Chain Length Research Articles

Pure Component and Binary Mixture Adsorption of Light Alkanes and Alkenes on Zeolite NaX at Low Temperatures: Influence of Chain Length.

In this study, the separation of short-chain alkane/alkene pairs by fixed-bed adsorption on zeolite NaX at low temperatures is investigated. Experiments are carried out with pure components and mixtures of ethane/ethene, propane/propene, and n-butane/1-butene in the temperature range between -75 and +40 °C and partial pressures up to 450 Pa. For a short chain length, much stronger adsorption of the alkene is observed. In contrast, with an increase in chain length, the isotherms of alkanes and alkenes of the same chain length become more similar. In addition, a greater influence of temperature on capacity is seen, the shorter the chain length is. In binary mixtures, a strong competition occurs at high total loadings with the alkene displacing the alkane. A characteristic curve is formed for the selectivity in the mixture, which shifts to higher temperatures with an increase in the chain length.

Volatile-char interactions during biomass pyrolysis: Effects of functionalized graphitized carbon nanotubes on volatile distribution of cellulose and its model compounds

Volatile-char interactions are prevalent in biomass pyrolysis processes. To gain deeper insights into their impact on biomass pyrolysis volatile distribution, interactions between volatile compounds and char during flash pyrolysis of glucose, cellobiose, and cellulose were investigated using a pyrolysis–gas chromatography/mass spectrometry detection technique, by modifying both the chain lengths of the raw materials and the functional groups of graphitized multi-walled carbon nanotubes (CNTs). The results reveal that volatile-char interactions markedly influence the distribution of the final pyrolysis products derived from glucose-based compounds. In the presence of any type of CNTs, dehydrated saccharides in the primary products, particularly levoglucosan (LG), exhibit the highest sensitivity to the interactions. Consequently, primary products such as LG and 5-hydroxymethylfurfural (HMF) undergo secondary pyrolysis, yielding compounds such as levoglucosenone (LGO) and 5-methyl-2-furancarboxaldehyde (FCM). Additionally, CNTs without functional groups are advantageous for the production of expensive LGO (The relative abundance reached 9.65%), whereas the relative abundance of FCM increases significantly with hydroxyl-, carboxyl-, and amino-modified carbon nanotubes. Particularly, the relative abundance of FCM is highest in the presence of amino-modified carbon nanotubes, regardless of whether the feedstock is glucose, cellobiose, or cellulose, with values of 25.14%, 23.32%, and 4.23%, respectively. Furthermore, consistent changes in product distribution trends among different glucose-based compounds under identical CNT conditions suggest that glycosidic bonds have minimal impact on volatile-char interactions.

Practical preparation of unsaturated very-long-chain fatty acids (VLCFAs) and very-long-chain alkene pollinator attractants

To prepare very-long-chain fatty acids and alkenes (VLCFAs and VLC alkenes) that are known pollinator attractants for sexually deceptive orchids, and biosynthetic precursors thereof, we applied a methodology allowing us to prepare monounsaturated VLCFAs with chain lengths up to 28 carbons and VLC alkenes up to 31 carbons. We implemented a coupling reaction between commercially available terminal alkynes and bromoalkanoic acids to prepare VLCFAs, allowing the products to be formed in two steps. For VLC alkenes, with many alkyltriphenylphosphonium bromides commercially available, we applied a Wittig reaction approach to prepare (Z)-configured monoenes in a single step. Using practical methods not requiring special reagents or equipment, we obtained 11 VLCFAs in > 90% isomeric purity, and 17 VLC alkenes in > 97% isomeric purity. Such general and accessible synthetic methods are essential for chemical ecology and biochemistry research to aid researchers in unambiguously identifying isolated semiochemicals and their precursors.

Aggression to Biomembranes by Hydrophobic Tail Chains under the Stimulus of Reductant.

Stimulus-responsive materials hold significant promise for antitumor applications due to their variable structures and physical properties. In this paper, a series of peptides with a responsive viologen derivative, Pep-CnV (n = 1, 2, 3) were designed and synthesized. The process and mechanism of the interaction were studied and discussed. An ultraviolet-visible (UV) spectrophotometer and fluorescence spectrophotometer were used to study their redox responsiveness. Additionally, their secondary structures were measured by Circular Dichroism (CD) in the presence or absence of the reductant, Na2SO3. DPPC and DPPG liposomes were prepared to mimic normal and tumor cell membranes. The interaction between Pep-CnV and biomembranes was investigated by the measurements of surface tension and cargo leakage. Results proved Pep-CnV was more likely to interact with the DPPG liposome and destroy its biomembrane under the stimulus of the reductant. And the destruction increased with the length of the hydrophobic tail chain. Pep-CnV showed its potential as an intelligent antitumor agent.

Impact of four surfactants on the uptake of per- and polyfluoroalkyl substances (PFAS) by red fescue grass

Per- and polyfluoroalkyl substances (PFAS) pose great risks to human health and the ecosystem, necessitating effective remediation strategies such as phytoremediation. Surfactants, due to their ability to increase the bioavailability of hydrophobic contaminants, are considered as potential agents to improve phytoremediation for PFAS. In this research, we explored the impact of four surfactants (sodium dodecyl sulfate (SDS), rhamnolipid, Triton X-100, and Glucopone 600 CS UP) on plant growth and the uptake of PFAS by red fescue over 110 days. The results showed that while surfactants at lower concentrations did not negatively affect plant growth, the highest dose (2,500 mg/kg) significantly reduced the dry weight of plant shoots. Although none of the four surfactants led to an increased overall removal efficiency of ∑PFAS by red fescue over 110 days, SDS did enhance the uptake of PFAS compounds with long carbon chain lengths. With SDS addition at 2,500 mg/kg, the average fold increases of long chain PFAS removal were 1.99 for perfluorooctanoic acid (PFOA), 2.44 for perfluorononanoic acid (PFNA), 2.11 for perfluorodecanoic acid (PFDA), 1.52 for perfluoroundecanoic acid (PFUnA), 1.88 for perfluorohexanesulphonic acid (PFHxS), and 2.97 for perfluorooctanesulfonic acid (PFOS). The research indicated that using surfactants, such as SDS at appropriate doses could improve phytoremediation effectiveness in mitigating long-chain PFAS, which is a known challenge in soil remediation.

An ionic liquid in Core-shell structure: Halogen-free, metal-free bifunctional catalyst for olefin epoxidation and CO2 cycloaddition

We synthesized a core-shell resin structure with abundant architecture and excellent thermal stability through polymerization. Imidazole ionic liquid with varying carbon chain lengths was immobilized on the surface, resulting in the preparation of metal-free, halogen-free core-shell catalysts with different carbon chain lengths via HCO3- exchange. Characterization using FT-IR, XPS, and various techniques revealed the exceptional performance of our synthetic catalyst in terms of its internal structure. After extensive experimentation, we discovered that the synthesized catalyst exhibits dual functionality for epoxidation and CO2 cycloaddition reactions without requiring solvents or co-catalysts. The epoxidation system demonstrated remarkable conversion rates and selectivity while also exhibiting strong recyclability in heterogeneous reactions, according to kinetic parameters, the reaction order of styrene, TBHP and catalyst during epoxidation is approximately 1, the reference factor for this reaction was calculated to be 6.7×109 (L2·mol−2·min−1), with an activation energy of 48.9 kJ/mol obtained from analyzing reaction rates at different temperatures. In the CO2 cycloaddition reaction, our catalyst exhibited an advantage in catalyzing ring-opening reactions, achieving a conversion rate of 95 % for styrene oxide within six hours along with over 99 % selectivity towards cyclic carbonate formation. It is suggested that the epoxide reaction is carried out in steps, and it is inferred that the catalyst PS-ImC4HCO3 and TBHP are produced into peroxy intermediate active species TBA and HCO4, and the reaction between HCO4- and styrene is the determination step of the total reaction. The reaction rate constant k=0.009 of the absolute step is calculated based on the global optimization algorithm

Predicting bioconcentration factors (BCFs) for per- and polyfluoroalkyl substances (PFAS)

The bioconcentration factor (BCF) is an important parameter that gives information regarding the ability of a contaminant to be taken up by organisms from the water. Per- and polyfluoroalkyl substances (PFAS) are widespread in the environment, causing concern regarding their impact on human health. Due to the lack of available bioaccumulation data for most compounds in the PFAS group, we developed a quantitative structure-property relationship (QSPR) model to predict the log BCF for fish (taxonomic class Teleostei), based on experimental data available for the most studied 33 representatives of this group of compounds. Furthermore, we implemented the developed model to predict log BCF for an external dataset of 2209 PFAS. Consequently, 1045 PFAS were found not to be bioaccumulative, 208 were classified as bioaccumulative, and 956 were predicted to be very bioaccumulative. Finally, we obtained the high correlation (R2 = 0.844) between the log BCFs obtained in laboratory and field studies for 13 PFAS. In silico analyses indicate that PFAS bioconcentration depends on the size (chain length – number of CF2 groups in alkyl tail/chain) of a molecule, as well as on the atomic distribution properties. In general, long-chain PFAS - above 8 and 6 carbon atoms for perfluorinated carboxylic acids (PFCAs)and perfluorinated sulfonic acids (PFSAs), respectively - tend to bioconcentrate more compared to the short-chain ones. In conclusion, predicting BCF on fish is possible for a wide range of fluorinated compounds, which can be further used for estimating PFAS behavior in the environment.

Phase equilibrium data for semiclathrate hydrates formed with n-propyl, tri-n-butylammonium bromide and tri-n-butyl, n-pentylammonium bromide under methane, carbon dioxide and nitrogen gas pressure

Semiclathrate hydrates are water-based materials formed from aqueous solutions of ionic substances. To enhance the gas capture performance of these materials, it is necessary to direct focus on the cation, which is a key part of construction of the hydrogen-bonding framework. In this paper, we focus on the partly-asymmetric cations, i.e., the n-propyl, tri-n-butylammonium bromide (N3444Br) and tri-n‑butyl, n-pentylammonium bromide (N4445Br), which are yet to be subjected to gas hydrate formation. The three phase equilibrium (gas–hydrate–liquid) conditions for the systems of (N3444Br or N4445Br) + H2O + (CH4, CO2 or N2) in the range of the pressure and mass fractions of the aqueous solutions between 1 and 11 MPa and 0.10–0.40, respectively, are reported. In all the systems, the semiclathrate hydrates were successfully formed under gas pressure. It was demonstrated that both the N3444Br and N4445Br salts promoted hydrate formation under these gases, while in the case with lean aqueous solutions N3444Br acted as an inhibitor of methane hydrate formation in pure water system. The present data are compared with the literature data, and the effect of the side chain length on the phase behavior of the semiclathrate hydrate phase is discussed.

Experimental and theoretical insight into the use of maleic anhydride copolymer and modified sulfamic acid for removing oilfield blockage

In the process of oil production, the problem of oilfield production decline due to blockage is becoming more and more serious. To improve the exploitation efficiency of traditional fuel, it is very important to remove the blockage and inhibit the formation of the blockage. In this study, the primary constituents of the blockages in this oilfield were identified as asphaltene (organic blockage) and calcium carbonate (CaCO3, inorganic blockage). To address these blockages, maleic anhydride copolymer (MAC-1, MAC-2, and MAC-3) with different chain lengths were polymerized by maleic anhydride and allyl polyoxyethylene ether, which were used to disperse organic blockages. Additionally, modified sulfamic acid (MSA-1, MSA-2, and MSA-3) with different chain lengths were synthesized by sulfamic acid, polyethylene glycol, and lauroyl chloride, which were used to dissolve inorganic blockages. The efficacy of these agents in terms of blockage removal, scale inhibition capability, corrosion rate, and compatibility with formation water were comprehensively evaluated. Results showed that MAC-2, which possesses a moderate chain length, and MSA-1, which has a shorter chain length, demonstrated an optimal synergistic effect on blockage dissolution at concentrations of 4 wt% for MAC-2 and 5 wt% for MSA-1. The dissolution rate of this combination was 81.18 %, with a scale inhibition rate of 95.7 %. The corrosion rate increased with temperature, and the agents maintained good compatibility with the formation water. To elucidate the mechanism underlying the effectiveness of MAC, the interaction between MAC and asphaltene was simulated by molecular dynamics (MD). These simulations indicated that MAC-2 and asphaltene exhibit the highest interaction energy (-64.2618 kcal/mol). Furthermore, we investigated the dissolution kinetics of CaCO3 in MSA solutions and determined that the reaction between MSA and CaCO3 was first-order, with a reaction rate constant of 1.6 × 10−2 min−1. The insights gained from this study offer a valuable experimental and theoretical foundation for enhancing productivity in similar oilfields.

Weakened functional group activity enables the uniform distribution of the gel electrolyte to achieve the high-performance of Li-ion batteries

Electrolyte gelation is considered to be one of the main routes to solve the safety problem of liquid electrolytes. However, the distribution of gel polymer electrolyte (GPE) on the surface of electrodes and the mechanism of their effect on the performance of battery are still unknown. Here, methyl methacrylate (MMA) containing methyl (-CH3) and methyl-2-cyanoacrylate (MCA) containing cyanide (-CN) are employed as representative monomers to explore the relationship between gel distribution and battery performance. Due to the stronger electron-withdrawing properties, PMCA gel has shorter chain length and greater shrinkage, showing many cracks on the electrode surface, while PMMA gel can evenly cover the surfaces of electrodes. As a result, the capacity retention rate of 1.4 Ah NCM811/Gr pouch cells with PMMA is 93.5% for 500 cycles at 25 °C and 91.5% for 600 cycles at 60 °C, which these of the cells with PMCA are 58.8% for 266 cycles at 25 °C and 69.1% for 327 cycles at 60 °C. XPS analysis of the electrode sheets before and after cycling reveal that the PMCA-electrode has a large number of rzero valent lithium element precipitation, whereas the PMMA-electrode has the more stable interface film. This study indicates that the uniform distribution of gel electrolyte with -CH3 functional group on the electrode surface can improve the electrochemical performance of NCM811/Gr battery, which has the guiding significance.

Experimental and molecular simulation study on the influence of chain length and anion structure of ionic liquids on the wettability of highly hydrophobic bituminous coal

The wettability of bituminous coal is critical for the coal dust suppression and can be apparently modulated by ionic liquids. However, the modulation mechanism still remains elusive. Here, a combination of macroscopic experiments, mesoscopic characterization, and microscopic simulations (quantum mechanics and molecular dynamics) are leveraged to parse the effect on the wettability of coal dust surfaces of three novel ionic liquids ([C12MIm]Br, [BMIm]Br, [BMIm]Cl) featuring the varying chain lengths and anions in the coal-water system. The results show that the selected ionic liquids exert a distinct bridging function from traditional surfactants which invoke the hydrogen bonding interaction. This ionic liquids-mediated bridging mechanism heavily depends on their chain length structure, which can firstly penetrate deeply the internal pores of coal dusts and then adsorb on the coal surfaces to rapidly strike a dynamic equilibrium. Ionic liquids interacting with coal dust can primarily reduce the energy difference between polar and nonpolar interactions within coal dust, thereby enhancing the electrostatic interactions between coal dust and water molecules and effectively improving coal dust wetting properties. These findings provide a theoretical basis for the rational design of high-performance ionic liquids for coal mine dust control.

Functional Peptides from Yak Milk Casein: Biological Activities and Structural Characteristics.

The average content of casein in yak milk is 40.2 g/L. Casein can be degraded by enzymatic digestion or food processing to produce abundant degradation peptides. International researchers have studied the degradation peptides of yak milk casein by using multiple techniques and methods, such as in vitro activity tests, cellular experiments, proteomics, bioinformatics, etc., and found that the degradation peptides have a wide range of functional activities that are beneficial to the human body, such as angiotensin-converting enzyme (ACE) inhibitory, antioxidant, anti-inflammatory, antidiabetic, antimicrobial, anticancer, and immunomodulatory activities, etc., and it has been proved that the types and strengths of functional activities are closely related to the structural characteristics of the peptides. This paper describes the characteristics of yak milk proteins, the functional activities, and mechanism of action of degraded peptides. Based on the types of functional activities of yak milk casein degradation peptides, we classified and elucidated the effects of structural factors, such as peptide molecular weight, peptide length, amino acid sequence, physicochemical properties, electrical charge, hydrophobicity, spatial conformation, chain length, and the type of enzyme on these activities. It reveals the great potential of yak milk casein degradation peptides as functional active peptide resources and as auxiliary treatments for diseases. It also provides important insights for analyzing yak casein degradation peptide activity and exploring high-value utilization.

Spatiotemporal coordination of antigen presentation and co-stimulatory signal for enhanced anti-tumor vaccination

Controlled-release systems enhance anti-tumor effects by leveraging local antigen persistence for antigen-presenting cells (APCs) recruitment and T cell engagement. However, constant antigen presentation alone tends to induce dysfunction in tumor-specific CD8+ T cells, neglecting the synergistic effects of co-stimulatory signal. To address this, we developed a soft particle-stabilized emulsion (SPE) to deliver lipopeptides with controlled release profiles by adjusting their hydrophobic chain lengths: C6-SPE (fast release), C10-SPE (medium release), and C16-SPE (slow release). Following administration, C6-SPE release antigen rapidly, inducing early antigen presentation, whereas C16-SPE's slow-release delays antigen presentation. Both scenarios missed the critical window for coordinating with the expression of CD86, leading to either T cell apoptosis or suboptimal activation. In contrast, C10-SPE achieved a spatiotemporally synergetic effect of the MHC-I-peptide complex and co-stimulatory signal (CD86), leading to effective dendritic cell (DC) activation, enhanced T cell activation, and tumor regression in EG7-OVA bearing mice. Additionally, co-delivery of cytosine-phosphate-guanine (CpG) with SPE provided a sustained expression of the CD86 window for DC activation, improving the immune response and producing robust anti-tumor effects with C6-SPE comparable to C10-SPE. These findings highlight that synchronizing the spatiotemporal dynamics of antigen presentation and APC activation may confer an optimal strategy for enhanced vaccinations.

Characterization of caseinate-pectin complex coacervates as a carrier for delivery and controlled-release of saffron extract

In this work, microcapsules were developed by the complex coacervation of sodium caseinate and pectin as a carrier for saffron extract. Parameters such as Zeta potential, dynamic light scattering, and microscopic techniques were investigated for their influence on the formation of these complexes. Furthermore, Fourier transform infrared (FTIR) analysis confirmed the reaction mechanism between the protein and tannic acid or saffron extract. The study revealed that core/shell and protein/polysaccharide (Pr/Ps) ratios play a role in the encapsulation efficiency (EE) and loading capacity (LC) of saffron extract, with EE and LC ranging from 48.36 to 89.38% and 1.14 to 5.55%, respectively. Thermal gravimetric analysis revealed that the degradation temperature of saffron increased significantly with microencapsulation. The use of tannic acid for hardening the microcapsules led to an increase in size from 13 μm to 27 μm. Rheological findings indicated that shear-thinning behavior in the coacervates, with cross-linking, has a minor effect on the interconnected elastic gel structures. However, cross-linking improved the microcapsules' thermal and structural properties. The increase in polymer chain length due to cross-linking and the presence of the guest molecule (saffron extract) resulted in higher rheological moduli, reflecting enhanced entanglements and correlating well with the thermal, structural, and microstructural properties of the coacervates. Kinetic release studies showed a slower release in the gastric phase compared to the intestinal phase, with the Ritger–Peppas model effectively describing saffron extract release, highlighting a dominant swelling and dissolution release mechanism. Therefore, the NaCas/HMP coacervate wall materials made saffron stable in the gastric stage and sustainably release. It in the intestinal stage, promoting excellent absorption of saffron in simulated digestion.Graphical

Impact of the alkyl side-chain length on solubility, interchain packing, and charge-transport properties of amorphous π-conjugated polymers

Increasing the length of alkyl side chains is a typical way to improve the solubility of π-conjugated polymers designed for use in solution-processed devices. However, these modifications have also been reported to alter the film morphology. Given that the mechanism leading to improved solubility is not well documented yet and the nanoscale (local) morphologies of amorphous π-conjugated polymer films are difficult to characterize experimentally, here, we combine molecular dynamics simulations and long-range corrected density functional theory calculations to examine at the molecular scale the impact that the alkyl side-chain length has on polymer solubility and film morphologies. As a representative example, we consider poly(thieno[3,4-c]pyrrole-4,6-dione-alt-3,4-difluorothiophene) (PTPD[2F]T) with two different lengths of the alkyl side chains on the thieno[3,4-c]pyrrole-4,6-dione (TPD) moieties, i.e., 2-hexyldecyl (2HD) and 2-decyltetradecyl (2DT). A detailed analysis of polymer–solvent and polymer–polymer interactions provides a picture that describes the underlying mechanism for improved solubility in going from 2HD to 2DT. We then underline an intrinsic characteristic that decreasing the side-chain length brings a greater extent of backbone planarity and lesser side chain-TPD interactions, which leads to higher interchain π-π packing density and order, while the interchain π-π packing patterns remain similar in the two films. These morphologies are discussed in terms of the charge-transport properties between neighboring PTPD[2F]T chains, which point to a higher electron mobility in the PTPD[2F]T films with shorter alkyl side chains. Overall, our findings offer guidance in the field of solution-processed electronic devices by pointing out that the polymer alkyl side-chain length could be minimized to improve carrier mobility while ensuring polymer solubility.

Migratory-derived resources induce elongated food chains through middle-up food web effects

BackgroundSeasonal movements of animals often result in the transfer of large amounts of energy and nutrients across ecosystem boundaries, which may have large consequences on local food webs through various pathways. While this is known for both terrestrial- and aquatic organisms, quantitative estimates on its effects on food web structure and identification of key pathways are scarce, due to the difficulty in obtaining replication on ecosystem level with negative control, i.e. comparable systems without migration.MethodsIn this study, we estimate the impact of Arctic charr (Salvelinus alpinus) migration on riverine ecosystem structure, by comparing multiple streams with strictly resident populations above natural migration barriers with streams below those barriers harboring partially migratory populations. We compared density estimates and size structure between above and below populations. Diet differences were examined through the analysis of stomach contents, changes in trophic position were examined by using stable isotopes. To infer growth rate of resident individuals, back-growth calculation was performed using otoliths.ResultsWe find higher densities of small juveniles in partially migratory populations, where juvenile Arctic charr show initially lower growth, likely due to higher intraspecific competition. After reaching a size, where they can start feeding on eggs and smaller juveniles, which are both more frequent in partially migratory populations, growth surpasses that of resident populations. Cannibalism induced by high juvenile densities occurred almost exclusively in populations with migration and represents an altered energy pathway to the food web. The presence of large cannibalistic charr feeding on smaller ones that have a similar trophic level as charr from strictly resident populations (based on stomach content) coupled with steeper δ15N-size regression slopes illustrate the general increase of food chain length in systems with migration.ConclusionsOur results thus suggest that the consumption of migration-derived resources may result in longer food chains through middle-up rather than bottom-up effects. Furthermore, by occupying the apex of the food chain and feeding on juvenile conspecifics, resident individuals experience reduced competition with their young counterparts, which potentially balances their fitness with migratory individuals.

High-Efficiency Purification and Morphology Regulation of CaSO4·2H2O Crystals from Phosphogypsum.

Phosphogypsum is a solid waste with great environmental stockpile pressure produced by the wet production of phosphoric acid. Although there are various methods to purify and utilize phosphogypsum, the means for environmentally friendly, low energy consumption, and high value-added utilization still need to be further explored. Here, CaSO4·2H2O crystal was directly purified and regulated from phosphogypsum by using the anti-solvent method. The antisolvent can be adsorbed in the c-axis direction of the crystal and further inhibit the growth rate in this direction, resulting in a change in the morphology of the crystal. By adjusting the polarity and chain length of the anti-solvent, the morphology of CaSO4·2H2O crystal can change from butterfly-like flake crystals to hexagonal prism-like crystals. When n-propanol with long chain was used as the anti-solvent, the morphology of the CaSO4·2H2O crystal showed a hexagonal prism with a specific surface area of 19.98 m2/g and a Cu2+ loading efficiency of 52.67%. The encouraging results open up new possibilities for the application of phosphogypsum.

A highly efficient oxygen tolerant visible-light mediated RAFT polymerization

Recently, oxygen-tolerant reversible addition-fragmentation chain transfer (RAFT) polymerization has attracted increasing attention in polymer chemistry. Inspired by the monomers containing glycol ethers group have high polymerization rates and even achieved a desirable oxygen tolerance. Herein, we proposed a simple, effective, low-cost, and eco-friendly strategy to accomplish the oxygen-tolerant visible-light activated RAFT polymerization of acrylates and acrylamides in a mixed solution of glycol ether and water at ambient temperature. This photo-mediated RAFT polymerization does not require additives, prior deoxygenation, or inert gas protection. The acrylates and acrylamides with high conversion under irradiation for 2 h, and the resulting polymers were narrow unimodal and narrow molecular weight distributions (PDI<1.3). In addition, the “living” and well-controlled behaviors of this oxygen-tolerant photo-mediated RAFT polymerization were demonstrated through water content in solvents, headspace, initial concentration of monomers, various monomers, chain lengths, light ON/OFF experiment, and high-end group fidelity of block copolymers. This RAFT polymerization also opens up a wide avenue for the industrial production of functional polymeric materials via an in situ chain extension strategy. These results indicate that the mixed solution of glycol ethers and water are effective green media for promoting photo-mediated RAFT polymerization without additives or tedious degassing processes.

Impact of freeze-thaw cycles on the physicochemical properties and structure-function relationship of potato starch with varying granule sizes in frozen dough

Starch, as a critical component of dough, significantly influences quality preservation during the freezing process. In particular, the fine structure of potato (B-type) starch in frozen processing is a subject of considerable interest. This study aims to investigate the intrinsic differences of B-type starch and the impact of freeze-thaw (F/T) treatment on its molecular structure and physicochemical properties. Chain length distribution and X-ray photoelectron spectroscopy were utilized to examine the structural characteristics of natural potato starch with different granule sizes. Furthermore, the fine structure, thermal properties, and rheological properties of the isolated starches after F/T treatment were analyzed. The results indicate that potato starch with smaller particle sizes exhibits higher surface CC and PO content along with a higher proportion of very short chains (DP < 6, 8.17 %) and long B chains (DP > 25, 20.68 %). The study found that after F/T treatment, the surface of small-sized starch granules was initially damaged, exhibiting threads on the surface centered on the umbilical point. Following F/T treatment, both the crystallinity (very large (VL): 24.52–18.36 %; small (S): 17.03–16.69 %) and short-range order (VL: 2.97–2.61; S: 2.71–2.35) of starch particle size decreased. Both the amylose content (20.88–14.57 %) and ΔH (10.15–8.62 J/g) of isolated starch after freeze-thaw-treated dough exhibited a decrease to varying degrees. With the exception of the fifth cycle, small-size starch particles exhibited relatively higher G' and G" values and showed significant changes as a result of F/T treatment, demonstrating high hardness and complex viscosity. Clarifying the physicochemical properties of potato starches with different granule sizes is expected to expand their applications in frozen dough.

Development of chemical categories for per- and polyfluoroalkyl substances (PFAS) and the proof-of-concept approach to the identification of potential candidates for tiered toxicological testing and human health assessment

Per- and Polyfluoroalkyl substances (PFAS) are a class of manufactured chemicals that are in widespread use and many present concerns for persistence, bioaccumulation and toxicity. Whilst a handful of PFAS have been characterized for their hazard profiles, the vast majority have not been extensively studied. Herein, a chemical category approach was developed and applied to PFAS that could be readily characterized by a chemical structure. The PFAS definition as described in the Toxic Substances Control Act (TSCA) section 8(a)(7) rule was applied to the Distributed Structure-Searchable Toxicity (DSSTox) database to retrieve an initial list of 13,054 PFAS. Plausible degradation products from the 563 PFAS on the non-confidential TSCA Inventory were simulated using the Catalogic expert system, and the unique predicted PFAS degradants (2484) that conformed to the same PFAS definition were added to the list resulting in a set of 15,538 PFAS. Each PFAS was then assigned into a primary category using Organisation for Economic Co-operation and Development (OECD) structure-based classifications. The primary categories were subdivided into secondary categories based on a chain length threshold (>=7 vs < 7). Secondary categories were subcategorized using chemical fingerprints to achieve a balance between total number of structural categories vs.level of structural similarity within a category based on the Jaccard index. A set of 128 terminal structural categories were derived from which a subset of representative candidates could be proposed for potential data collection, considering the sparsity of relevant toxicity data within each category, presence on environmental monitoring lists, and the ability to identify plausible manufacturers/importers. Refinements to the approach taking into consideration ways in which the categories could be updated by mechanistic data and physicochemical property information are also described. This categorization approach may be used to form the basis of identifying candidates for data collection with related applications in QSAR development, read-across and hazard assessment.