Aliphatic Research Articles

Experimental Correlation between Apparent pKa and Gelation Propensity in Amphiphilic Hydrogelators Derived from l-Dopa.

We report the gelation propensity of three gelators derived from l-dihydroxyphenylalanine (l-Dopa), where the amino group is derivatized with three different fatty acids (lauric acid, palmitic acid, and azelaic acid). The long aliphatic side chains should introduce additional van der Waals interactions among the molecules, contributing to the self-assembly process. The hydrogels have been prepared with the pH change method, and both the hydrogels and the corresponding aerogels have been analyzed using several techniques. In any case, Lau-Dopa provides stronger hydrogels compared with the other gelators. This property may be ascribed to its tendency to efficiently form supramolecular β-sheet structures, as outlined by the ECD, IR, and SEM analyses. Moreover, the preliminary measurement of the apparent pKa displays for Lau-Dopa two plateaux, as previously observed for, one at about pH 12 and a second one at pH 7.5. Thus, its pKa results in two apparent pKa shifts of ∼8.5 and ∼4 pH units above the theoretical pKa, as a consequence of a multistep self-assembly pathway that correlates, in the final β-sheet-based hydrogel, with a high degree of order and stability.

Biodegradability of unheated and laboratory heated dissolved organic matter.

Following wildfires, partially combusted biomass remains on the forest floor and erosion from the landscape can release dissolved pyrogenic organic matter (dPyOM) to surface waters. Therefore, post-fire alterations to dissolved organic matter (DOM) in aquatic systems may play a vital role in DOM stability and biogeochemical cycles. Dissolved PyOM biodegradation remains poorly understood and is expected to vary with combustion temperature and fuel source. In this study laboratory heating and leaching of forest floor materials (soil and litter) were used to compare the biodegradability of unheated, low (250 °C), and moderate (450 °C) temperature leachates. Inoculation experiments were performed with river microbes. Dissolved organic carbon (DOC) and nitrogen (DON), inorganic nitrogen, and DOM optical properties were monitored for 38 days. Inoculation experiments showed significantly greater DOC biodegradation of low and moderate temperature samples (64% and 71%, respectively) compared to unheated samples (32%). The greater DOC biodegradation may be explained by lower molecular weight DOM composition of heated leachates which was supported by higher initial E2/E3 ratios (absorbance at 250 nm/365 nm). Further, the observed decrease in the E2/E3 ratio after incubation suggests biodegradation of smaller compounds. This trend was greater for heated samples than unheated DOM. Specific ultraviolet absorbance increased after incubation, suggesting biodegradation of aliphatic compounds. Inoculated moderate temperature samples showed the greatest DON degradation (74%), followed by low temperature (58%) and unheated (51%) samples. Overall, results suggest that low and moderate temperature dPyOM was more biodegradable than unheated DOM, which may have implications for aquatic biogeochemical cycling, ecosystem function, and water quality in fire-impacted watersheds.

Structure characteristics and combustion kinetics of the co-pyrolytic char of rice straw and coal gangue

Co-combustion is a technology that enables the simultaneous and efficient utilization of biomass and coal gangue (CG). Nevertheless, the factors that affect the combustibility of co-pyrolytic char, which represents the rate-determining step of the entire co-combustion process, remain unclear. This study investigates the impact of the physicochemical properties of co-pyrolytic char, including pore structure, carbon structure, and alkali metals, on the combustion characteristics. The TGA analysis indicates that the ignition and burnout temperatures of the co-pyrolytic char increase as the CG mixing ratio increases, resulting in a prolonged combustion. This is due to the fact that the carbon structure of the co-pyrolytic char becomes increasingly aromatic, accompanied by a reduction in aliphatic hydrocarbons and oxygen-containing groups as the CG mixing ratio increases. Furthermore, the high ash content of the CG is another significant factor contributing to the observed reduction in combustibility. The reaction between mullite, quartz in CG, and alkali metals in biomass results in the formation of aluminosilicate, which reduces the catalytic ability of alkali metals. Furthermore, the char combustion kinetics are analyzed by the KAS method, and the results indicate that the introduction of CG increases the activation energy of the entire char combustion process. The activation energy of the 80RS20CG is within the range of 102.22–164.99 kJ/mol, while the RS char is within the range of 89.87–144.67 kJ/mol.

Vesicles exhibit high-performance removal of per-and polyfluoroalkyl substances (PFAS) depending on their hydrophobic groups

The removal of per- and polyfluoroalkyl substances (PFAS) from drinking water is urgently needed. Here, we demonstrated high performance of vesicles on PFAS adsorption. Vesicles used in this study were enclosed amphiphile bilayers keeping their hydrophobic groups inside and their hydrophilic groups outside in water. The distribution coefficient Kd of perfluorooctane sulfonic acid (PFOS) for vesicles was 5.3 × 105 L/kg, which is higher than that for granulated activated carbon (GAC), and Kd of perfluorooctanoic acid (PFOA) for vesicles was 103–104 L/kg. The removal efficiencies of PFOA and PFOS adsorption on DMPC vesicles were 97.1 ± 0.1% and 99.4 ± 0.2%, respectively. The adsorption behaviors of PFOA and PFOS on vesicles were investigated by changing the number of cis-double bonds in the hydrophobic chains of the vesicle constituents. Moreover, vesicles formed by membranes in the different phases were also tested. The results revealed that, when vesicles are formed of a membrane in the liquid-crystalline (liquid-like) phase, the adsorption amounts of both PFOA and PFOS increased as the cis-double bond in the hydrocarbon chains decreased, which is considered due to molecular shape similarity. When vesicles are formed of a membrane in the gel (solid-like) phase, they do not adsorb PFAS as much as in the liquid-crystalline phase, even though the hydrocarbon chains do not have any cis-double bond. Our findings demonstrate that vesicles can be utilized as PFAS adsorbents by optimizing the structure of vesicle constituents and their thermodynamical phase. Indeed, the vesicles (DMPC) were demonstrated that they can adsorb PFOA and PFOS, and be coagulated by a coagulant even in environmental water. The coagulation will enable the removal of PFOA and PFOS from the water after adsorption.

Ionizable STING-Activating Nanoadjuvants Enhance Tumor Immunogenicity and Potentiate Immunotherapy Efficacy in Solid Tumors.

Therapeutic strategies that induce inflammatory responses in immunologically "cold" tumors have the potential to improve immunotherapeutic outcomes. Pharmacologically activating the STING pathway induces innate immunity, subsequently enhancing tumor immunogenicity. Here, we developed a nanoadjuvant with tumor-restricted pharmacology that rapidly activated STING and reshaped the tumor microenvironment (TME). The non-nucleotide STING agonist MSA-2 was chemically engineered with a piperazine motif linked by a saturated hydrocarbon chain of varying lengths to produce ionizable prodrugs that were further developed into nanoadjuvants. Compared with state-of-the-art liposomes, the nanoadjuvant displayed prolonged retention in the circulation and improved intratumoral delivery. In the acidic TME, the nanoadjuvant underwent polyethylene glycol deshielding, enabling efficient extravasation and penetration into tumors. Concomitantly, the STING prodrug escaped from the endo/lysosome compartment to partition into the cytosol for spontaneous esterase-catalyzed drug activation. In mouse models of syngeneic and chemically induced colorectal cancers, nanoparticle treatment provoked robust STING-mediated antitumor immunity, shifting the tumor immune landscape from immunosuppressed to tumoricidal. Additionally, the nanoadjuvant demonstrated antitumor efficacy in triple-negative breast cancer, which was further enhanced by the addition of immune checkpoint inhibitors. Collectively, this study demonstrates the safety and immune stimulating effects of a STING-activating nanoadjuvant, supporting the clinical evaluation of this STING immunotherapeutic alone and in combination with other immunotherapies.

Genome and metabolome analysis of Bacillus sp. Hex-HIT36: a newly screened functional microorganism for the degradation of 1-Hexadecene in industrial wastewater

1-Hexadecene has been detected at a level of mg/L in both influent and effluent of wastewater treatment plants situated in chemical/pharmaceutical industrial parks, which poses a potential threat to the environment. However, few reports are available on aerobic metabolic pathways and microorganisms involved in 1-Hexadecene degradation. In this study, a new strain of 1-Hexadecene-degrading bacteria, Bacillus sp. Hex-HIT36 (HIT36), was isolated from the activated sludge of a wastewater treatment plants located in an industrial park. The physicochemical properties and degradation efficacy of HIT36 were investigated. HIT36 was cultured on a medium containing 1-Hexadecene as a sole carbon source; it was found to remove ∼67% of total organic carbon as confirmed by mass spectrometric analysis of intermediate metabolites. Metabolomic and genomic analysis showed that HIT36 possesses various enzymes, namely, pyruvate dehydrogenase, dihydropolyhydroxyl dehydrogenase, and 2-oxoglutarate-2-oxoiron oxidoreductase (subunit alpha), which assist in the metabolization of readily available carbon source or long chain hydrocarbons present in the growth medium/vicinity. This suggests that HIT36 has efficient long-chain alkane degradation efficacy, and understanding the alkane degradation mechanism of this strain can help in developing technologies for the degradation of long-chain alkanes present in wastewater, thereby assisting in the bioremediation of environment.

Mechanism insight into the conversion between COS and thiophene during CO2 gasification of carbon-based fuels

Thiophene is the organic sulfur with good thermal stability in carbon-based fuel, clarifying the conversion mechanism between thiophene and COS is beneficial for achieving in-situ sulfur fixation during CO2 gasification of carbon-based fuels, but the mechanism has rarely been reported. Therefore, calculations based on density functional theory were performed and 16 reaction paths were proposed in this research, clarifying the decomposition mechanism of thiophene and re-fixation mechanism of COS. The attachment of CO2 will lead to the destruction of the thiophene ring and the generation of COS, and CO2 adsorption is the rate-determined step, while the carbon atom that adjacent sulfur atom is the reaction active site. However, the energy barriers of CO2 addition reactions are lower than those of CO2 adsorption reactions, and the energy barrier of reactions occurring on the aliphatics are lower than that occurring on the aromatics. The combination of CO2 and thiophene will thermodynamically lead to the generation of COS and CO. Moreover, gaseous sulfur generated from thiophene decomposition will be converted mutually, while H2S will not be converted into COS. Furthermore, COS will be captured by char, forming solid organic sulfur. The re-fixation of COS will occur on aliphatic chains from the decomposition of aromatics.

The Preservation and Spectral Detection of Historic Museum Specimen Microbial Mat Biosignatures Within Martian Dust: Lessons Learned for Mars Exploration and Sample Return.

The key building blocks for life on Mars could be preserved within potentially habitable paleo-depositional settings with their detection possible by utilizing mid-infrared spectroscopy; however, a definite identification and confirmation of organic or even biological origin will require the samples to be returned to Earth. In the present study, Fourier-transform infrared (FTIR) spectroscopic techniques were used to characterize both mineralogical and organic materials within Mars dust simulant JSC Mars-1 and ancient Antarctic cyanobacterial microbial mats from 1901 to 1904 Discovery Expedition. When FTIR spectroscopy is applied to cyanobacterial microbial mat communities, the resulting spectra will reflect the average biochemical composition of the mats rather than taxa-specific spectral patterns of the individual organisms and can thus be considered as a total chemical analysis of the mat colony. This study also highlights the potential difficulties in the detection of these communities on Mars and which spectral biosignatures will be most detectable within geological substrates. Through the creation and analysis of a suite of dried microbial mat material and Martian dust simulant mixtures, the spectral signatures and wavenumber positions of CHx aliphatic hydrocarbons and the C-O and O-H bands of polysaccharides remained detectable and may be detectable within sample mixtures obtained through Mars Sample Return activities.

Alkanols Regulate the Fluidity of Phospholipid Bilayer in Accordance to Their Concentration and Polarity.

In spite of the widespread use of alkanols as penetration enhancers, their effect on vesicular formulations remains largely unexplored. These can affect the stability and integrity of the phospholipid bilayers. In this study, we have investigated the interaction of linear (ethanol, butanol, hexanol, octanol) and branched alkanols (t-amylol and t-butanol) with three phospholipids (soya lecithin, SL; soy L-α-phosphatidylcholine, SPC; and 1,2-dipalmitoyl-sn-glycero-3-phosphocholine, DPPC). Thermodynamic and structural aspects of these interactions were studied as a function of the alkanol concentration and chain length. Our interpretations are based on isothermal titration calorimetry (ITC) and dynamic light scattering (DLS) experiments. We observed one-site interactions wherein hydroxyl and acyl groups interacted with the polar and nonpolar regions of the phospholipid, respectively. The stability and structural integrity of bilayers appeared to be dependent upon (a) the hydrocarbon chain length and concentration of alcohols, and (b) the degree of unsaturation in the phospholipid molecule. We found that these interactions triggered a reduction in the enthalpy which was compensated by increased entropy, keeping free energy negative. Drop in enthalpy indicates reversible disordering of the bilayer which enables the diffusion of alcohol without triggering destabilization. Ethanol engaged predominantly with the interface, and it resulted in higher enthalpic changes. Interactions became increasingly unfavorable with longer alcohols - a cutoff point was recorded with hexanol. The overall sequence of membrane disordering capability was recorded as follows: ethanol < butanol < octanol < hexanol. Octanol's larger size restricted its penetration in the bilayer, and hence it caused less enthalpic changes relative to hexanol. This could also be verified from the trends in the area ratio of these vesicles obtained from the DLS data. Branched alkanols displayed a lower binding affinity with the phospholipids relative to their linear counterparts. These data are useful while contemplating the inclusion of short-chain alcohols as penetration enhancers in phospholipid vesicles.

Pyrolysis of high-density polyethylene: Degradation behaviors, kinetics, and product characteristics

Pyrolysis is a promising technology for converting plastic waste into valuable raw materials while offering a potential solution to the global plastic pollution crisis. In this study, the thermal pyrolysis of high-density polyethylene (HDPE) is investigated in a drop tube reactor under nearly isothermal conditions. The impact of reaction temperature and gas/volatile residence time on carbon conversion and product distribution is examined across a range of 500–900 °C and 3.6–32.2 s, respectively. Non-condensable gas products detected by online mass spectrometry are H2, CH4, C2H4, C2H6, C3H6, and C3H8. At elevated temperatures and prolonged residence time, H2 yield reaches as high as 8.6 wt% of the initial HDPE mass due to intensified cracking reactions of C2–C3 hydrocarbons and long-chain aliphatic compounds. Consequently, pyrolysis tars consist mainly of polycyclic aromatic hydrocarbons (PAHs) with 5–7 rings, accompanied by visible coke deposition within the reactor. HDPE decomposition to volatiles is an endothermic process and it is complete at a temperature between 492 °C and 525 °C, depending on the heating rate employed, from non-isothermal thermogravimetric analysis and differential scanning calorimetry (TGA-DSC) measurements. The thermal degradation of HDPE pellets follows the two-dimensional nucleation growth model for conversion levels up to 0.8 with an apparent activation energy of 259–270 kJ/mol and a pre-exponential factor of 4.83 × 1017–1.37 × 1019 min−1, determined from various isoconversional methods such as Flynn-Wall-Ozawa (FWO), Kissinger-Akahira-Sunose (KAS), and Starink, along with Criado's master plots. These findings provide valuable insights into optimizing process parameters and refining reactor design for pyrolysis, which can be integrated with gasification and reforming processes to enhance hydrogen production on a larger scale.

Molecular and Phytochemical Characteristics of Flower Color and Scent Compounds in Dog Rose (Rosa canina L.).

This study delves into the chemical and genetic determinants of petal color and fragrance in Rosa canina L., a wild rose species prized for its pharmacological and cosmetic uses. Comparative analysis of white and dark pink R. canina flowers revealed that the former harbors significantly higher levels of total phenolics (TPC) and flavonoids (TFC), while the latter is distinguished by elevated total anthocyanins (TAC). Essential oils in the petals were predominantly composed of aliphatic hydrocarbons, with phenolic content chiefly constituted by flavonols and anthocyanins. Notably, gene expression analysis showed an upregulation in most genes associated with petal color and scent biosynthesis in white buds compared to dark pink open flowers. However, anthocyanin synthase (ANS) and its regulatory gene RhMYB1 exhibited comparable expression levels across both flower hues. LC-MS profiling identified Rutin, kaempferol, quercetin, and their derivatives as key flavonoid constituents, alongside cyanidin and delphinidin as the primary anthocyanin compounds. The findings suggest a potential feedback inhibition of anthocyanin biosynthesis in white flowers. These insights pave the way for the targeted enhancement of R. canina floral traits through metabolic and genetic engineering strategies.

Synthesis of metal-free heteroatom (N, P, O, and B) doped biochar catalysts for enhanced catalytic co-pyrolysis of walnut shells and palm oil fatty acid distillate to produce high-quality bio-oil

In the current study, sugarcane bagasse-derived biochar catalysts were synthesized by doping with metal-free heteroatoms including nitrogen, phosphorus, oxygen, and boron and their efficacy was tested for catalytic co-pyrolysis of walnut shells (WS) and palm oil fatty acid distillate (PFAD) using Py-GC/MS. The biochar catalysts’ properties and their effectiveness on co-pyrolytic bio-oil (overall product distribution, selectivity towards aliphatic and aromatic hydrocarbons, and carbon number ranges) were extensively examined. Among the various catalysts considered, boron-doped biochar (BCB) demonstrated effective performance due to an improved surface area, porosity, and acidity and resulted in a significantly increased hydrocarbon yield, particularly in the gasoline and diesel range, and preference for aromatic over aliphatic hydrocarbons. The optimum bio-oil quality was achieved at a feedstock-to-catalyst ratio of 2:1 and a pyrolysis temperature of 750 °C, with a hydrocarbon yield of 90.8% and aromatic hydrocarbon selectivity of 63.5%. Overall, the study underscores the role of BCB in fostering deoxygenation, decarboxylation, and aromatic selectivity via thermal and catalytic pathways, highlighting the potential of non-metallic doped biochars for bio-oil upgrading.

Distribution and characterization of products obtained from pyrolysis of cooked food waste- Impact of heating rate

This work offers a comprehensive investigation of the pyrolysis products—liquid, gas, and solid derived from cooked food waste (CFW) at different heating rates (15-100°C/min). The heating rate significantly influenced the yield of pyrolysis products. The maximum yield of bio-oil (oil + aqueous) was achieved at a heating rate of 50°C/min, py-gas at 100°C/min, and biochar at 15°C/min. The yields were 34wt% for bio-oil, 30wt% for py-gas, and 32wt% for biochar. Analysis of the bio-oil revealed significant proportions of fatty acids (Methyl-methyltetradecanoate) and esters (Oleic acid ethyl ester), constituting 25%, and 26% at 15°C/min but declining with increasing heating rates. Another ester (9-Octadecenoic acid methyl ester) was found across all heating rate with highest concentration of 33% at 100°C/min. Aliphatic hydrocarbons (Octane, Dodecene, Heptadecane, Tetradecyne, Undecane, Dimethylhepta-1,3-triene, Tetradecane, Nonadecane), constituted highest concentration of 12% at 25°C/min and aromatic hydrocarbons (Toluene) showed maximum presence of 4% at 50°C/min. The aqueous phase showcased cyclic nitrogenated compounds (Piperidine), anhydrosugars (DGP), and furanics (Furanmethanol), with the highest concentrations of 46%, 12%, and 38%, respectively observed at 100°C/min. Instantaneous py-gas analysis indicated an elevated presence of CO2 and CO in the initial pyrolysis stages (up to 70min) followed by higher H2 in the latter stages (>70min). While increasing heating rates (15 to 100°C/min) boosted cumulative fractions of CO2 and CO, the highest H2 fraction was observed at 50°C/min. The proximate and ultimate analysis of biochars indicated increased ash, fixed carbon, HHV and H/C compared to raw CFW. The surface area and morphology were positively influenced by an increase in heating rate, resulting in a microporous biochar having maximum surface area of 340.6 m2/g at 50°C/min.

Fatty acid-derived ionic liquids as soft and sustainable antimicrobial agents

In this study, two sustainability goals are addressed: 1) developing new soft antimicrobial agents (to control antimicrobial resistance) and 2) using natural bio-derived components for this purpose. Fatty acids of bio-renewable origin (stearin, palm kernel and coconut oils) were found to be excellent starting materials for obtaining ester-functionalized ionic liquids (ILs) and mixtures. A series of soft antimicrobial agents based on imidazolium, pyridinium and cholinium ILs with long alkyl ester chains were synthesized, and their properties were examined. The length of the alkyl chain had a notable effect on the physicochemical and biological properties of the synthesized materials. The introduction of a butyl linker and an ester bond lowered the melting point, increased the antimicrobial effectiveness and reduced the cytotoxicity compared to those of non-functionalized ILs with the same hydrocarbon chain. ILs and mixtures with medium chain lengths (C12, C13 and C15) were recognized as promising substitutes for demanding cationic antimicrobial agents. The presence of an ester bond connecting the polar head and hydrophobic tail can promote the breakdown of amphiphilic molecules into less toxic initial compounds. These findings make an important contribution to the development of new, effective amphiphiles with broad-spectrum antimicrobial activity and lower environmental impact.

Aliphatic and cyclic hydrocarbons in urban street dust from Riyadh city, Saudi Arabia: Levels, distribution, and sources

Dust particles contain diverse natural and anthropogenic organic compounds and act as local collectors of pollutants, particularly in urban settings. Samples of street dust were collected from various sites in Riyadh city in 2023. These samples were extracted using a dichloromethane–methanol mixture, and the resulting extracts were subjected to analysis through gas chromatography–mass spectrometry (GC–MS). The primary compounds identified included n-alkanes, methyl n-alkanoates (FAMEs), hopanes, steranes, polycyclic aromatic hydrocarbons (PAHs), plasticizers, tobacco miscellanies, and an unresolved complex mixture (UCM). Vegetation detritus constituted the primary natural source of organic compounds, ranging from 7.4 ± 3.5% to 15.0 ± 4.0%, and included fractional n-alkanes and FAMEs. Petroleum-related products from vehicular emissions, oil combustion, and spills were predominant, accounting for 73.3 ± 5.1% to 87.5 ± 4.8%, and included partial n-alkanes, hopanes, steranes, PAHs, and UCMs. Litterings from discarded plastics and tobacco smoking varied from 5.2 ± 1.3% to 12.0 ± 5.3%, and included phthalates, nicotine, and cotinine, as well as recreational drinks (coffee and tea beverages containing caffeine). The occurrence and distribution of natural and anthropogenic extractable organic matter in this arid urban area were influenced by local vegetation and human activities. The prevalence of anthropogenic organic compounds in Riyadh city's street dust depended on the location and type of urban activity, with elevated levels observed in high-traffic and industrial zones. Consequently, further investigations are necessary to understand the potential health effects of anthropogenic organic matter on city residents.

Spectro-photometry of Phobos simulants: I. Detectability of hydrated minerals and organic bands

Previous Mars Reconnaissance Orbiter and Mars Express observations of Phobos and Deimos, the moons of Mars, have improved our understanding of these small bodies. However, their formation and composition remain poorly constrained. Physical and spectral properties suggest that Phobos may be a weakly thermal-altered captured asteroid but the dynamical properties of the martian system suggest a formation by giant collision similar to the Earth moon. In 2027, the JAXA’s MMX mission aims to address these outstanding questions.We undertook measurements with a new simulant called OPPS (Observatory of Paris Phobos Simulant) which closely matches Phobos reflectance spectra from the visible to the mid-infrared wavelength range. The simulant was synthesized using a mixture of olivine, saponite, anthracite, and coal.Since observation geometry strongly influences the photometry and spectra of the light reflected from planetary surfaces, we evaluated the parameters obtained by modeling the phase curves – obtained through laboratory measurements – of two different Phobos simulants (UTPS-TB and OPPS) using Hapke IMSA model. Our results show that the photometric properties of Phobos simulants are not fully consistent with those of carbonaceous chondrites and martian meteorites. We also investigated the detection of volatiles/organic compounds and hydrated minerals, as the presence of such components is expected on Phobos in the hypothesis of a captured primitive asteroid. To investigate their detectability, we examined the variability of the 3.28μm and 3.42μm absorption bands related to aliphatic/aromatic carbon (as a proxy of organic material), as well as the 2.7μm O-H feature in a Phobos laboratory spectroscopic simulant. The results indicate that a significant amount of organic compounds is required for the detection of C-H bands at 3.4μm. The bands at 3.28 and 3.42μm are faint (less than 2%) when ∼3 wt% of organic compounds are present in the simulant and are likely undetectable by the MIRS spectrometer onboard the MMX mission. When the concentration of aliphatic and aromatic compounds is increased to 6 wt%, a positive detection starts to become more plausible using remote sensing infrared spectroscopy. In contrast, the 2.7μm absorption band, due to hydrated minerals, is much deeper and easier to detect than C-H organic features at the same concentration levels. The feature is still clearly detectable even when the simulant contains only 3 vol.% of phyllosilicates, corresponding to 0.7 wt% OH groups.Posing limits on detectability of some possible key components of Phobos surface will be pivotal to prepare and interpret future observations of the MIRS spectrometer as well as TENGOO and OROCHI cameras onboard MMX mission.

Pyrolysis-catalysis of waste tire to enhance the aromatics selectivity via metal-modified ZSM-5 catalysts

Excessive untreated waste tires (WT) have posed threats to the environment and human health. Pyrolysis-catalysis, as a promising treatment technology, could convert WT into high-valued products such as pyrolysis oil. Moreover, BTX compounds (Benzene, toluene, and xylene) were important raw materials in the chemical industry. In order to sharply increase the BTX selectivity in the pyrolytic oil, transition metals (Ni and Fe) were impregnated on the ZSM-5 catalyst. Furthermore, this paper also explored the effect of catalysis modes, catalysts-to-feedstock mass ratios, and catalysis temperatures on the distribution of the aromatics in the WT pyrolysis-catalysis oil. The results suggested that the optimal operating parameters for BTX compound production with a selectivity of 39.87% were in-situ mode, catalysis temperature=600 °C, and catalyst-to-feedstock mass ratio=1:1 by applying Ni/ZSM-5. According to the GC-MS identification results, it proposed that the Diels-Alder reaction of isoprene and cracking and recombination of limonene in the aliphatic hydrocarbon pool were the main paths to generate the aromatics, while the addition of ethylene radicals in the monocyclic aromatic hydrocarbon (MAH) and polycyclic aromatic hydrocarbon (PAH) pools was dominant in the growth of the aromatics. The study provided a viable approach for upgrading WT to produce high-value aromatic products.

Degradation of Waste Tetra Pak Packaging with Hydrothermal Treatment in Sub-/Supercritical Water.

Tetra pak packaging is one of the most frequently used types of packaging in the food industry. The recycling of the tetra pak packaging waste presents a difficult task because of its multi-layered, multi-component structure. In this study, the degradation of tetra pak packaging in subcritical (SubCW) and supercritical (SCW) water was investigated. The experiments were carried out in one (SCW) or two stages (SubCW and SCW), whereby the influence of the reaction temperature and time on the yield and composition of the products obtained was investigated. The maximum oil phase yield achieved in a one-stage and a two-stage degradation process was 60.7% and 65.5%, respectively. The oil and gas phases were composed of different types of hydrocarbons. Higher temperature and longer time led to higher amounts of saturated aliphatic hydrocarbons in both the oil and gas phases. The aqueous phase contained sugars (glucose, fructose) and sugar derivatives (levulinic acid, glyceraldehyde, furfurals). Based on these results, the degradation pathway of waste tetra pak packaging in SubCW and SCW was proposed. The results of the study show that the degradation of waste tetra pak packaging with SubCW and SCW is a promising recycling process.

Waterborne bio-based UV-thermal dual-curable coatings with excellent mechanical properties and thermal resistance based on citric acid modified epoxidised soybean oil

Waterborne bio-based UV-curable coatings have attracted enormous attentions due to their environment friendliness and safety. However, residual neutralizing agents, long-chain aliphatic hydrocarbons derived from epoxidised soybean oil, and the oxygen inhibition inherent in the UV curing process often cause poor thermal resistance and mechanical properties of the epoxidised soybean oil-based waterborne bio-based UV-curable coatings. Herein, the epoxidised soybean oil was hydrophilized by citric acid and poly (ethylene glycol) diglycidyl ether without the use of neutralising agents. The hydrophilized epoxidised soybean oil was subsequently compounded with bisphenol A epoxy resin to prepare high-performance waterborne bio-based epoxy methacrylates. Finally, a high-performance waterborne bio-based UV-thermal dual-curable coating was obtained by blending waterborne bio-based epoxy methacrylates with waterborne isocyanate curing agent. The results demonstrated that waterborne bio-based epoxy methacrylates possess high bio-based content, low viscosity, and remarkable storage stability. Furthermore, waterborne bio-based UV-thermal dual-curable coatings with high cross-linking density exhibited outstanding mechanical properties and thermal resistance. For example, the waterborne bio-based UV-thermal dual-curable coatings P0805I4 exhibits a breaking elongation of 30.75%, maximum tensile strength of 16.68 MPa, T10% at 285.33°C, and adhesion class level of 0. Our research not only introduces high-performance waterborne bio-based UV-thermal dual-curable coatings, thereby extending the application domains of soybean oil-derived waterborne bio-based coatings, but also presents a valuable strategy for advancing high-performance, sustainable, waterborne, and environmentally friendly materials.

Evolution and generation mechanism of retained oil in lacustrine shales: A combined ReaxFF-MD and pyrolysis simulation perspective

To accurately investigate the evolution characteristics and generation mechanism of retained oil, the study analyzed organic-rich lacustrine shale samples from the Paleogene Kongdian Formation in Cangdong Sag, Bohai Bay Basin. This analysis involves Rock-Eval pyrolysis, pyrolysis simulation experiments, Gas Chromatograph Mass Spectrometer (GC–MS), and reactive molecular dynamics simulations (ReaxFF). The results revealed the retained oil primarily consisted of n-alkanes with carbon numbers ranging from C14 to C36. The generation of retained oil occurred through three stages. A slow growth stage of production rate was observed before reaching the peak of oil production in Stage I. Stage II involved a rapid increase in oil retention, with C12–C17 and C24–C32 serving as the primary components, increasing continuously during the pyrolysis process. The generation process involved the cleavage of weak bonds, including bridging bonds (hydroxyl, oxy, peroxy, imino, amino, and nitro), ether bonds, and acid amides in the first stage (Ro =0.50%–0.75%). The carbon chains in aromatic ring structures with heteroatomic functional groups breaks in the second stage (Ro =0.75%–1.20%). In the third stage (Ro =1.20%–2.50%), the ring structures underwent ring-opening reactions to synthesize iso-short-chain olefins and radicals, while further breakdown of aliphatic chains occurred. By coupling pyrolysis simulation experiments and molecular simulation technology, the evolution characteristics and bond breaking mechanism of retained oil in three stages were revealed, providing a reference for the formation and evolution mechanism of retained oil.