Increasing Carbon Chain Length Research Articles

Loading of antibiotic molecules into organically modified layered calcium silicate

Loading of antibiotic molecules into organically modified layered calcium silicate

Insight into the dissolution behavior of valsartan (form E) in twelve pure solvents: Solubility, modelling and molecular simulation

Valsartan is an angiotensin II receptor antagonist used to treat hypertension. Crystals of valsartan were prepared and the stability of the valsartan (form E) at different solvents and temperatures was investigated. The solid-liquid equilibrium solubility of valsartan (form E) in twelve pure solvents was determined by a dynamic method at the temperature from 278.15 K to 323.15 K. Among the solvents used in the experiment, the solubility of valsartan (form E) was found to be highest in methanol and lowest in acetonitrile. In straight-chain alcohols, the solubility decreases with the increase of carbon chain length. The modified Apelblat model, λh model and NRTL model were used to correlate the solubility data. The thermodynamic properties of the mixing process such as Gibbs free energy, enthalpy and entropy were estimated by applying the NRTL model. The KAT-LSER model was adopted to explore solvent effects. Hirshfeld surface analysis and molecular electrostatic potential (ESP) were employed to visualize close contacts and charge distribution of valsartan and solvents. In addition, molecular dynamics (MD) simulation was performed to calculate intermolecular interactions between solute and solvent. Radial distribution function (RDF) and the mean square displacement (MSD) analyses were also carried out to explore molecular association and molecular diffusion.

Study on multiscale structures and digestibility of cassava starch and medium-chain fatty acids complexes using molecular simulation techniques

Effect of complexation of three medium-chain fatty acids (octanoic, decylic and lauric acid, OA, DA and LA, respectively) on structural characteristics, physicochemical properties and digestion behaviors of cassava starch (CS) was investigated. Current study indicated that LA was more easily to combine with CS (complex index 88.9%), followed by DA (80.9%), which was also consistent with their corresponding complexed lipids content. Following the investigation of morphology, short-range ordered structure, helical structure, crystalline/amorphous region and fractal dimension of the various complexes, all cassava starch-fatty acids complexes (CS-FAs) were characterized with a flaked morphology rather than a round morphology in native starch (control CS). X-ray diffraction demonstrated that all CS-FAs had a V-type crystalline structure, and nuclear magnetic resonance spectroscopy confirmed that the complexes made from different fatty acids displayed similar V6 or V7 type polymorphs. Interestingly, small-angle X-ray scattering analysis revealed that α value became greater following increased carbon chain length of fatty acids, indicating the formation of a more ordered fractal structure in the aggregates. Changes in rheological parameters G′ and G′′ indicated that starch complexed with fatty acids was more likely to form a gel network, but difference among three CS-FAs complexes was significant, which might be contributed to their corresponding hydrophobicity and hydrophilicity raised from individual fatty acids. Importantly, digestion indicated that CS-LA complexes had the lowest hydrolysis degree, followed by the greatest RS content, indicating the importance of chain length of fatty acids for manipulating the fine structure and functionality of the complexes.

Insights into solid–liquid equilibrium behavior of 2′,4′-Dichloro-5′-fluoroacetophenone

2′,4′-Dichloro-5′-fluoroacetophenone is a key intermediate in the preparation of ciprofloxacin hydrochloride, a broad-spectrum quinolone antibacterial drug. Wherein, crystallization and solid–liquid equilibrium thermodynamics play an irreplaceable role in the separation and purification of 2′,4′-Dichloro-5′-fluoroacetophenone. Therefore, in this work, the solubility of 2′,4′-Dichloro-5′-fluoroacetophenone was measured by dynamic method in eight different solvents and range from 273.15 K to 288.15 K. The results showed that the solubility of 2′,4′-Dichloro-5′-fluoroacetophenone increased with increasing temperature. Further analysis showed that the solubility of 2′,4′-Dichloro-5′-fluoroacetophenone increased with increasing carbon chain length in ester solvents. Single crystals of 2′,4′-Dichloro-5′-fluoroacetophenone were successfully prepared and the result reveals that the Cl⋯H, O⋯H, and F⋯H interactions dominated the packing and long-range order of the crystals. Then, different thermodynamic models were employed to describe the thermodynamic behavior of 2′,4′-Dichloro-5′-fluoroacetophenone. The calculated ARD% and RMSD values show that the correlation results are in good agreement with the experimental data, and the Van’t Hoff equation has the best regression performance. Finally, it is interesting to find that the contribution of entropy and enthalpy change to dissolution of 2′,4′-Dichloro-5′-fluoroacetophenone tends to be equal with increasing temperature.

Electrochemical oxidation degradation of xanthate and its mechanism: Effects of carbon chain length and electrolyte type

There are a lot of residual flotation reagents such as xanthate remaining in the mineral processing wastewater, which must be deeply removed for recycling or discharge. However, there are few studies using electrochemical oxidation to remove xanthate. This article employs the electrochemical oxidation method to treat simulated xanthate-containing wastewater, which investigates the mechanisms involved in removing four xanthate homologues under different electrolyte conditions. Results show that under 1 g/L of Na2SO4, current density of 40 mA/cm2, initial pH of 7.0, and initial concentration of xanthates 1 mM, four alkyl xanthates can be completely removed within 60 min. The COD removal and TOC removal can reach 71.42%–88.61% and 54.23%–81.50%, respectively. By contrast, NaCl electrolyte is more favorable for xanthate degradation. The generated SO42− concentration can reach 145.4 mg/L at 60min, resulting in the sulfur mineralization ratio (ηs) of 75.72%. Regardless of the electrolyte type, as the carbon chain length increases, the xanthate degradation rate accelerates, accompanied by higher COD and TOC removal. The results of UV–vis spectra and LC–MS indicate that intermediate substances such as xanthate peroxides and alcohols are first formed in the process, ultimately leading to the complete mineralization of small molecule substances such as SO42−, CO2, and H2O. The fate of S and Cl elements confirms it. EPR and probe fluorescence spectroscopy results indicate that in Na2SO4 electrolyte, the main active substances are ·OH and a small amount of SO4∙–. Additionally, the production of ·OH increases as the electrolysis time is prolonged. In NaCl electrolyte, ·OH undergoes a series of reactions with Cl− to convert into Cl∙ and active chlorine, which constitute the primary reactive oxygen species.

Assessment of Fetal Exposure and Elimination of Perfluoroalkyl and Polyfluoroalkyl Substances: New Evidence from Paired Serum, Placenta, and Meconium Samples.

Multiple pieces of evidence have shown that prenatal exposure to perfluoroalkyl and polyfluoroalkyl substances (PFASs) is closely related to adverse birth outcomes for infants. However, difficult access to human samples limits our understanding of PFASs transport and metabolism across the human placental barrier, as well as the accurate assessment of fetal PFASs exposure. Herein, we assess fetal exposure to 28 PFASs based on paired serum, placenta, and meconium samples. Overall, 21 PFASs were identified first to be exposed to the fetus prenatally and to be metabolized and excreted by the fetus. In meconium samples, 25 PFASs were detected, with perfluorooctane sulfonate and perfluorohexane sulfonic acid being the dominant congeners, suggesting the metabolism and excretion of PFASs through meconium. Perfluoroalkyl sulfonic acids might be more easily eliminated through the meconium than perfluorinated carboxylic acids. Importantly, based on molecular docking, MRP1, OATP2B1, ASCT1, and P-gp were identified as crucial transporters in the dynamic placental transfer of PFASs between the mother and the fetus. ATSC5p and PubchemFP679 were recognized as critical structural features that affect the metabolism and secretion of PFASs through meconium. With increasing carbon chain length, both the transplacental transfer efficiency and meconium excretion efficiency of PFASs showed a structure-dependent manner. This study reports, for the first time, that meconium, which is a noninvasive and stable biological matrix, can be strong evidence of prenatal PFASs exposure.

Contamination status, partitioning behavior, ecological risks assessment of legacy and emerging per- and polyfluoroalkyl substances in a typical heavily polluted semi-enclosed bay, China

The contaminant status, spatial distribution, partitioning behavior, and ecological risks of 26 legacy and emerging perfluoroalkyl and polyfluoroalkyl substances (PFASs) in Laizhou Bay, China were investigated. The concentrations of ∑PFASs in surface and bottom seawater ranged from 37.2 to 222 ng/L and from 34.2 to 305 ng/L with an average of 116 ± 62.7 and 138 ± 93.8 ng/L, respectively. There were no significant differences in the average concentrations between the surface and bottom seawater (P > 0.05). Perfluorooctanoic acid (PFOA) and short-chain PFASs dominated the composition of PFASs in seawater. The concentrations of ∑PFASs in sediments ranged from 0.997 to 7.21 ng/g dry weight (dw), dominated by perfluorobutane sulfonate (PFBS), perfluorobutanoic acid (PFBA), and long-chain PFASs. The emerging alternatives of perfluoro-1-butane-sulfonamide (FBSA) and 6:2 fluorotelomer sulfonic acid (6:2 FTSA) were detected for the first time in Laizhou Bay. The ∑PFASs in seawater in the southwest of the bay were higher than those in the northeast of the bay. The ∑PFASs in sediments in the northeast sea area were higher than those in the inner area of the bay. Log Kd and log Koc values increased with increasing carbon chain length for PFASs compounds. Ecological risk assessments indicated a low ecological risk associated with HFPO-DA but a moderate risk associated with PFOA contamination in Laizhou Bay. Positive matrix factorization (PMF) analysis revealed that fluoropolymer manufacturing, metal plating plants, and textile treatments were identified as major sources contributing to PFASs contamination.

Profiles and transplacental transfer of per- and polyfluoroalkyl substances in maternal and umbilical cord blood: A birth cohort study in Zhoushan, Zhejiang Province, China

Per- and polyfluoroalkyl substances (PFAS) can pass through the placental barrier and pose health risks to fetuses. However, exposure and transplacental transfer patterns of emerging PFAS remain unclear. Here, 24 PFAS were measured in paired maternal whole blood (n = 228), umbilical cord whole blood (n = 119) and serum (n = 120). Orthogonal partial least-squares discriminant analysis (OPLS-DA) was used to differentiate PFAS between different matrices. The transplacental transfer (TPT) of PFAS was calculated using cord to maternal whole blood concentration ratios. PFOS and PFOA were still the dominant PFAS in maternal samples. The emerging PFAS had higher TPT than PFOS and PFOA. Moreover, PFAS with the same chain length but different functional groups and C-F bonds showed different TPT, such as PFOS and PFOSA (C8, median: 0.090 vs. 0.305, p < 0.05) and PFHxS and 4:2 FTS (C6, median: 0.220 vs. 1.190, p < 0.05). A significant sex difference in 4:2 FTS (median: boys 1.250, girls 1.010, p < 0.05) were found. Furthermore, we observed a significant U-shaped trend for the TPT of carboxylates with increasing carbon chain length. PFAS showed a compound-specific transfer through placental barrier and a compound-specific distribution between different matrices in this study.

Multi-media distribution and risk assessment of per- and polyfluoroalkyl substances in the Huai River Basin, China

The widespread existence, environmental persistence, and risks of per- and polyfluoroalkyl substances (PFASs) have attracted widespread attention. Herein, the distribution and risk assessment of PFASs were investigated from the Huai River Basin. The ranges in different media were 29.83–217.96 (average of 75.82 ± 35.64 ng/L) in water, 0.17–9.55 ng/g (2.56 ± 2.83 ng/g) in sediments, and 0.21–9.76 ng/g (3.43 ± 3.07 ng/g) in biota. Perfluoropentanoic acid (PFPeA) was the most prevalent PFAS in surface water, followed by perfluorooctanoic acid (PFOA) and perfluorobutanoic acid (PFBA), accounted for 42.62 %, 22.23 % and 17.72 % of the total concentrations of the PFASs analyzed, respectively. PFBA was dominant in sediments, accounting for 60.37 % of the total concentrations of the PFASs analyzed. Perfluorooctane sulfonate (PFOS) was the main pollutant in biota, and the highest concentration (5.09 ng/g) was found in Channa argus. Considering the measured concentrations in water, sediments and biota, the sediment-water partition coefficients (log Kd) and bioaccumulation factors (BAF) of PFASs were determined. The log Kd of the PFASs differed among those with a different carbon chain length, C7-C11 PFASs were more likely to be adsorbed onto sediments as the carbon chain length increases, and PFUnDA and PFDA showed the higher BAF value in Channa argus. PFASs in the Huai River Basin posed an acceptable ecological risk, and long-chain PFAS contamination provided green algae with a higher potential ecological risk. Compared to drinking water, aquatic products constituted a higher PFASs threat to human health, especially for children. The highest HQ was found in PFOS, with an HQmax of 0.97–4.32. Residents in the Huai River Basin should reduce their intake of Channa argus, Coilia nasus, and Carassius auratus, children aged 2 to 4 are limited to consuming no more than 6.9 g/d, 9.7 g/d, and 16.6 g/d, respectively.

Effect of molar ratio and alkyl chain length on the aggregation behavior of imidazolium-based ionic liquid surfactants/SDS systems

In our previous publication (https://doi.org/10.1016/j.jcis.2019.04.023), the volumes and concentrations of syringe and sample cell in Isothermal titration calorimetry (ITC) limit the molar ratios and concentrations during the titration process. The molar ratios and concentrations of sodium dodecylsulfate (SDS) are almost higher than those of the ionic liquids (ILs) throughout the titration process. From the perspective of SDS molar ratios and concentrations, when the molar ratios and concentrations of the imidazolium-based ILs exceed those of SDS, the research remains unexplored. This aspect of the research has been consistently neglected, yet it is crucial for a fundamental understanding of self-assembly structure transitions. For these mixed systems, the phase behavior, zero-shear viscosity, and dynamic viscoelasticity of the system do not increase with the increasing carbon chain length of imidazolium ILs. The variation in carbon chain length exhibits an optimal value (1-octyl-3-methylimidazolium chloride ([OMIM]Cl)/SDS system), which may be related to the balance between the electrostatic attraction among headgroups and the hydrophobic interactions among hydrophobic chains. To enhance a deeper comprehension of the variations in macroscopic properties across the entire range of mole ratios, enthalpy changes and cryogenic Transmission Electron Microscopy (cryo-TEM) were employed to study the mixed systems. When 100.0 mM imidazolium-based ILs were titrated into 12.5 mM SDS solution, the titration curves consistently exhibited a plateau. During this plateau, SDS micelles undergo disassembly and reassemble into vesicle structures of different sizes. The formation of vesicles is a continuous process until the imidazolium ILs is completely consumed. We propose a straightforward and feasible method to determine the molecular ratios of surfactants responsible for constructing vesicle structures in different alkyl chain lengths systems by fitting the enthalpy changes at different stages. Through this approach, the molecular ratios of SDS and 1-Hexyl-3-methylimidazolium chloride ([HMIM]Cl), 1-Octyl-3-methylimidazolium chloride ([OMIM]Cl), and 1-Dodecyl-3-methylimidazolium chloride ([DMIM]Cl) in the vesicle structures are 1:1, 4:5 and 7:10, respectively.

Effect of substrate composition on physicochemical properties of the medium-long-medium structured triacylglycerol.

Nutritional and functional qualities and applications of structured lipids (SL) depend on the composition and molecular structure of fatty acids in the glycerol backbone of triacylglycerol (TAG). However, the relationship between the substrate composition and physicochemical qualities of SL has not been revealed. The investigation aims to disclose the effect of substrate composition on the physicochemical properties of medium-long-medium structured lipids (MLM-SLs) by enzymatic interesterification of Lipozyme TLIM/RMIM. The medium-long-chain triacylglycerol (MLCT) yield could reach 70.32%, including 28.98% CaLCa (1,3-dioctonyl-2-linoleoyl glyceride) and 24.34% CaOCa (1,3-didecanoyl-2-oleoyl glyceride). The sn-2 unsaturated fatty acid composition mainly depended on long-chain triacylglycerol (LCT) in the substrate. The increased carbon chain length and double bond in triacylglycerol decreased its melting and crystallization temperature. The balanced substrate composition of MCT/LCT increased the size and finer crystals. Molecular docking simulation revealed that the MLCT molecule mainly interacted with the catalytic triplets of Lipozyme TLIM (Arg81-Ser83-Arg84) and the Lipozyme RMIM (Tyr183-Thr226-Arg262) by OH bond. The oxygen atom of the ester on the MLCT molecule was primarily bound to the hydrogen of hydroxyl and amino groups on the binding sites of Lipozyme TLIM/RMIM. The intermolecular interplay between MLCT and Lipozyme RMIM is more stable than Lipozyme TLIM due to the formation of lower binding affinity energy. This research clarifies the interaction mechanism between MLCT molecules and lipases, and provides an in-depth understanding of the relationship between substrate composition, molecular structure and physicochemical property of MLM-SLs. © 2023 Society of Chemical Industry.

In vitro plasma hydrolysis of phenolic esters and their absorption kinetics in rats: Controlled release of phenolic compounds and enhanced health benefits

Phenolic esters are considered as promising functional food ingredients. However, their digestion, absorption and metabolism are still unclear. Tyrosol acyl esters (TYr-Es), hydroxytyrosol acyl esters (HTy-Es) and alkyl gallates (A-GAs) were hydrolyzed by carboxylesterase in plasma and exhibited slow release of polyphenols (phenolic acids). In vitro hydrolysis degrees initially increased and then decreased with the increasing carbon chain length (C2-C16). TYr-Es exhibited higher hydrolysis degrees compared to HTy-Es, and hydrolysis degrees of TYr-Es and HTy-Es were markedly higher than those of A-GAs. Due to the fast hydrolysis rates of TYr-Es and HTy-Es, they were undetectable in all rat plasma samples collected at several times within 24 h after administration. Whereas, A-GAs could be detected in rat plasmas and three absorption peaks were found in the pharmacokinetic profiles. Importantly, the T1/2, MRT, AUC0-∞, AUC0-t in octyl gallate group were longer (or stronger) than those in propyl gallate and dodecyl gallate groups.

Molecular dynamics simulation study of the effect of molecular structure of warm mix additive on lubricating properties

Based on tribological theory, molecular dynamics (MD) simulation is used to characterize the lubrication behavior of warm mix additive at the friction interface between asphalt and aggregate from the molecular scale. The base asphalt lubricating film model and the warm mix asphalt lubricating film model were established respectively. The asphalt-mineral interfacial shear friction system was constructed using two types of lubricating film models and SiO2 (001) friction surface. The effects of shear rate, system temperature and the hydrophobic end carbon chain length of the warm mix additive on the lubricating property of the simulated system were investigated, and the mechanism of warm mix additive was further revealed. The results show that the higher the shear rate, the greater the shear stress on the surface of the lubricating film. The shear stress on the surface of the warm mix asphalt lubricating film is significantly smaller than the base asphalt lubricating film. The system temperature has no noticeable effect on the shear stress. Additionally, with increasing hydrophobic end carbon chain length of the warm mix additive, the shear stress of the warm mix asphalt lubricating film decreases. The temperature of the lubricating film gradually rises from the interface to the inside, reaching a maximum value at the film's centre. The temperature inside the base asphalt lubricating film rises with an increasing shear rate. In contrast, the temperature distribution inside the warm mix asphalt lubricating film is relatively constant within a specific range. The cohesive energy of asphalt lubricating film and its adsorption energy on the SiO2 surface both decrease with an increasing shear rate, and the temperature has little effect on the cohesive energy and adsorption energy. With the increase of the hydrophobic end carbon chain length of the warm mix additive, the adsorption energy of warm mix asphalt lubricating film increases and then decreases, the self-diffusion coefficient decreases first and then increases, and the cohesive energy increases gradually. The number density distribution shows a stronger affinity between warm mix additive and SiO2. In conclusion, this paper reveals the lubrication mechanism of surfactant warm mix additive, which can provide reference and guidance for subsequent scholars to further study the warm mixing mechanism by MD method, as well as for the study of asphalt-aggregate interfacial behavior.

Adsorption of quaternary ammonium salt hydrophobic modifiers on the α-quartz (001) surface: a density functional theory study

To investigate the adsorption mechanism of quaternary ammonium salt on the α-quartz (001) sur-face, the adsorption models of hydrophobic modifiers 1231, 1431, 1631 and 1831 were constructed and simulated using the density functional theory (DFT). Results indicate that the adsorption energy of quaternary ammonium salt increases with the increase of carbon chain length, and the adsorption energy reaches the maximum at 18 carbon atoms; however, the adsorption capacity of 1631 is weak owing to the carbon chain deflection. Based on the Mulliken bond population analysis, reagent 1831 has the strongest interaction with α-quartz (001) surface compared with 1231, 1431 and 1631; and during the adsorption process, charge transfer and electrostatic attraction occur between the reagent and α-quartz (001) surface with similar degrees of charge transfer observed. This study emphasizes that electrostatic attraction plays a key role in the adsorption process, while the week hydrogen bonding plays a secondary role.

Density Functional Theory Studies on New Possible Biobased Gemini Corrosion Inhibitors Derived from Fatty Hydrazide Derivatives.

Several new possible biobased corrosion inhibitors derived from fatty hydrazide derivatives were analyzed using quantum chemical calculations via the density functional theory method to investigate the chemical reactivity and inhibition efficiencies against corrosion in metal steel. The study confirmed that the fatty hydrazides showed significant inhibitive performances based on their electronic properties, revealing band gap energies of 5.20 to 7.61 eV between the HOMO and LUMO. These energy differences decreased from 4.40 to 7.20 eV when combined with substituents of varying chemical compositions, structures, and functional groups, associated with higher inhibition efficiency. The most promising fatty hydrazide derivatives are terephthalic acid dihydrazide combined with a long-chain alkyl chain, which resulted in the lowest energy difference of 4.40 eV. Further inspection showed that the fatty hydrazide derivatives' inhibitive performances increased with increasing carbon chain length [from 4 (4-s-4) to 6 (6-s-6)], with a concomitant increase and decrease in hydroxyl and carbonyl groups, respectively. Fatty hydrazide derivatives containing aromatic rings also showed increased inhibition efficiencies following their contribution to improve the compounds' binding ability and adsorption on the metal surface. Overall, all data were consistent with previously reported findings, envisaging the potential of fatty hydrazide derivatives as effective corrosion inhibitors.

Competitive double bond isomerization and competitive esterification of C8 to C18 linear 1-alkenes on amberlyst®15 catalyst: Calculation of relative adsorption coefficients in two concurrent reactions

Relative initial reaction rates for both double bond isomerization and direct esterification with heptanoic acid were determined for the series of linear 1-alkenes from 1-octene to 1-octadecene. In competitive reactions between two 1-alkenes on Amberlyst®15 catalyst at 90 °C, rates for both double bond isomerization and esterification decreased with increasing carbon chain length. Data suggested each 1-alkene had two different adsorption coefficients on the catalyst, one for an isomerization site and one for a site for the addition reaction. Results were consistent with previous data suggesting that Amberlyst®15 catalyst has two different types of active sites.

Nationwide distribution of per- and polyfluoroalkyl substances (PFAS) in road dust from India

In India, information on the occurrence and distribution of legacy and emerging per- and polyfluoroalkyl substances (PFAS) is deficient. In the present study, nationwide 79 road dust samples were collected from 12 states and 1 union territory for the analysis of 34 PFAS. Overall, total concentrations of 21 quantified PFAS (∑21PFAS) ranged 23–861 pg/g (median: 116 pg/g), with perfluorooctane sulfonic acid (PFOS) being predominant (median: 19.9 pg/g). Short to long chain perfluoroalkyl carboxylic acids (PFCAs; C4 − C18) were detected, where the concentrations of PFAS decreased with the increase in PFAS carbon chain length. ∑21PFAS was highest in road dust from urban area (n = 27; median: 230 pg/g), followed by suburban (n = 21; median: 126 pg/g) and rural areas (n = 31; median: 76 pg/g), suggesting environmental impacts of industriallization and urbanization on PFAS distribution. PFAS composition in rural road dust was significantly different from those in suburban and urban samples (p < 0.01). Regarding 4 geographical regions of India, PFAS in road dust showed spatial difference where higher concentrations were found in South India compared to other regions. ∑21PFAS were positively associated with city-wise population of India (rs = 0.40, p < 0.01). Strong to moderate positive correlation was observed between ∑21PFAS, fluorotelomer sulfonic acids, and PFCAs (rs = 0.23, 0.30, and 0.28, respectively; p < 0.05) and the total state-wise vehicles in India, suggesting that vehicles exhaust or non-exhaust (e.g., vehicle tire debris and polishing material) might contribute to the PFAS occurrence in Indian road dust. Toddlers (2–5 years) had the highest estimated daily intake of ∑PFAS via road dust ingestion under average-case and worst-case scenarios (0.55 and 1.16 pg/kg bw/day, respectively). This is the first time to evaluate PFAS in Indian road dust nationwide, aiding to provide first-hand data for human exposure to PFAS in India.

Microwave synthesis of carbon dots in ten choline chloride-based deep eutectic solvents: Effect of solvent molecular structure on carbon dots fluorescence and sensing properties

Deep eutectic solvents (DESs) have showed great interest in carbon dots synthesis. Surface and optical characteristics of carbon dots (CDs) can be influenced by solvent during the synthesis. In this study, microwave method was used for CDs synthesis in ten choline chloride based DESs. Glucose was used as a cheap carbon source. Surface functional groups, optical and fluorescence properties of ten CDs were compared. Quantum yield (QY) of the prepared CDs in choline chloride/urea, choline chloride/glycerol and choline chloride/thiourea DESs were 41.3, 38.7 and 35.5%, respectively. Doping of nitrogen and sulfur atoms in the CDsDES1, CDsDES2 and CDsDES4 enhanced the photoluminescence performance. TEM, FT-IR, EDXS and fluorescence spectroscopy were used for CDs characterization. Results showed that molecular structure of hydrogen bond donor (HBD) had important influence on the CDs properties and doping. The hydrogen bond strength and hydrogen donor ability of DES reduce by the increase of carbon chain length of HBD. DESs with short carbon chain and high content of –NH2 and –OH produce CDs with higher QYs. Some of these CDs were also used as fluorescent nano-probes.

Identification and yield of metabolites of chlorinated paraffins incubated with chicken liver microsomes: Assessment of their potential to convert into metabolites

Chlorinated paraffins (CPs) are emerging environmental pollutants. Although metabolism has been shown to affect the differential accumulation of short-chain (SCCPs), medium-chain (MCCPs) and long-chain (LCCPs) CPs in birds, CP metabolites have rarely been reported and the extent to which they are formed is still unclear. In this study, single and mixed CP standards were incubated with chicken liver microsomes in vitro to study the generation of CP metabolites. Putative aldehyde/ketone and carboxylic acid metabolites identified by mass spectroscopy data were shown to be false positive results. Phase I metabolism of CPs first formed monohydroxylated ([M-Cl+OH]) and then dihydroxylated ([M-2Cl+2OH]) products. The yields of monohydroxylated metabolites of CPs decreased with increasing carbon chain length and chlorine content at the initial stage of reaction. Notably, the yield of monohydroxylated metabolites of SCCPs with 51.5% Cl content reached 21%, and that of 1,2,5,6,9,10-hexachlorodecane (C10H16Cl6) was as high as 71%. Thus, monohydroxy metabolites of CPs in birds should not be ignored, especially those of SCCPs. This study provides important data that could support improvements to the ecological/health risk assessment of CPs.

Alkyl Chain Length‐Dependent Amine‐Induced Crystallization for Efficient Interface Passivation of Perovskite Solar Cells

AbstractEfficient surface passivation of perovskite solar cells (PSC) using treatment with ammonium salts is demonstrated as an efficient method to enhance the device performance, owing to the affinity between the amine group and [PbI6]4− octahedron. However, due to their high solubility in polar solvents (DMF/DMSO), ammonium salts are more difficult to use in passivation of the interface between the electron transport layer and perovskite thin film in n‐i‐p structured PSCs. In this report, this work successfully links the amine group with a fullerene through a series of increasing carbon chain length, from two to twelve methylene units (FC‐X, X = 2, 6, 12), and then introduce the synthesized molecules as interface passivation layers into SnO2‐based planar n‐i‐p PSCs. Results show that the interface passivation effect is highly dependent on the side‐chain length, and the longer chain length amine‐functionalized fullerene is more beneficial for the device performance. A power conversion efficiency as high as 21.2% is achieved by using FC‐12. The surface energy, perovskite crystallite size and electron transfer capacity correlate with the linker chain length. This work develops an amine‐induced anchored crystallization of perovskite to unravel the mechanism of this passivation effect. As expected, enhanced device stability is also observed in the FC‐12 passivated PSCs.