysis of neural CS/DS and optimized and validated the method for the structural analysis of octasaccharides that were released from brain proteoglycans by β-elimination and pooled after chain depolymerization using chondroitin AC lyase. The IMS MS data revealed the separation of CS/DS octamers into mobility families based on the amount of sulfation. Among the discovered oversulfated domains, of major biological importance is the pentasulfated-[4,5-Δ-GlcAGalNAc(IdoAGalNAc)3], for which the (-) nanoESI IMS CID MS/MS analysis disclosed through the presence of distinct drift times, the incidence of two isomers. Moreover, the generated fragment ions revealed an uncommon trisulfated motif and an uncommon pentasulfated motif. Hence, using IMS MS and CID MS/MS, novel brain-related CS/DS domains of atypical sulfation patterns were discovered and structurally characterized in detail.

Altering structure and enzymatic resistance of high-amylose maize starch by irradiative depolymerization and annealing with palmitic acid as V-type inclusion compound

This study explored a new physical modification approach to regulate enzymatic resistance of high-amylose starch for potentially better nutritional outcomes. High-amylose maize starch (HAMS) was subjected to chain depolymerization by electron beam irradiation (EBI), followed by inducing ordered structure through annealing in palmitic acid solution (APAS). APAS treatment significantly promotes the formation of ordered structure. Starch after the combinative modification showed up to 5.2 % increase in total crystallinity and up to 1.2 % increase in V-type fraction. The EBI-APAS modification led to increased gelatinization temperature (from 66.1 to 87.6 °C) and reduced final digested percentage under in vitro stimulated digestion conditions. The moderate extent of depolymerization resulted in higher enzymatic resistance, indicating that the extent of depolymerization is crucial in EBI-APAS modification. Pearson analysis showed a significant correlation between gelatinization onset temperature and digestion kinetic parameter (k1, rate constant of fast-phase digestion). Overall, the result suggests that ordered structures of degraded molecules induced by the combinative modification contribute to the enzymatic resistance of starch. This study sheds lights on future applications of EBI-APAS approach to regulate multi-scale structures and nutritional values of high-amylose starch.

The alterations in granule, shell, blocklets, and molecular structure of pea starch induced by ultrasound

Understanding the alterations to starch multi-scale structure induced by ultrasound treatment can help in determining the effective application of ultrasound in functional-starch preparation. This study aimed to comprehensively characterize and understand the morphological, shell, lamellae, and molecular structures of pea starch granules treated by ultrasound under different temperatures. Scanning electron microscopy and X-ray diffraction analyses showed that UT (ultrasound treatment) did not change C-type of crystalline, but caused a pitted surface and endowed a looser structure and higher enzyme susceptibility as the temperature increased above 35 °C for pea starch granules. Fourier transform infrared spectroscopy and small-angle X-ray scattering analyses revealed that UT reduced the short-range ordering and increased the thickness of semi-crystalline and amorphous lamellae by inducing starch chain depolymerization, which was manifested by molecule weight and chain length distribution analysis. The sample ultrasound-treated at 45 °C had the higher proportion of B2 chains compared with the other ultrasound-treated samples because the higher ultrasonic temperature altered the disruption sites of starch chains.

Impact of pin‐to‐plate cold plasma depolymerization on the gelation and functional attributes of guar galactomannan

AbstractThe present study aimed to investigate the impact of pin‐to‐plate cold plasma on the gelation and functional attributes of guar seed galactomannan. The guar galactomannan was subjected to 170 and 230 V treatment for 30 and 60 min and investigated for the gel characteristics and functional properties. The cold plasma treatment incurred galactomannan chain depolymerization with a reduction in the degree of polymerization (DP) ranging from 7.33% to 48.99%. The water contact angle (WCA) reduced from 110.93° to 95.54°, thus increasing the hydration capacity (36.73–45.90 g/g). These mechanisms diminish the gel viscosity (from 798. 227 cP of UT to 334.65 cP at 230‐60) and the viscoelastic moduli (G′ andG″) indicating the low strength of gels from plasma‐treated galactomannan (PT‐GG). This further influenced the least gelation concentration, foam capacity, and foam stability. However, the critical strain (from 11.83% [UT] to 41% [230‐60]), cross‐over frequency (from 3.39 Hz [UT] to 15.3 Hz [230‐60]), and degradation activation energy (from 18.445 kJ/mol [UT] to 21.721 kJ/mol [230‐60]) of the PT‐GG were increased (from 18.445 kJ/mol [UT] to 21.721 kJ/mol [230‐60]) signifying the increased stability of gels by intramolecular and electrostatic forces. Thus, the cold plasma‐induced depolymerization and hydrophilic modification of galactomannan influence the gelation and functional attributes which widen the potential applications of the hydrocolloid.Practical ApplicationsDepolymerized guar gum is industrially known for its specific applications such as low‐viscosity source of dietary fiber, stabilizers, complex forming, and encapsulating agents. This study shows the potential of cold plasma processing as an eco‐friendly sustainable technology for producing depolymerized guar gum which can be applied as a source of fiber in enteral feed formulations, stabilizers in low viscous spreads and sauces, and also in thermo‐reversible gel networks due to its thermal gel transition attributes.

Investigating the effects of pre- and post-electron beam treatment on the multiscale structure and physicochemical properties of dry-heated buckwheat starch

This study presents the effects of dry heat (DH) assisted by pre-and post-electron beam (EB) treatment on buckwheat starch's multiscale structural, physicochemical, and digestive properties. The granule integrity and crystal shape were not affected by the investigated treatments. However, DH and EB treatments decreased amylose content, crystallinity, molecular weight, swelling power, thermal transition temperatures and gelatinization enthalpy while increasing solubility and the content of A chain, B1 chain, and resistant starch. EB application to DH starch promoted subsequent structural changes and enhanced starch properties compared to samples DH-processed alone. In addition, EB-induced starch chain depolymerization and structural rearrangement had sequential effects. EB pre-treatment reduced DH starch's amylose content, molecular weight, and swelling power while enhancing the content of A- chain, rapidly digestible starch, and resistant starch compared with EB post-treatment. This innovative study provides a theoretical basis for the potential applicability of EB irradiation in modifying the properties of DH starch.

Enzyme Synergy in Transient Clusters of Endo- and Exocellulase Enables a Multilayer Mode of Processive Depolymerization of Cellulose.

Biological degradation of cellulosic materials relies on the molecular-mechanistic principle that internally chain-cleaving endocellulases work synergistically with chain end-cleaving exocellulases in polysaccharide chain depolymerization. How endo–exo synergy becomes effective in the deconstruction of a solid substrate that presents cellulose chains assembled into crystalline material is an open question of the mechanism, with immediate implications on the bioconversion efficiency of cellulases. Here, based on single-molecule evidence from real-time atomic force microscopy, we discover that endo- and exocellulases engage in the formation of transient clusters of typically three to four enzymes at the cellulose surface. The clusters form specifically at regular domains of crystalline cellulose microfibrils that feature molecular defects in the polysaccharide chain organization. The dynamics of cluster formation correlates with substrate degradation through a multilayer-processive mode of chain depolymerization, overall leading to the directed ablation of single microfibrils from the cellulose surface. Each multilayer-processive step involves the spatiotemporally coordinated and mechanistically concerted activity of the endo- and exocellulases in close proximity. Mechanistically, the cooperativity with the endocellulase enables the exocellulase to pass through its processive cycles ∼100-fold faster than when acting alone. Our results suggest an advanced paradigm of efficient multienzymatic degradation of structurally organized polymer materials by endo–exo synergetic chain depolymerization.

Electron beam irradiation regulates the structure and functionality of ball-milled corn starch: The related mechanism

The ball milling (BM), electron beam irradiation (EBI), the combination of them, and their effects on granules morphology, multiscale structure, physicochemical properties, and digestibility of corn starch are discussed in this paper. Both BM and EBI reduced crystallinity, amylopectin molecular weight (Mw), pasting viscosities, gelatinization temperatures, and resistant starch (RS) content, but increased amylose Mw and rapidly digestible starch content. BM treatment damages the starch granules, which makes them easier to attack by free radicals of subsequent EBI treatment. In addition, the BM pretreatment promoted starch chain depolymerization and crystalline structure destruction, reinforcing the joint effect of subsequent EBI treatment. Therefore, BM-EBI-starches exhibited lessened crystallinity, amylopectin Mw, pasting viscosities, gelatinization temperatures, enthalpy and RS content than native and single-treated starch. This paper would like to reference potential industrial applications of BM and EBI technologies to modify starch.

Eco-friendly recycling of silicon−rich lye: Synthesis of hierarchically structured calcium silicate hydrate and its application for phosphorus removal

Silicon−rich lye (SRL), a byproduct generated from pre−treatment of coal−based solid waste (CSW), was considered as a preponderant silicon source to prepare hierarchically nanostructured calcium silicate hydrate (C-S-H). Through the novel mild−causticization synthesis strategy, C-S-H was prepared under optimal caustic process conditions at time of 3 h, temperature of 80 °C, Ca/Si of 1.25:1, and active CaO to obtain a conversion rate of Si up to 97.33 % during the high−value utilization of SRL. The synthesized C-S-H possesses abundant mesoporous structure and massive exchangeable active sites, whose formation is advanced through an appropriate elevation regulation of caustic temperature and time. The silicate chain depolymerization occurs to C-S-H prepared in the highly alkaline system at higher caustic temperature, longer caustic period, especially at existence of massive sodium ions, but it presents higher polymerization degree at more aluminum co-existing. The adsorption capacity up to 119.27 mg/g for C-S-H presents a valid removal performance toward phosphorus in the wastewater than massive present reports. The removal mechanism of phosphorus can be identified as the surface chemisorption and formation of calcium phosphate co-precipitation. This study can provide considerable and potential guidance to the coordinated disposal between industrial solid wastes and wastewater purification.

Processive Enzymes Kept on a Leash: How Cellulase Activity in Multienzyme Complexes Directs Nanoscale Deconstruction of Cellulose.

Biological deconstruction of polymer materials gains efficiency from the spatiotemporally coordinated action of enzymes with synergetic function in polymer chain depolymerization. To perpetuate enzyme synergy on a solid substrate undergoing deconstruction, the overall attack must alternate between focusing the individual enzymes locally and dissipating them again to other surface sites. Natural cellulases working as multienzyme complexes assembled on a scaffold protein (the cellulosome) maximize the effect of local concentration yet restrain the dispersion of individual enzymes. Here, with evidence from real-time atomic force microscopy to track nanoscale deconstruction of single cellulose fibers, we show that the cellulosome forces the fiber degradation into the transversal direction, to produce smaller fragments from multiple local attacks (“cuts”). Noncomplexed enzymes, as in fungal cellulases or obtained by dissociating the cellulosome, release the confining force so that fiber degradation proceeds laterally, observed as directed ablation of surface fibrils and leading to whole fiber “thinning”. Processive cellulases that are enabled to freely disperse evoke the lateral degradation and determine its efficiency. Our results suggest that among natural cellulases, the dispersed enzymes are more generally and globally effective in depolymerization, while the cellulosome represents a specialized, fiber-fragmenting machinery.

Modification of gingival proteoglycans by reactive oxygen species: potential mechanism of proteoglycan degradation during periodontal diseases

Reactive oxygen species (ROS) overproduction and oxidative stress are increasingly being implicated in the extracellular matrix (ECM) degradation associated with chronic inflammatory conditions, such as periodontal diseases. The present study investigated the effects of ROS exposure on the proteoglycans of gingival tissues, utilizing an in vitro model system comprised of supra-physiological oxidant concentrations, to ascertain whether gingival proteoglycan modification and degradation by ROS contributed to the underlying mechanisms of ECM destruction during active gingivitis. Proteoglycans were purified from ovine gingival tissues and exposed to increasing H2O2 concentrations or a hydroxyl radical (·OH) flux for 1 h or 24 h, and ROS effects on proteoglycan core proteins and sulfated glycosaminoglycan (GAG) chains were assessed. ROS were capable of degrading gingival proteoglycans, with ·OH species inducing greater degradative effects than H2O2 alone. Degradative effects were particularly manifested as amino acid modification, core protein cleavage, and GAG chain depolymerization. Proteoglycan core proteins were more susceptible to degradation than GAG chains with H2O2 alone, although core proteins and GAG chains were both extensively degraded by ·OH species. Proteoglycan exposure to ·OH species for 24 h induced significant core protein amino acid modification, with decreases in glutamate, proline, isoleucine, and leucine; and concomitant increases in serine, glycine, and alanine residues. As clinical reports have previously highlighted proteoglycan core protein degradation during chronic gingivitis, whereas their sulfated GAG chains remain relatively intact, these findings potentially provide further evidence to implicate ROS in the pathogenesis of active gingivitis, complementing the enzymic mechanisms of periodontal tissue destruction already established.

Polymer degradation: a short review

Abstract The reader will find basic knowledge about the degradation of polymers, its causes, course and consequences in a broader context, as indicated through the list of the chapter titles: Introduction; Depolymerization; Initiated cleavage (degradation) of macromolecules; Thermal degradation; Photochemical degradation; Mechanochemical degradation; Oxidative degradation; Polymer burning; Kinetics of cleaving macromolecules when chain depolymerization is negligible; Degradation in polymer recycling; Protection of polymers against degradation.

Development of a Specific and Sensitive HPAEC-PAD Method for Quantification of Vi Polysaccharide Applicable to other Polysaccharides Containing Amino Uronic Acids.

Typhoid fever is a major cause of morbidity and mortality in developing countries. Vaccines based on the Vi capsular polysaccharide are licensed or in development against typhoid fever. Vi content is a critical quality attribute for vaccines release, to monitor their stability and to ensure appropriate immune response. Vi polysaccharide is a homopolymer of α-1,4-N-acetylgalactosaminouronic acid, O-acetylated at the C-3 position, resistant to the commonly used acid hydrolysis for sugar chain depolymerization before monomer quantification. We previously developed a quantification method based on strong alkaline hydrolysis followed by High Performance Anion Exchange Chromatography-Pulsed Amperometric Detection analysis, but with low sensitivity and use for quantification of an unknown product coming from polysaccharide depolymerization. Here we describe the development of a method for Vi polysaccharide quantification based on acid hydrolysis with concomitant use of trifluoroacetic and hydrochloric acids. A Design of Experiment approach was used for the identification of the optimal hydrolysis conditions. The method is 100-fold more sensitive than the previous one, and specifically, resulting in the formation of a known product, confirmed to be the Vi monomer both de-O- and de-N-acetylated by mono- and bidimensional Nuclear Magnetic Resonance spectroscopy and mass spectrometry. Accuracy and precision were determined, and chromatographic conditions were improved to result in reduced time of analysis. This method will facilitate characterization of Vi-based vaccines. Furthermore, a similar approach has the potential to be extended to other polysaccharides containing 2-amino uronic acids, as already verified here for Shigella sonnei O-antigen, Streptococcus pneumoniae serotype 12F, and Staphylococcus aureus types 5 and 8 capsular polysaccharides.

Effects of Degraded Optical Fiber Sheaths on Thermal Aging Characteristics of Transformer Oil

With the development of fiber optic sensing technology, optical fiber sensors have been widely used in online monitoring of power transformers. To investigate the influence of aging fiber sheaths on transformer oil, two kinds of special optical fibers with thermoplastic polyester elastomer (TPEE) and poly tetra fluoroethylene (PTFE) as sheaths underwent thermally accelerated aging in transformer oil at 130 °C. The volume resistivity, dielectric dissipation factor (DDF), and breakdown voltage of the oil were measured to indicate insulation strength. The water content and acid value of the oil were measured and fitted to predict the aging tends. The thermal aging characteristics of the oil were quantitatively compared and results showed two kinds of optical fibers could exacerbate all the physical and chemical parameters of oil, and the TPEE sheath had a more significant impact on the oil. The reasons contributing to such phenomenon were analyzed using Fourier transform infrared spectroscopy (FTIR) and scanning electron microscopy (SEM). Both TPEE and PTFE were depolymerized in high-temperature transformer oils, producing water and small molecule hydrocarbon groups. The accumulation of small hydrocarbon groups promoted positive feedback of pyrolysis in the oil. The free hydrogen produced by oil pyrolysis increased the acidity of the oil, which in turn increased the solubility of the water produced by sheath depolymerization. The chain depolymerization of TPEE was more severe than that of PTFE, further exacerbating the deterioration of TPEE-containing oil.

Tailoring poly(butylene 2,5-thiophenedicarboxylate) features by the introduction of adipic acid co-units: Biobased and biodegradable aliphatic/aromatic polyesters

A class of eco-friendly copolyesters based on poly(butylene 2,5-thiophenedicarboxylate) (PBTF) is presented. The main goal of the study was to enhance the biodegradation rate of PBTF homopolymer. To this purpose, aliphatic sequences based on adipic acid have been introduced in the macromolecular backbone. The synthesized polymers have been characterized from thermal and structural point of view and their properties have been compared to those of the two homopolymers, i.e. PBTF and poly(butylene adipate). The peculiar microstructure of PBTF, due to the presence of an uninduced 2D-ordered phase, i.e. meso-phase, impacted also the copolymers' behavior, e.g. causing an increase of the materials' stiffness.Biodegradation rate in compost increased with the increase of mobile aliphatic sequences that allowed for an easier access to the ester bonds by the enzymes responsible for chain depolymerization. Lastly, gas permeability resulted strictly dependent on copolymer composition. Copolymers rich in thiophenedicarboxylate co-units displayed a gas barrier behavior comparable to poly(ethylene furanoate), while with the increase of adipate content the permeability increased, remaining however competitive with respect to that of polyolefines and polylactic acid.

Glass formation and structure of calcium antimony phosphate glasses and those doped with tellurium oxide

An approximate glass-forming region in the P2O5–Sb2O3–CaO ternary system was determined. The properties and structure of two compositional series of (A) (75−x)P2O5–xSb2O3–25CaO (x = 20, 25, 30, 35 mol%) and (B) 45P2O5–30Sb2O3–(25−x)CaO–xTeO2 (x = 5, 10, 15, 20 mol%) were studied systematically. Thermal properties were investigated by means of differential scanning calorimetry (DSC). The densities of all samples were measured by Archimedes’ method using distilled water as the immersion liquid. The water durability of the glasses was described by their dissolution rate (DR) in the distilled water at 90 °C for some time periods. Density, thermal stability and water durability were improved with the addition of Sb2O3 and TeO2. Structural studies were carried out by X-ray diffraction (XRD), infrared spectroscopy and Raman spectroscopy. The phosphate chain depolymerization occurred with the increase of Sb2O3 and the Q2 structural units transformed to the Q1 and Q0 structural units with the addition of TeO2.

Kinetic aspects of chain growth in Fischer-Tropsch synthesis.

Microkinetics simulations are used to investigate the elementary reaction steps that control chain growth in the Fischer-Tropsch reaction. Chain growth in the FT reaction on stepped Ru surfaces proceeds via coupling of CH and CR surface intermediates. Essential to the growth mechanism are C-H dehydrogenation and C hydrogenation steps, whose kinetic consequences have been examined by formulating two novel kinetic concepts, the degree of chain-growth probability control and the thermodynamic degree of chain-growth probability control. For Ru the CO conversion rate is controlled by the removal of O atoms from the catalytic surface. The temperature of maximum CO conversion rate is higher than the temperature to obtain maximum chain-growth probability. Both maxima are determined by Sabatier behavior, but the steps that control chain-growth probability are different from those that control the overall rate. Below the optimum for obtaining long hydrocarbon chains, the reaction is limited by the high total surface coverage: in the absence of sufficient vacancies the CHCHR → CCHR + H reaction is slowed down. Beyond the optimum in chain-growth probability, CHCR + H → CHCHR and OH + H → H2O limit the chain-growth process. The thermodynamic degree of chain-growth probability control emphasizes the critical role of the H and free-site coverage and shows that at high temperature, chain depolymerization contributes to the decreased chain-growth probability. That is to say, during the FT reaction chain growth is much faster than chain depolymerization, which ensures high chain-growth probability. The chain-growth rate is also fast compared to chain-growth termination and the steps that control the overall CO conversion rate, which are O removal steps for Ru.

Nanophotonic structure formation by dry e-beam etching of the resist: resolution limitation origins

A wide range of structures for nanophotonics and optoelectronics can be formed by dry e-beam etching of the resist (DEBER). High resist sensitivity due to chain depolymerization reaction provides efficient etching with high throughput of the method. The structures obtained by the DEBER in this research are well-rounded diffraction gratings, binary gratings and staircase profiles. The major disadvantage of DEBER is poor lateral resolution, which may be caused by different physical mechanisms. Four groups of possible mechanisms leading to the resolution limitation are determined and the influence of some mechanisms is estimated.

Generalized kinetic analysis of heterogeneous PET glycolysis: Nucleation-controlled depolymerization

The kinetics of poly(ethylene terephthalate) depolymerization by glycolysis has been commonly modeled as a second-order reaction. However, the occurrence of an activation stage and anomalous kinetic behavior does not fit into this reaction model. Utilizing the concept of reference theoretical master plots, we show in terms of generalized kinetics that the chain depolymerization can be controlled by a nucleation-based kinetic behavior. We associate the reported anomalous “activation” stage and chain scission-induced recrystallization in PET glycolysis with the induction period and chain reordering processes during polymer nucleation and growth. The kinetic profile and microscopic images of the polymer surface during degradation support the mechanism of sporadic nucleation and lamellar thickening. Using the matching nucleation-based conversion function we obtained an activation energy of 29 kJ/mol, the closest value reported so far to the experimental and simulated activation energy of thermal and glycolytic breakage of a PET ester bond.

Aggregates of α‐chymotrypsinogen anneal to access more stable states

Non-native protein aggregates present a variety of problems in fundamental and applied biochemistry and biotechnology, from quality and safety issues in pharmaceutical development to their association with a number of chronic diseases. The aggregated, often amyloid, protein state is often considered to be more thermodynamically and kinetically stable than (partially) unfolded or folded monomers except under highly denaturing conditions. However, evolution of the structure and stability of aggregated states has received much less attention. Here it is shown that under mildly-denaturing conditions (elevated temperature or [urea]), where the native monomer (N) is slightly favored compared to the unfolded state (U), α-chymotrypsinogen A (aCgn) non-native aggregates undergo a structural relaxation or annealing process to reach even more stable states. The annealed aggregates are more resistant to dissociation than aggregates that do not undergo this relaxation process. Aggregates without annealing dissociate via linear chain depolymerization, and annealing is accelerated under conditions that promote slow dissociation (partially denaturing conditions). This is consistent with a free energy landscape with multiple barriers and local minima that allows for a kinetic competition between aggregate dissociation and structural relaxation to more stable aggregate states. This highlights added complexities for protein refolding or aggregate dissociation processes, and may explain why it is often difficult to completely recover monomeric protein from aggregates.

Advanced Nanoscale Characterization of Cement Based Materials Using X-Ray Synchrotron Radiation: A Review

We report various synchrotron radiation laboratory based techniques used to characterize cement based materials in nanometer scale. High resolution X-ray transmission imaging combined with a rotational axis allows for rendering of samples in three dimensions revealing volumetric details. Scanning transmission X-ray microscope combines high spatial resolution imaging with high spectral resolution of the incident beam to reveal X-ray absorption near edge structure variations in the material nanostructure. Microdiffraction scans the surface of a sample to map its high order reflection or crystallographic variations with a micron-sized incident beam. High pressure X-ray diffraction measures compressibility of pure phase materials. Unique results of studies using the above tools are discussed—a study of pores, connectivity, and morphology of a 2,000 year old concrete using nanotomography; detection of localized and varying silicate chain depolymerization in Al-substituted tobermorite, and quantification of monosulfate distribution in tricalcium aluminate hydration using scanning transmission X-ray microscopy; detection and mapping of hydration products in high volume fly ash paste using microdiffraction; and determination of mechanical properties of various AFm phases using high pressure X-ray diffraction.