Carbon Chain Research Articles

Impact of Cu complex anions on CuZnAl intercalated hydrotalcite-like catalysts for low-carbon alcohols synthesis from syngas

Elucidating the structure-performance relationship of catalysts for low-carbon alcohols synthesis from syngas is crucial for designing efficient catalysts. In this study, CuO particle size, reducibility, and the number of oxygen vacancies could be adjusted by changing intercalated Cu complex anions, thereby affecting the catalyst's performance. The characterization results indicated that the insertion of [Cu(C2O4)2]2- between ZnAl layered double hydroxide resulted in the largest CuO particles (26.5 nm), leading to an increase in the metallic copper surface area. Consequently, the highest CO conversion (13.0 %) was achieved without altering alcohol distribution. On the other hand, when [Cu(EDTA)]2- was inserted, the catalyst possessed the smallest CuO particle size (8.9 nm), more abundant oxygen vacancies, and enhanced interaction between Cu species and ZnO, which promoted carbon chain growth and resulted in a high C2+OH proportion of 75.8 %. Our study thus provides a new perspective on catalyst structures for the syngas production of low-carbon alcohols.

Optimizing Recovery of Fracturing Fluid in Unconventional and Tight Gas Reservoirs Through Innovative Environmentally Friendly Flowback Additives

Hydraulic fracturing, a method used to stimulate oil and gas from shale and tight formations, faces challenges like fluid blockage and fast declining oil or gas production rates due to the significant impact of capillary forces on water retention. To address this, surfactants and microemulsions are commonly employed as flowback additives to reduce surface and interfacial tension, enhancing water recovery during hydraulic fracturing. The effectiveness of flowback additives is highly impacted by harsh subsurface conditions, such as high salinity and high temperature. This study aims to assess the performance and effectiveness of methylimidazolium chloride-based ionic liquids as flowback additives at high salinities and temperatures.Different experimental analysis were conducted to screen different concentrations of methylimidazolium chloride-based ionic liquids (X1, X2, and X3). Surface tension measurements were conducted to estimate the critical micelles concentrations. A spinning drop tensiometer (SDT) was utilized to measure interfacial tension, in addition, contact angle measurements were used to evaluate the impact of the flowback additive on the wettability and the displacing behavior. Seawater was used as the base fracturing fluid with a salinity of 57,000 ppm and temperatures up to 90°c for all experiments. Coreflood experiments were conducted using tight formations to evaluate the regained hydrocarbon permeability and the fracturing fluid recovery in the presence of flowback additives.Various formulations, with surface tension values ranging from 30 to 45 mN/m and CMC values between 0.5 and 1 gallon per thousand units (gpt), were examined. The lowest interfacial tension value, notably 3 mN/m, was achieved with the X3 formulation. Ionic liquids demonstrated favorable surface tension reduction, where longer carbon chains led to lower values. Introducing diverse ions, especially divalent ions, enhanced the performance of ionic liquids. Interfacial tension measurements indicated a significant reduction with the addition of X3 to both 5 wt% KCl and the fracturing base fluid. Contact angle measurements revealed a shift towards greater water-wettability after treating the rock with flowback additives. Moreover, the use of ionic liquids improved permeability by 25%, enhancing fluid recovery to around 56%.According to our results, methylimidazolium chloride-based ionic liquids can be used as environmentally friendly flowback additives, especially in harsh conditions of high temperature and high salinity where the conventional additives are not suitable. This will contribute to the development of more sustainable and environmentally conscious practices in hydraulic fracturing operations. Ultimately, the utilization of these additives can help mitigate water blockage, reduce formation damage, and enhance shale gas production.

Synthesis and mechanism of quaternary ammonium salts based on porphyrin as high-performance copper levelers

The molecular structure and energy distribution of organic compounds have a great influence on their adsorption capacity on the metal surface. However, there are still insufficient researches on the influence of energy distribution on adsorption properties of organic molecules. Herein, a family of porphyrin derivatives (TPyP-Et, TPyP-Oct, TPyP-Bn and TPyP-Al) bearing quaternary ammonium groups were synthesized for the first time as promising levelers for through-hole copper electrodeposition. Electrochemical tests revealed that all four TPyP derivatives displayed enhanced electrochemical properties. Theoretical calculations and molecular dynamics simulations were carried out to investigate the physisorption capacity and chemical reaction activity of the TPyP molecules, as well as the adsorption capacity on the surface of the copper layer. Through optical and scanning electron microscopy as well as X-ray diffractometry, it was demonstrated that TPyP molecules are effective electroplating levelers. TPyP-Oct, with its longer carbon chain substituent, exhibited superior hole-filling performance in practical PCB experiments among the four compounds. This study expandes the application range of porphyrin compounds, analyzes the influence of organic molecular adsorption properties in copper electrodeposition, and provides theoretical guidance for the future study of organic compounds adsorbed on metal surfaces.

Synthesis of Dendrimer-Like Molecules with Partial Carbon Chain via Iterative Single Unit Monomer Insertions.

Carbon-chain dendritic polymers hold unique properties and promising applications. However, synthesizing carbon-chain dendrimers, beyond conjugated ones, remains a challenge. Here, the use of the iterative single unit monomer insertion technique for synthesizing 2.5 generation partial-carbon-chain dendrimers (G2.5) is described, utilizing bismaleimide as the core, a maleimide-trithiocarbonate conjugate as the branching unit, and indene as the spacer unit, following a divergent growth strategy. The optimized conditions for synthesizing the maleimide-trithiocarbonate branching unit are a bismaleimide to trithiocarbonate ratio of 5:1 and a reaction time of 30 min. The structures are verified using 1H nuclear magnetic resonance, gel permeation chromatography, and matrix-assisted laser desorption/ionization-time of flight mass spectra. A four-arm star polymer is then synthesized using the G2.5 as the core. This synthesis of a partial-carbon-chain dendrimer establishes a foundational step toward creating all-carbon-chain ones and may open new application avenues in material science.

나노 크기의 금속 유기 골격체, ZIF-8 합성을 위한 이온성 액체 마이크로에멀젼 합성법의 체계적 연구

Porous Metal-Organic Frameworks (MOFs) are composed of metal ions and organic ligands. Recently, nano-sized MOFs have been widely utilized in biomedical fields, including biosensing and drug delivery. Researchers are primarily focusing on reducing their particle sizes to the nanoscale with a uniform size distribution. An ionic liquid microemulsion, the one of the MOF synthesis mehtods is in the limelight as an effective way with the following advantages: grain size uniformity and eco-friendliness. In this work, systematic study to control grain size, morphology, and yield of ZIF-8 (Zeolitic Imidazolate Framework-8) through ionic liquid microemulsion method was conducted in the new systems ‘water / surfactant (TX-100 or AOT) / CnmimX (n, the number of carbon = 2, 3, 4, 6, 8, 10 / X = Cl, Br, I)’. Furthermore, not only how the type of anion of ionic liquids, the length of carbon chain in them, the type of surfactants and the mass ratio change of the components affect the ZIF-8 synthesis results, respectively, was analyzed quantitatively through several characterization methods such as PXRD, TEM, DLS and FT-IR. Through this study, we aim to shed light on the infinite possibility of ionic liquid microemulsion method to synthesize desired size of nano-size MOF with uniformity.

Interphase Engineering via Solvent Molecule Chemistry for Stable Lithium Metal Batteries

AbstractLithium metal battery has been regarded as promising next‐generation battery system aiming for higher energy density. However, the lithium metal anode suffers severe side‐reaction and dendrite issues. Its electrochemical performance is significantly dependant on the electrolyte components and solvation structure. Herein, a series of fluorinated ethers are synthesized with weak‐solvation ability owing to the duple steric effect derived from the designed longer carbon chain and methine group. The electrolyte solvation structure rich in AGGs (97.96 %) enables remarkable CE of 99.71 % (25 °C) as well as high CE of 98.56 % even at −20 °C. Moreover, the lithium‐sulfur battery exhibits excellent performance in a wide temperature range (−20 to 50 °C) ascribed to the modified interphase rich in LiF/LiO2. Furthermore, the pouch cell delivers superior energy density of 344.4 Wh kg−1 and maintains 80 % capacity retention after 50 cycles. The novel solvent design via molecule chemistry provides alternative strategy to adjust solvation structure and thus favors high‐energy density lithium metal batteries.

Interphase Engineering via Solvent Molecule Chemistry for Stable Lithium Metal Batteries.

Lithium metal battery has been regarded as promising next-generation battery system aiming for higher energy density. However, the lithium metal anode suffers severe side-reaction and dendrite issues. Its electrochemical performance is significantly dependant on the electrolyte components and solvation structure. Herein, a series of fluorinated ethers are synthesized with weak-solvation ability owing to the duple steric effect derived from the designed longer carbon chain and methine group. The electrolyte solvation structure rich in AGGs (97.96 %) enables remarkable CE of 99.71 % (25 °C) as well as high CE of 98.56 % even at -20 °C. Moreover, the lithium-sulfur battery exhibits excellent performance in a wide temperature range (-20 to 50 °C) ascribed to the modified interphase rich in LiF/LiO2. Furthermore, the pouch cell delivers superior energy density of 344.4 Wh kg-1 and maintains 80 % capacity retention after 50 cycles. The novel solvent design via molecule chemistry provides alternative strategy to adjust solvation structure and thus favors high-energy density lithium metal batteries.

Effect of Fatty Acid Unsaturation on the Intermolecular Weak Interaction at the Low-Rank Coal-Water Interface: Density Functional Theory Calculations and Experimental Study.

The study on the effect of fatty acid saturation on low-rank coal (LRC) flotation is still limited. In this investigation, density functional theory (DFT) combined with Zeta potential and Fourier transform infrared spectroscopy (FTIR) was used to study the mechanism of intermolecular weak interaction at the LRC-water interface of fatty acids (decanoic acid (DA), undecylenic acid (UA), and phenyl propionic acid (PA)) with different saturations and different dodecane (D) composition hydrocarbon oil-fatty acid mixed collectors (D-DA, D-UA, D-PA). The findings demonstrated that the hydrogen bond interaction and electrostatic interaction between the UA/PA with unsaturated bonded carbon chains and the LRC molecular fragments/water molecules were stronger than DA without a saturated bond carbon chain, and UA/PA strengthened its interaction with water molecules on the whole, even PA molecules would preferentially interact with water molecules. The unsaturated bond had a minimal impact on the adsorption of the LRC hydrophobic site, and the strength of the hydrogen bond between the mixed collector and LRC is D-DA > D-UA > D-PA. In the actual flotation process, the strong hydrogen bonding and electrostatic interaction between UA/PA and water molecules weaken the collection performance of the mixed collector D-UA/D-PA for LRC, which also confirmed the research results of DFT, FTIR, and Zeta.

Organic Acid‐Assisted Preparation of Hydroxyapatite‐supported Ni Catalysts for Arene Hydrogenation

Developing non‐noble metal catalysts that can efficiently and selectively hydrogenate arenes remains a significant challenge. In this study, we developed efficient Ni catalysts for the arene hydrogenation based on an organic acid‐regulated impregnation strategy. These easily accessible Ni catalysts demonstrated exceptional efficiency, selectivity, reusability, and good substrate compatibility. The influence of carbon chain lengths and side‐chain hydroxyl or amino groups on dicarboxylic acids used in the catalyst preparation was comprehensively investigated. Characterizations and kinetic studies demonstrated the influence of organic acids on the size of Ni nanoparticles, the proportion of metallic nickel, and the strength of surface acidity. These factors influenced the activation of arene and hydrogen, thereby affecting the hydrogenative activity. Notably, hydroxyapatite‐supported Ni catalyst, assisted by tartaric acid (Ni‐TA/HAP) with an appropriate tartaric acid‐to‐nickel ratio, resulted in relatively smaller Ni nanoparticles, an increased proportion of Ni0, and more acidic sites, thereby exhibiting the best hydrogenation performance.

Mechanisms for the separation of Li+ and Mg2+ from salt lake brines using TBP and TOP systems

The tributyl phosphate (TBP)/FeCl3 system has been widely used for lithium extraction from high‑magnesium salt lakes. However, at high TBP concentrations, the Li/Mg selectivity is significantly lower. This study revealed that at high TBP concentrations, TBP alone extracted Mg2+ to form MgCl2·6TBP as the main product, thus affecting the extraction efficiency of Li+. On this basis, a neutral phosphate with long carbon chains, trioctyl phosphate (TOP), was used to replace TBP. The separation capacity and extraction mechanism of the TOP/FeCl3 system were studied, and density functional theory (DFT) calculations were employed to model the cationic complexes of the TOP and TBP systems. The results showed that in the presence of FeCl3, the extraction efficiency of Li+ (ELi) reached 91 %, and the Li/Mg separation factor (βLi/Mg) was 5688. In contrast, in the TBP/FeCl3 system with the same concentration, the ELi and βLi/Mg values were much lower at 74 % and 239, respectively. Furthermore, the TOP complex of Li+ had shorter Li − O bond lengths and a more negative binding energy, while that formed with Mg2+ had longer Mg − O bond lengths and the smallest HOMO–LUMO gap, indicating that TOP bonded more stably with Li+ and was less prone to Mg2+ extraction than TBP.

Simultaneous size and defect control of metal-organic framework by deep eutectic solvent for efficient perfluoroalkyl substances adsorption: Delving into mechanism

This study reports an environment-friendly protocol to prepare a metal–organic framework (MOF) with simultaneously controlled particle size and open metal site for adsorption removal of perfluoroalkyl substances (PFASs). The successful preparation of UiO-66 with defect and crystal size modulation was achieved using a green and straightforward method, adjusting the components and molar ratios of ammonium salt/glycolic acid deep eutectic solvents (DESs). The corresponding modulation mechanism primarily relied on the combined regulation of the deprotonation and competitive coordination abilities of the eutectic solvent components. The adsorption process was thoroughly examined using spectral analyses, adsorption behavior profiling, and ab initio molecular dynamics simulations. The results revealed that PFAS adsorption is driven by combined capturing effects, such as CF–π, acid/base coordination, C–F⋯Zr, hydrogen bonding, and hydrophobic interactions. Our findings were not thus that the smaller the crystal size of MOF and the higher the defect concentration in the material, the better the PFAS adsorption performance. The result demonstrated the combined effect of these adsorbent features on PFAS mixtures. Furthermore, they revealed unique differences in sorption properties between these targets with different carbon chain lengths. Extensive defects in DES-based UiO-66 led to larger pores, increasing the availability of many adsorption sites and aiding in PFAS adsorption and diffusion. Nevertheless, the surplus of larger pores in the substance increased the competitive adsorption, reducing the total quantity of PFASs absorbed. Furthermore, various interactions and a less restrictive configuration increased the contact of functional groups with adsorbates, substantially enhancing the adsorption. This study investigates the basic questions about how PFAS molecules are adsorbed on DES-based MOFs and the relationship among the structure, properties, and performance to improve the efficiency of this novel adsorbent.

ВЛИЯНИЕ СТРОЕНИЯ ЛИНЕЙНЫХ УГЛЕВОДОРОДОВ НА ТЕМПЕРАТУРУ САМОВОСПЛАМЕНЕНИЯ

Using experimental data available in the literature the auto-ignition temperature of saturated and unsaturated hydrocarbons with different molecular structures is analyzed. Based on modern research of hydrocarbons oxidation with different structures at high temperatures, the connection between chemical structure, bond strength in the molecule and radical mechanisms of oxidation processes with the auto-ignition temperature is shown. It is noted that the branching of molecules contributes to the temperature of self-ignition increase, that is, an increase in their composition of methyl groups, tertiary and quaternary carbon atoms located nearby in the carbon chain. Double and triple bonds, starting from C5, strengthen the molecule. The elongation of both the main chain and the chain of substituents reduces the auto-ignition temperature of the compound.

Identification of plastic-degrading bacteria in the human gut

Environmental pollution caused by the excessive use of plastics has resulted in the inflow of microplastics into the human body. However, the effects of microplastics on the human gut microbiota still need to be better understood. To determine whether plastic-degrading bacteria exist in the human gut, we collected the feces of six human individuals, did enrichment cultures and screened for bacterial species with a low-density polyethylene (LDPE) or polypropylene (PP)-degrading activity using a micro-spray method. We successfully isolated four bacterial species with an LDPE-degrading activity and three with a PP-degrading activity. Notably, all bacterial species identified with an LDPE or PP-degrading activity were opportunistic pathogens. We analyzed the microbial degradation of the LDPE or PP surface using scanning electron microscopy and confirmed that each bacterial species caused the physical changes. Chemical structural changes were further investigated using X-ray photoelectron spectroscopy and Fourier-transform-infrared spectroscopy, confirming the oxidation of the LDPE or PP surface with the formation of carbonyl groups (C=O), ester groups (CO), and hydroxyl groups (-OH) by each bacterial species. Finally, high temperature gel permeation chromatography (HT-GPC) analysis showed that these bacterial species performed to a limited extent depolymerization. These results indicate that, as a single species, these opportunistic pathogens in the human gut have a complete set of enzymes and other components required to initiate the oxidation of the carbon chains of LDPE or PP and to degrade them. Furthermore, these findings suggest that these bacterial species can potentially biodegrade and metabolize microplastics in the human gut.

The study on synthesis and vitro hypolipidemic activity of novel berberine derivatives nitric oxide donors

Berberine was used as the lead compound in the present study to design and synthesize novel berberine derivatives by splicing bromine bridges of different berberine carbon chain lengths coupled nitric oxide donors, and their lipid lowering activities were assessed in a variety of ways. This experiment synthesized 17 new berberine nitric oxide donor derivatives. Compared with berberine hydrochloride, most of the compounds exhibited certain glycerate inhibitory activity, and compounds 6a, 6b, 6d, 12b and 12d showed higher inhibitory activity than berberine, with 6a, 6b and 6d having significant inhibitory activity. In addition, compound 6a linked to furazolidone nitric oxide donor showed better NO release in experiments; In further mechanistic studies, we screened and got two proteins, PCSK9 and ACLY, and docked two proteins with 17 compounds, and found that most of the compounds bound better with ATP citrate lyase (ACLY), among which there may be a strong interaction between compound 6a and ACLY, and the interaction force was better than the target drug Bempedoic Acid, which meaning that 6a may exert hypolipidemic effects by inhibiting ACLY; moreover, we also found that 6a may had the better performance in gastrointestinal absorption, blood-brain barrier permeability, Egan, Muegge class drug principle model calculation and bioavailability.

Codelivery of CPT and siPHB1 with GSH/ROS Dual-Responsive Hybrid Nanoparticles Based on a [12]aneN3-Derived Lipid for Synergistic Lung Cancer Therapy.

The combination of small-interfering RNA (siRNA)-mediated gene silencing and chemotherapeutic agents for lung cancer treatment has attracted widespread attention in terms of a greater therapeutic effect, minimization of systemic toxicity, and inhibition of multiple drug resistance (MDR). In this work, three amphiphiles, CBN1-CBN3, were first designed and synthesized as a camptothecin (CPT) conjugate and gene condensation agents by the combination of CPT prodrugs and di(triazole-[12]aneN3) through the ROS-responsive phenylborate ester and different lengths of alkyl chains (with 6, 9, 12 carbon chains for CBN1-CBN3, respectively). CBN1-CBN3 were able to be self-assembled into liposomes with an average diameter in the range of 320-240 nm, showing the ability to effectively condense siRNA. Among them, CBN2, with a nine-carbon alkyl chain, displayed the best anticancer efficiency in A549 cells. In order to give nanomedicines a stealth property and PEGylation/dePEGylation transition, a GSH-responsive PEGylated TPE derivative containing a disulfide linkage (TSP) was further designed and prepared. A combination of CBN2/siRNA complexes and DOPE with TSP resulted in GSH/ROS dual-responsive lipid-polymer hybrid nanoparticles (CBN2-DP/siRNA NPs). In present GSH and H2O2, CBN2-DP/siRNA NPs were decomposed, resulting in the controlled release of CPT drug and siRNA. In vitro, CBN2-DP/siPHB1 NPs showed the best anticancer activity for suppression of about 75% of A549 cell proliferation in a serum medium. The stability of CBN2-DP/siRNA NPs was significantly prolonged in blood circulation, and they showed effective accumulation in the A549 tumor site through an enhanced permeability and retention (EPR) effect. In vivo, CBN2-DP/siPHB1 NPs demonstrated enhanced synergistic cancer therapy efficacy and tumor inhibition as high as 71.2%. This work provided a strategy for preparing lipid-polymer hybrid NPs with GSH/ROS dual-responsive properties and an intriguing method for lung cancer therapy.

Enhancing Phototoxicity in Human Colorectal Tumor Cells Through Nanoarchitectonics for Synergistic Photothermal and Photodynamic Therapies.

Phototherapies are promising for noninvasive treatment of aggressive tumors, especially when combining heat induction and oxidative processes. Herein, we show enhanced phototoxicity of gold shell-isolated nanorods conjugated with toluidine blue-O (AuSHINRs@TBO) against human colorectal tumor cells (Caco-2) with synergic effects of photothermal (PTT) and photodynamic therapies (PDT). Mitochondrial metabolic activity tests (MTT) performed on Caco-2 cell cultures indicated a photothermal effect from AuSHINRs owing to enhanced light absorption from the localized surface plasmon resonance (LSPR). The phototoxicity against Caco-2 cells was further increased with AuSHINRs@TBO where oxidative processes, such as hydroperoxidation, were also present, leading to a cell viability reduction from 85.5 to 39.0%. The molecular-level mechanisms responsible for these effects were investigated on bioinspired tumor membranes using Langmuir monolayers of Caco-2 lipid extract. Polarization-modulation infrared reflection-absorption spectroscopy (PM-IRRAS) revealed that the AuSHINRs@TBO incorporation is due to attractive electrostatic interactions with negatively charged groups of the Caco-2 lipid extract, resulting in the expansion of surface pressure isotherms. Upon irradiation, Caco-2 lipid extract monolayers containing AuSHINRs@TBO (1:1 v/v) exhibited ca. 1.0% increase in surface area. This is attributed to the generation of reactive oxygen species (ROS) and their interaction with Caco-2 lipid extract monolayers, leading to hydroperoxide formation. The oxidative effects are facilitated by AuSHINRs@TBO penetration into the polar groups of the extract, allowing oxidative reactions with carbon chain unsaturations. These mechanisms are consistent with findings from confocal fluorescence microscopy, where the Caco-2 plasma membrane was the primary site of the cell death induction process.

Selective CO2 hydrogenation to liquid fuels over Na-decorated FeMgMnOx catalyst with high carbon efficiency

Direct synthesis of liquid fuels (C5+ hydrocarbons) through CO2 hydrogenation has attracted considerable interest. However, it is plagued by high selectivity of C1 by-products (CO and CH4) and low reaction activity. Herein, we report that Na-decorated Fe catalysts promoted by combination of Mg and Mn and investigate their synergistic effect in the catalytic CO2 hydrogenation reaction. The optimized amounts of promoters result in a significant improvement in the catalytic performance of NaFe2O3. The CO2 conversion increases by 1.6-fold, while the total selectivity of CO and CH4 is suppressed to below 21.3 %. The characteristic results reveal the enhanced surface alkalinity and electron transfer favor CO2 adsorption and tuned the local H/C ratio in the vicinity of iron species, thus remarkably promoting the carbon chain growth and limiting the production of C1 products. This study offers a promising approach to modulating the metal electronic environment and improving carbon efficiency for CO2 hydrogenation reactions.

Evidences for the influence from key chemical structures of per- and polyfluoroalkyl substances on their environmental behaviors

This study carried out the atmospheric and precipitation observation in Beijing for nearly one year, and firstly simultaneously observed the pollution characteristics of PFASs and their main isomers, focusing on their gas-particle partitioning mechanism and dry and wet deposition characteristics. After deducting PFASs in the aqueous phase of particulate matter, the gas-particle partitioning coefficients (−7.04 to −5.49) were about 3–4 units smaller than before (−2.77 to −1.51), and all were smaller than 0, which indicated that each PFAS and isomer were more distributed in the gas phase. Dry deposition was dominant in the atmospheric deposition of each PFAS and isomer with relative contribution of 66 ± 17%, but the relative contribution of dry deposition was significantly different. It was found that the gas-particle partitioning coefficient can be influenced by key chemical structures such as carbon chain length, functional group type, and isomer structure. Furthermore, the gas-particle partitioning can influence the dry and wet deposition of PFASs. Specifically, PFASs with longer carbon chains, carboxylic acid functional group (compared to sulfonic acid functional group) or PFOA branched chain structures had larger gas-particle partitioning coefficients and can be more distributed in the hydrophobic phase of particulate matter, and their relative contributions of dry deposition were smaller.

Behavior of calcium lignosulfonate under oxygen pressure acid leaching condition

The behavior of calcium lignosulfonate (CLS) in the oxygen pressure acid leaching process of ZnS concentrate was investigated using total organic carbon assessment (TOC), UV–visible spectrophotometry, Fourier transform infrared spectroscopy (FTIR), and gas chromatography-coupled mass spectrometry (GC–MS) as characterization methods. The effect of the CLS degradation products on zinc electrowinning was also discussed. The results showed that the temperature was positively correlated with the degradation of CLS, while the initial acidity had only significant effects in the range of 0–50 g/L and oxygen partial pressure range of 0–0.1 MPa. At an oxygen partial pressure of 0.2 MPa, an acidity of 160 g/L, and a reaction temperature of 150 °C, about 82.4% of CLS was degraded. In the oxygen pressure acid leaching process, CLS underwent polymerization and decomposition reactions, and its aromatic rings and side chain groups were damaged to varying degrees. At 120 °C, CLS was partially converted into sulfonic acids, phenols, and esters of higher molecular weights. At 150 °C, CLS further degraded into lower-molecular-weight aromatic ethers and sulfonic acids with shorter carbon chains. These organics were relatively stable and were the main sources of organic compounds during the oxygen pressure leaching process of zinc concentrates. The addition of CLS had a significant negative impact on zinc electrowinning, which was related to the adsorption of CLS on the cathode surface, enhancing cathodic polarization and inhibiting zinc reduction kinetics.

Integration of ultrashort-chain compounds into the biomonitoring of per- and polyfluorinated substances in human plasma and serum

Ultrashort-chain (USC) per- and polyfluoroalkyl substances (PFAS) are small and very polar compounds with carbon chain lengths of shorter than C4. Their ubiquitous and high levels of occurrence in environmental aquatic systems have raised significant concern in conjunction with long-chain PFAS contamination. Measuring USC PFAS in blood can not only monitor human exposure but also serves as a valuable tool for studying the potential risks associated with USC PFAS exposure. The high polarity of USC PFAS poses a challenge to current analytical practices based on the reversed-phase liquid chromatography, primarily due to insufficient chromatographic retention. In this study, a simple and reliable workflow was developed for the simultaneous analysis of C1 to C10 perfluoroalkyl carboxylic and sulfonic acids, along with four alternative PFAS, in human plasma and serum. The chromatographic analysis was conducted using a polar-embedded reversed-phase LC column. Fetal bovine serum (FBS) was chosen for method validation due to its absence of all analytes, except for trifluoroacetic acid (TFA). Subsequently, a TFA isotope, 13C-TFA, was employed as a surrogate to assess the method accuracy for TFA in FBS. A single-step sample preparation procedure, conducted by mixing 100 µL of FBS with 200 µL of methanol, was demonstrated to be effective for the accurate and precise analysis of fortified FBS samples. Ten isotopes of C3 to C10 PFAS, serving as extracted internal standards, were added to the samples at 1 ppb to validate the accuracy of the entire workflow. Calibration standards were prepared in reverse osmosis water due to its cleanliness for all analytes. Phosphate-buffered saline was incorporated into the calibration standard solution to achieve similar chromatographic performance between standard and sample solutions. The calibration ranges varied among different analytes, spanning from 0.05 – 40 ppb, 0.1 – 40 ppb, 0.25 – 40 ppb, and 0.5 – 40 ppb. Method accuracy and precision were evaluated at three fortification levels, ranging from 0.4 to 30 ppb. All analytes and extracted internal standards exhibited recovery values within 20 % of the nominal concentration across all fortification levels. Satisfactory method precision was demonstrated with%RSD values <12 %. The validated method was applied to measure PFAS in NIST 1950 and 1957 standard reference human plasma and serum, affirming the established workflow is suitable for accurate quantification of C1 to C10 PFAS in human plasma and serum matrices.