Partial Degradation Research Articles

Establishment and application of characteristic degradation fingerprint for the quality control of Compound Banlangen Granules polysaccharides.

Compound Chinese medicine preparation is a complex multi-component system. The traditional methods such as physicochemical identification and quantification of several main index components cannot provide adequate quality evaluation for Compound Banlangen Granules. The objective of this work was to establish a characteristic degradation fingerprint of Compound Banlangen Granules polysaccharides, and the reference fingerprint was obtained from the model samples prepared using prescription medicinal herbs from different origins. The partial degradation products of Compound Banlangen Granules polysaccharides were profiled by capillary zone electrophoresis, and the quality difference of polysaccharides of these preparations was compared by cluster analysis and principal component analysis. It was found that the contents and the characteristic degradation fingerprints of the polysaccharides from 25 batches of Compound Banlangen Granules of 17 manufacturers were significantly different. The quality of Compound Banlangen Granules polysaccharides was evaluated by the characteristic degradation fingerprint tool with satisfactory results. The present method provides a reference for the quality control strategy development of polysaccharides in other compound Chinese medicine preparations.

The hidden role of dissolved organic carbon in the biogeochemical cycle of carbon in modern redox-stratified lakes

Abstract. The dissolved organic carbon (DOC) reservoir plays a critical role in the C cycle of marine and freshwater environments because of its size and implication in many biogeochemical reactions. Although it is poorly constrained, its importance in ancient Earth's C cycles is also commonly invoked. Yet DOC is rarely quantified and characterized in modern stratified analogues. In this study, we investigated the DOC reservoirs of four redox-stratified alkaline crater lakes in Mexico. We analyzed the concentrations and isotopic compositions of DOC throughout the four water columns and compared them with existing data on dissolved inorganic and particulate organic C reservoirs (DIC and POC). The four lakes have high DOC concentrations with great variability between and within the lakes (averaging 2 ± 4 mM; 1 SD, n=28; i.e., from ∼ 15 to 160 times the amount of POC). The δ13CDOC signatures also span a broad range of values from −29.3 ‰ to −8.7 ‰ (with as much as 12.5 ‰ variation within a single lake). The prominent DOC peaks (up to 21 mM), together with their associated isotopic variability, are interpreted as reflecting oxygenic and/or anoxygenic primary productivity through the release of excess fixed carbon in three of the lakes (Alberca de los Espinos, La Preciosa, and Atexcac). By contrast, the variability of [DOC] and δ13CDOC in the case of Lake Alchichica is mainly explained by the partial degradation of organic matter and the accumulation of DOC in anoxic waters. The DOC records detailed metabolic functions such as active DIC-uptake and DIC-concentrating mechanisms, which cannot be inferred from DIC and POC analyses alone but which are critical to the understanding of carbon fluxes from the environment to the biomass. Extrapolating our results to the geological record, we suggest that anaerobic oxidation of DOC may have caused the very negative C isotope excursions in the Neoproterozoic. It is, however, unlikely that a large oceanic DOC reservoir could overweigh the entire oceanic DIC reservoir. This study demonstrates how the analysis of DOC in modern systems deepens our understanding of the C cycle in stratified environments and helps to set boundary conditions for the Earth's past oceans.

Antimicrobial properties of the essential oil of Schinus areira (Aguaribay) against planktonic cells and biofilms of S. aureus

The essential oil (EO) of Schinus areira L. (Anacardiaceae) leaves has shown antibacterial activity against Staphylococcus aureus. In this study, we aimed to unravel the mechanisms of its antibacterial action by using bacterial cells and model membranes. First, the integrity of the S. aureus membrane was evaluated by fluorescence microscopy. It was observed that there was an increase in the permeability of cells that was dependent on the EO concentration as well as the incubation time. For a deep comprension of the action of the EO on the lipids, its effect on the membrane fluidity was evaluated on DMPC (1,2-dimyristoyl-sn-glycero-3-phosphocholine): DMPG (1,2-dimyristoyl-sn-glycero-3-phospho-1′-rac-glycerol) (5:1) liposomes by dynamic light scattering and by using Laurdan doped liposomes. The results indicate that EO produces changes in lipid membrane packing, increasing the fluidity, reducing the cooperative cohesive interaction between phospholipids and increasing access of water or the insertion of some components of the EO to the interior of the membrane. In addition, the potential effect of EO on intracellular targets, such as the increase of cytosolic reactive oxygen species (ROS) and DNA damage, were analyzed. The EO was capable of increasing the production of ROS as well as inducing a partial DNA degradation. Finally, the effect of EO on S. aureus biofilm was tested. These assays showed that EO was able to inhibit the biofilm formation, and also eradicate preformed biofilms. The results show, that the EO seems to have several bacterial targets involved in its antibacterial activity, from the bacterial membrane to DNA. Furthermore, the antibacterial action affects not only planktonic cells but also biofilms; reinforcing the potential application of this EO.

Comparative predictive power of serum vs plasma proteomic signatures in feto-maternal medicine

Blood proteins are frequently measured in serum or plasma, because they provide a wealth of information. Differences in the ex vivo processing of serum and plasma raise concerns that proteomic health and disease signatures derived from serum or plasma differ in content and quality. However, little is known about their respective power to predict feto-maternal health outcomes. Predictive power is a sentinel characteristic to determine the clinical use of biosignatures. This study aimed to compare the power of serum and plasma proteomic signatures to predict a physiological pregnancy outcome. Paired serum and plasma samples from 73 women were obtained from biorepositories of a multinational prospective cohort study on pregnancy outcomes. Gestational age at the time of sampling was the predicted outcome, because the proteomic signatures have been validated for such a prediction. Multivariate and cross-validated models were independently derived for serum and plasma proteins. A total of 1116 proteins were measured in 88 paired samples from 73 women with a highly multiplexed platform using proximity extension technology (Olink Proteomics Inc, Watertown, MA). The plasma proteomic signature showed a higher predictive power (R=0.64; confidence interval, 0.42-0.79; P=3.5×10-6) than the serum signature (R=0.45; confidence interval, 0.18-0.66; P=2.2×10-3). The serum signature was validated in plasma with a similar predictive power (R=0.58; confidence interval, 0.34-0.75; P=4.8×10-5), whereas the plasma signature was validated in serum with reduced predictive power (R=0.53; confidence interval, 0.27-0.72; P=2.6×10-4). Signature proteins largely overlapped in the serum and plasma, but the strength of association with gestational age was weaker for serum proteins. Findings suggest that serum proteomics are less informative than plasma proteomics. They are compatible with the view that the partial ex-vivo degradation and modification of serum proteins during sample processing are an underlying reason. The rationale for collecting and analyzing serum and plasma samples should be carefully considered when deriving proteomic biosignatures to ascertain that specimens of the highest scientific and clinical yield are processed. Findings suggest that plasma is the preferred matrix.

Solvation–Reduction Coupling in Ca2+ Electroactivity in Glyme‐Based Electrolytes: A First Principles Study

AbstractThe electrochemical activity of solvated Ca2+ in glyme‐based electrolytes is investigated using grand canonical density functional theory approach and Fukui functions. The obtained results reveal that the length of glyme molecules has little effect on the reduction potentials, but has significant impacts on the effective electron transfer process. In short chain glymes, the transferred electron is located on a Ca2+ center and the organic part of the solvation sphere, leading to a direct Ca2+ reduction and a partial degradation of the glyme molecules. As the glyme's length increases, the reduction process turns into the formation of solvated electrons rather than Ca2+ reduction, unless a partial desolvation occurs. Consequently, an effective Ca2+ reduction in long chain glyme‐based electrolytes is controlled by a (partial) desolvation of the solvation sphere. These results can be used as guiding information to design new electrolytes having the Ca2+ reduction potential in an accessible voltage range together with an effective Ca2+ reduction process. The methodology developed in this study can be universally applied to investigate the thermodynamic and kinetic properties of other battery systems using metal anodes, which might lead to a paradigm shift in the design of prospective electrolytes for future battery technologies.

Accelerated Oxidative Degradation of Phosphonium-Type Ionic Liquid with l-Prolinate Anion: Degradation Mechanism and CO2 Separation Performance.

Amino acid ionic liquids (AAILs) are regarded as green alternatives to existing CO2-sorptive materials because amino acids are readily available from renewable sources in large quantities. For widespread applications of AAILs, including direct air capture, the relationship between the stability of AAILs, especially toward O2, and the CO2 separation performance is of particular importance. In the present study, the accelerated oxidative degradation of tetra-n-butylphosphonium l-prolinate ([P4444][Pro]), a model AAIL that has been widely investigated as a CO2-chemsorptive IL, is performed using a flow-type reactor system. Upon heating at 120-150 °C and O2 gas bubbling to [P4444][Pro], both the cationic and anionic parts undergo oxidative degradation. The kinetic evaluation of the oxidative degradation of [P4444][Pro] is performed by tracing the decrease in the [Pro]- concentration. Supported IL membranes composed of degraded [P4444][Pro] are fabricated, and the membranes retain CO2 permeability and CO2/N2 selectivity values in spite of the partial degradation of [P4444][Pro].

Structure of the humic acid-like compounds of raw and hydrothermally treated sewage sludge

Humic acids are of great interest in many fields; however, they are inhibitors of fermentative processes applied to hydrothermally treated sewage sludge. Hence, the structure and composition of soluble and bound humic acid-like fractions from raw and hydrothermally treated sewage sludge were studied. Lipid, polysaccharide, protein and aromatic fractions were identified, as well as a high nitrogen content (7–10 %) and low solubility in alkaline media. Thus, they do not strictly meet the chemical definition of ‘humic acids’. The soluble humic acid-like compounds had more aromatic and less protein content. Thermal hydrolysis of sewage sludge increased their aromaticity to the detriment of protein and polysaccharide fractions, while wet oxidation caused an increase in all structural fractions. Regarding the bound compounds, lipid, polysaccharide and aromatic fractions increased markedly during both treatments, although oxygen produced higher degradation of the protein fraction and, from 1 h, the partial degradation of aromatic compounds and an increase in the C/N atomic ratio (from 5.0 to 18.7 after 2 h). Therefore, hydrothermal treatments have a positive impact on the hydrolysate biodegradability due to the organic matter solubilisation, but also a negative impact linked to the higher solubilisation of the humic acid-like compounds and their structural changes.

Screening Microbial Interactions During Inulin Utilization Reveals Strong Competition and Proteomic Changes in Lacticaseibacillus paracasei M38

Competition for resources is a common microbial interaction in the gut microbiome. Inulin is a well-studied prebiotic dietary fiber that profoundly shapes gut microbiome composition. Several community members and some probiotics, such as Lacticaseibacillus paracasei, deploy multiple molecular strategies to access fructans. In this work, we screened bacterial interactions during inulin utilization in representative gut microbes. Unidirectional and bidirectional assays were used to evaluate the effects of microbial interactions and global proteomic changes on inulin utilization. Unidirectional assays showed the total or partial consumption of inulin by many gut microbes. Partial consumption was associated with cross-feeding of fructose or short oligosaccharides. However, bidirectional assays showed strong competition from L. paracasei M38 against other gut microbes, reducing the growth and quantity of proteins found in the latter. L. paracasei dominated and outcompeted other inulin utilizers, such as Ligilactobacillus ruminis PT16, Bifidobacterium longum PT4, and Bacteroides fragilis HM714. The importance of strain-specific characteristics of L. paracasei, such as its high fitness for inulin consumption, allows it to be favored for bacterial competence. Proteomic studies indicated an increase in inulin-degrading enzymes in co-cultures, such as β-fructosidase, 6-phosphofructokinase, the PTS D-fructose system, and ABC transporters. These results reveal that intestinal metabolic interactions are strain-dependent and might result in cross-feeding or competition depending on total or partial consumption of inulin. Partial degradation of inulin by certain bacteria favors coexistence. However, when L. paracasei M38 totally degrades the fiber, this does not happen. The synergy of this prebiotic with L. paracasei M38 could determine the predominance in the host as a potential probiotic.

Influence of polymer modification on intra-MOF self-diffusion in MOF-based mixed matrix membranes

Mixed-matrix membranes (MMMs) represent a promising membrane type for gas and liquid separations. Such membranes can be formed by dispersing crystals of metal–organic frameworks (MOFs) in polymers. For liquid separations, crosslinked polymers are desirable because crosslinking reduces polymer dilation and plasticization effects by liquid sorbates. However, polymer crosslinking processes can unfavorably change transport and related structural properties of MOF fillers. In this work, 13C pulsed field gradient (PFG) NMR was used to investigate possible changes in intra-MOF self-diffusion of p-xylene and o-xylene after MMM polymer crosslinking. The studied MMMs were formed by dispersing MOF crystals of the type ZIF-71 in Torlon (a poly(amide-imide)) or Matrimid (a polyimide) polymers. The reported PFG NMR data indicate that the polymer crosslinking process used does not influence the intra-ZIF diffusivities when all effects on these diffusivities that are related to diffusing molecules crossing over the crystal boundaries or reflected away from these boundaries are removed. In contrast, these data show that the crosslinking process resulted in a significant decrease of the effective size of ZIF-71 crystals inside the studied MMMs, especially in the ZIF-71/Matrimid MMM. This crystal size decrease is attributed to a partial degradation of the ZIF-71 crystals inside the MMMs due to the crosslinking process. This conclusion was found to be in agreement with the results of electron microscopy analysis. PFG NMR studies and data analysis similar to those presented here can be used for quantifying any types of MOF crystal degradation inside MOF-based MMMs.

Correlated disorder by defects clusters in LiNbO3 single crystals after crystal ion-slicing

LiNbO3 (LNO) is a material suitable for high-frequency and wideband RF filters as well as photonic applications due to its outstanding piezoelectric and optical properties. Applications such as thin-film bulk acoustic wave resonators or highly confined electro-optic modulators require thin films, which are still challenging to be obtained with the necessary crystalline quality by deposition methods. Alternatively to deposition, crystal ion-slicing (CIS) or Smart CutTM enables obtaining thin films hundreds of nanometers thick from the bulk single-crystal utilizing high-energy and dose implantation of light atoms. The price to pay is the partial degradation of the initial crystalline perfection, which translates to a degradation of the piezoelectric performance of the material if the CIS-induced damage is not eliminated.This work aims to understand the physics of the recrystallization process of the CIS-damaged LNO crystal upon thermal annealing. The study of the coherent and diffuse scattering by high-resolution X-ray diffraction, complemented by micro-Raman backscattering spectroscopy and Transmission Electron Microscopy (TEM), allowed to study the recovery of the crystallinity from the CIS-induced lattice strain and stress and the progressive reduction of the defects clusters dimension.

A comprehensive research of low-density bio-based rigid polyurethane foams from sugar beet pulp-based biopolyol: From closed-cell towards open-cell structure

The effective using of industrial agricultural crop residues in the polymer industry is still challenging. Herein, sugar beet pulp-based polyol (SBpol) was synthesized using an acid-catalyzed solvothermal liquefaction method, and then a series of bio-based rigid polyurethane foams (sPUFs) was produced using one-shot and free-rising technique by replacing up to 100 php of the petroleum-based polyol with biopolyol. The effects of an increasing amount of SBpol on the morphological, physico-mechanical, thermal, and flame retardant properties of sPUFs were evaluated. SEM pictures revealed that the cell windows of sPUFs opened as the amount of biopolyol increased, and in parallel with these results, the decreases in the closed-cell contents were determined. While the insulation properties of sPUFs containing up to 40 php biopolyol are superior, the mechanical properties of sPUFs containing 20 php biopolyol are higher than that of reference petroleum-based foam. The water absorption ratio of sPUF100 was almost 5 times higher than that of the reference foam at the end of 76 h due to the high porosity. A 6-week abiotic hydrolysis test showed that the sPUF100 sample started a partial degradation. Thermogravimetric analysis indicated that all the sPUFs were thermally stable at temperatures up to 247 °C. The flame retardant properties of sPUFs were not satisfactory because the addition of biopolyol increased both heat release rate and total smoke production; therefore, the flame resistance of sPUFs has to be increased by the incorporation of flame retardant chemicals. This study proves a useful, promising, and sustainable strategy for the development of sugar beet pulp-based polyurethane foams in the polyurethane industry.

Forest Health Assessment in Four Jordanian Reserves Located in Semi-Arid Environments

Healthy forests are essential to human life because they provide food, energy, and other benefits including carbon sequestration. The objective of this study was to assess the forests health status in Mediterranean ecosystems, specifically, arid to semi-arid. Four forest reserves directed by Royal Society for the Conservation of Nature, Jordan were evaluated. Plant health indicators [(gas exchange (photosynthesis, stomatal conductance, transpiration), chlorophyll, middy stem water potential (Ψsmd), relative water content], regeneration, lichens, plant disease, as well as soil variables (respiration CO2-C, electrical conductivity (EC), pH, microorganisms’ abundance) were measured. The Ψsmd values in those semi-arid/arid ecosystems were within the normal ranges (−0.3 to −1.3 MPa) in spring but was under extreme water stress (−1.6 to −5.3 MPa) in summer in three reserves. Similarly, gas exchange variables reduced by 25%–90% in summer (compared to spring) across the studied forests. Although the regeneration (seedling per 1000 m2) was higher than 100 in two forest (Ajloun and Dibbeen), the number of seedlings in hiking sites was extremely low in both forests. Soil health indicators reveled that soil respiration CO2-C were higher than 25 mg kg−1 in two forests [Ajloun, Dibbeen, (except hiking zone)]. The mean soil saprophytes (number g−1) ranged from 86 to 377 across the forests reserves. In addition, the mean arbuscular mycorrhizal fungi (spores 100g−1 soil) was between 350 and 877. Soil EC was consistently optimal (less than 0.5 dS m−1) and pH was slightly basic (7.5–8.3) across the reserves. The results revealed that the fluctuation of rainfall and anthropogenic pressures (grazing, hiking) led to partial forest degradation. When forests (Dana Biosphere Reserve) received 81 mm annual precipitation, Ψsmd values in Juniperus phoenicea at summer ranged from −4.4 to −5.3 MPa, regeneration and lichens were less than 20 per 1000 m2, and several trees were dead after infected with soil and air borne pathogens including wilt diseases and die back. Intensive hiking activities (Dibbeen forests, tourism area) and heavy grazing (Yarmouk frosts) reduced regeneration, lichens and soil respiration. Interestingly, the native species had better water relations (RWC, Ψsmd) and gas exchange performance than the introduced species. Overall, it is better to grow native species, and exclude anthropogenic pressure on the territory of introduced species. The conservation programs must persist to sustain several native historical forest trees including Juniperus phoenicea (>600 year old), Quercus ithaburensis (>500 year old), and Pinus halepensis (>100 year old) at Mediterranean semi-arid forests.

Development of biocatalytic microbial ecosystem (FPUS@RODMs@In-PAOREs) for rapid and sustainable degradation of various refractory organics

The removal of diverse refractory organics from complex industrial wastewater continues to be a challenge. Although biological treatments are commonly employed, only partial degradation and increasing emergence of nitrogenous compounds, i.e., nitrate (NO3) and nitrite (NO2) would pose severe toxicity to the intact microbes. Herein, an efficient biocatalytic microbial ecosystem (BCME) was designed over a porous bio-carrier made of a functional polyurethane sponge (FPUS). The BCME comprised a unique set of organisms (RODMs) with novel metabolism, efficiently degrading highly-concentrated aromatics. Strategic enzyme immobilization was utilized to introduce in-situ production and aggregation of the oxidation and reduction enzymes (In-PAOREs) onto the FPUS, thereby ensuing sustained functions of the RODMs community. The developed FPUS@RODMs@In-PAOREs system was found to enhance the refractory organics removal rate to 4 kg/m3/day, and it would be attributed to the enzymatic catalysis of refractory organics (2000 mg/L) accompanied by the removal of COD (1200 mg/L) and nitrogenous compounds (200 mg/L). Besides, the fluctuating concentration of extra polymeric substances (EPS) played a dual role through enhancing adhesion, promoting the development of a functional microbial ecosystem, and creating an EPS gradient within the FPUS bio-carrier. This differential distribution of enzymes was established to significantly boost biocatalysis activity reaching 400 U/g VSS.

High-resolution mass spectrometry identification of dye compounds and their degradation products in American cochineal from a historic shipping cargo

Cochineal dyes constitute paradigmatic organic compounds that guide in the elucidation of historic cultural and economical exchanges. This study combines liquid chromatography and high-resolution tandem mass spectrometry to assess the degradation products of the organic dyes of American cochineal collected from the cargo of a 16th century sunken wreck. The identification of biological materials of historical and archeological origin is often challenging due to molecular degradation. In this scenario, the mapping of the chemical routes underlying the fate of the organic and biochemical compounds employed as taxonomic biomarkers becomes of crucial importance. This work shows that, under harsh environmental conditions, the original carminic and (flavo)kermesic acid structures of cochineal dyes are prone to chemical transformation, typically losing the carboxylic acid and glucoside groups. The anthraquinone core is preserved in the majority of degradation products identified in this study, with eventual side chains reminiscent of a partial degradation of the glucoside moiety. The comparison of these observations with the analysis of modern cochineal samples allows us to lay out an updated chart of dye compounds and degradation products which should constitute a seminal benchmark for future biomolecular analysis of historic and archeological dye materials.

Microscopic Evidence of the Behavior of pH-sensitive Food-grade Polymeric Delivery Systems

Background: Colon delivery systems are designed for the oral delivery of active compounds in the large intestine. Food-grade copolymers Eudraguard® Biotic (EUGB) and control (EUGC) have been investigated to develop colloidal systems loading natural active ingredients. Methods: In this study, we evaluated the degradation process of these matrices in simulated gastric, intestinal and colonic conditions. Microparticles made of EUGB and EUGC, alone or in combination, were loaded with the model compound resveratrol (RSV). A parallel study was performed on in vitro RSV release and SEM analysis of microparticles kept at different pH values. Results: All systems ensured a limited gastric release of RSV (below 20%), presenting only small pores on the surface of microparticles treated with simulated gastric fluid. EUGB microparticles showed the maximum release in simulated colon fluid (SCF), showing a complete dissolution of the microparticle matrix. The EUGC-based system allowed a prolonged release of RSV over time, and in SCF, it showed only partial degradation. Using mixed EUGB/EUGC matrices, a prolonged RSV release was observed along the intestinal tract. Conclusion: Overall, EUGB and EUGC copolymers were able to modulate and localize the release of entrapped cargo in the small intestine and colon. They could have interesting applications in treating bowel diseases synergistically with other therapeutic strategies.

Recycling in Building Materials: Analysis of the Possibilities and Results of Using Recycled Glass Sand in Autoclaved Materials

The construction industry is particularly responsible for the appearance of the earth and the environment and for its partial degradation related to climate warming through the production of cement, brick burning, and the processing of substrates for the production of building materials (lime, gypsum, polystyrene, processed materials, etc.). An important aspect of the 21st century has been the overproduction and excessive use of natural resources, including sand. The purpose of this article is to analyze the possibility of using glass sand as a substitute for quartz sand in the production of materials resulting from hydrothermal treatment (so-called silicate bricks). The article is a review of the research conducted since 2016 on laboratory tests on the modification of silicate mass with glass sand from recycled bottle glass, the properties of the mass modified in this way (hydration temperature, consistency, and humidity of the mixture), its physical and mechanical properties, and its structural and potential durability, which is related to, e.g., the direction and degree of crystallization of the C-S-H phase. Tests of compressive strength, density, water absorption, oxide composition (XRF), structure (XRD), microstructure (SEM), and porosity (CT analysis using computer tomography) were carried out. A special point of the research was the use of geochemical modeling code in the form of the GEMS-PSI program in the process of analyzing the modification of silicate mass by glass sand, which is beneficial in limiting ineffective modifications, thus saving time, money, and energy. Studies have shown that the use of glass cullet has a positive effect on the consistency of the modified raw material mass, on the density (1.6–1.75 kg/dm3), and on the compressive strength (15.729–20.3 MPa), while the crystallization of the C-S-H phase occurs in the direction of natrolite and gyrolite, less frequently towards the M-S-H or brucite phase.

Swelling of sulfate-bearing soil: A case study of A1 highway pavement failure

Lime stabilization is one of the most commonly used methods for improving weak road subgrades, but it becomes very problematic in sulfate-bearing soils. This article presents results of a case study in which the sulfate attack was the most probable reason for a significant deformation of a highway pavement founded on lime-stabilized Doggerian clay. Macroscopic analysis revealed partial degradation of the concrete structure, a larger extent of stabilization than designed, and large gypsum crystals in the native soil. Chemical tests indicated a very high content of sulfates in the soil (> 10,000 mg/kg of SO4) and in the groundwater (> 3,000 mg/l of SO42-). The maximum free swelling strain (εvolmax = 3–6%) and the swelling pressure (pcmax = 56 kPa) of the clay, determined in the Wasiliew apparatus and the oedometer tests, were not large enough to be considered as the only cause of the pavement damage. Sand-cement and clay-lime mixtures, which simulated stabilized soil layers in the road profile, were observed for several months in oedometric tests, under various loading conditions. The swelling of Sa-Cem was negligible, but the Cl-Lim mixtures turned out to be much more expansive than the natural soil (εvolmax up to 21%, pcmax = 230 kPa) with a much longer duration of volume increase. The samples were flooded with distilled water or hard groundwater to clarify whether the constant access of the material to sulfates is important in the swelling process, but the results were unequivocal. X-ray diffraction revealed that the addition of lime resulted in the formation of secondary minerals: butlerite, portlandite, and ettringite. The presence and swelling of ettringite in the stabilized sub-base soil layers was eventually agreed to be the most probable reason for the pavement deformation. These results indicate the need to introduce an obligatory investigation of the level of sulfates in clayey subbase soils subject to lime stabilization.

Microwave-Accelerated McKenna Synthesis of Phosphonic Acids: An Investigation.

Phosphonic acids represent one of the most important categories of organophosphorus compounds, with myriad examples found in chemical biology, medicine, materials, and other domains. Phosphonic acids are rapidly and conveniently prepared from their simple dialkyl esters by silyldealkylation with bromotrimethylsilane (BTMS), followed by desilylation upon contact with water or methanol. Introduced originally by McKenna, the BTMS route to phosphonic acids has long been a favored method due to its convenience, high yields, very mild conditions, and chemoselectivity. We systematically investigated microwave irradiation as a means to accelerate the BTMS silyldealkylations (MW-BTMS) of a series of dialkyl methylphosphonates with respect to solvent polarity (ACN, dioxane, neat BTMS, DMF, and sulfolane), alkyl group (Me, Et, and iPr), electron-withdrawing P-substitution, and phosphonate-carboxylate triester chemoselectivity. Control reactions were performed using conventional heating. We also applied MW-BTMS to the preparation of three acyclic nucleoside phosphonates (ANPs, an important class of antiviral and anticancer drugs), which were reported to undergo partial nucleoside degradation under MW hydrolysis with HCl at 130-140 °C (MW-HCl, a proposed alternative to BTMS). In all cases, MW-BTMS dramatically accelerated quantitative silyldealkylation compared to BTMS with conventional heating and was highly chemoselective, confirming it to be an important enhancement of the conventional BTMS method with significant advantages over the MW-HCl method.

Partial enzymolysis affects the digestion of tamarind seed polysaccharides in vitro: Degradation accelerates and gut microbiota regulates

Two hydrolyzed fractions of tamarind seed polysaccharide (TSP), denoted ETSP1 (176.68 kDa) and ETSP2 (34.34 kDa), were prepared by partial degradation via endo-xyloglucanase, and then characterized and evaluated by simulated gastrointestinal digestion in vitro. The results showed that the hydrolyzed TSPs remained indigestible in gastric and small intestinal media, and were fermented by gut microbiota, similar to the native TSP (Mw = 481.52 kDa). Although the degradation of hydrolyzed TSPs was accelerated during fermentation with a decreasing degree of polymerization, the content of produced total short-chain fatty acids (SCFAs) decreased. After fermentation, the gut microbiota composition was modified, esp. the Firmicutes/Bacteroidetes ratio decreased (1.06 vs. 0.96 vs. 0.80) with a decreasing degree of polymerization, which implied that the potential anti-obesity prebiotic effect was enhanced. At the genus level, hydrolyzed TSPs maintained similar roles as native TSP, including promoting beneficial bacteria (Bifidobacterium, Parabacteroides, and Faecalibacterium) and inhibiting enteropathogenic bacteria (Escherichia-Shigella and Dorea). Moreover, ETSP1 had additional potential due to abundant Bacteroides vulgatus (LDA = 4.68), and ETSP2 might perform better as related to Bacteroides xylanisolvens (LDA = 4.40). All these results indicated the prebiotic potential of hydrolyzed TSP with detailed information about changes in degradation and gut microbiota based on enzyme-hydrolysis.

Degradation of thermoplastic cellulose acetate-based bioplastics by full-scale experimentation of industrial anaerobic digestion and composting

The ability of full-scale industrial plants to degrade bioplastics waste must be verified to exclude any negative effects on the quality of the process outputs. This study aims to assess the degradation of two thermoplastic cellulose acetate-based bioplastics, in pure and composite forms in both Anaerobic Digestion (AD) and Composting (C) industrial conditions. The main degradation occurred during AD, where a disintegration of about 36% and 50% was achieved from pure and composite thermoplastic cellulose acetate, respectively. The disintegration during C did not exceed 20% for both samples. The combined process resulted in a slightly higher degradation (58–40%) than that obtained in AD, revealing how the main alteration of samples occurred in an anaerobic environment. Despite this macroscopic degradation, the samples showed only minor superficial degradation as highlighted from SEM analysis. FT-IR spectroscopy, TGA andDSC analyses showed that the biodegradation mechanism involved mainly the plasticizer loss and deacetylation of the cellulose matrix, with only partial degradation of cellulose backbone However, both deacetylation and degradation were favored in AD and AD + C processes and from the presence of filler in anaerobic conditions. These results demonstrated how the degradation obtained on an industrial scale can differ significantly from those obtained in the laboratory scale, especially for pure thermoplastic cellulose acetate. Furthermore, current industrial AD and C process resulted not optimized for the treatment of thermoplastic cellulose acetate-based bioplastics. Hence, this works could help waste facilities managers to process emerging materials such as bioplastics in a more sustainable way.