Varying Chain Length Research Articles

Excited State Proton Transfer from Acidic Alcohols to a Quinoline Photobase Can Be Solvated by Non-Acidic Alcohol Solvents.

Photobases are a type of molecule that become more basic upon photoexcitation and can therefore be used to control proton transfer reactions with light. The solvation requirements for excited state proton transfer (ESPT) in photobase systems is poorly understood, which limits their applicability. Here, we investigate the solvation of the ESPT reaction using 5-methoxyquinoline (MeOQ), a well-studied photobase with an excited state pKa (pKa*) of approximately 15.1, as a model system. Previous studies have shown that, in addition to the acidic donor that donates a proton to the photoexcited MeOQ, an additional "auxiliary donor" is necessary to solvate the resulting alkoxide. We investigate whether a nonacidic hydrogen bond donor (an alcohol solvent that MeOQ cannot deprotonate in bulk) can act as the auxiliary donor for the MeOQ ESPT reaction. First, we use steady state spectroscopy, TCSPC, and electronic structure calculations to show that MeOQ can deprotonate the acidic donor 2,2,2-trifluoroethanol (TFE, pKa = 12.5) using ethanol as the auxiliary donor. We show that the degree of ESPT is largely predicted by the degree of ground state hydrogen bonding between the photobase and the acidic donor. Next, we study the deprotonation of the acidic donors TFE and 1,1,1,3,3,3-hexafluoroisopropanol (HFIP, pKa = 9.3) with MeOQ in a variety of nonacidic alcohol solvents of varying chain length and branching. MeOQ ESPT occurs to varying extents in all solvents, suggesting that all studied nonacidic alcohols can function as auxiliary donors. We show that the concentration of the acidic donor is strongly correlated with the degree of ESPT. These results are necessary fundamental steps toward the understanding of the photobase ESPT reaction and its wide application in a variety of chemical systems.

Simple strategy of the use of pharmaceutically functionalized ionic liquids in a new generation of polymer nanocarriers for the combined delivery of ionic p-aminosalicylate and ampicillin

Single and dual bioactive linear poly(ionic liquid)s (PIL) were synthesized for use as nanocarriers in drug delivery systems (DDS). These PILs were obtained through the (co)polymerization of the choline-based monomeric ionic liquids (MIL) with pharmaceutical anions possessing antibacterial properties, specifically [2-(methacryloyloxy)ethyl]trimethyl-ammonium with ampicillin and p-aminosalicylate (TMAMA/AMP and TMAMA/PAS). The copolymers exhibited varying chain lengths defined by a degree of polymerization (DPn = 122–370), and differing contents of ionic fraction and drugs (TMAMA 61–92 %, AMP 61–93 % and PAS 16–21 %). These parameters were adjustable by the monomer conversion (33–92 %) and the initial ratio of comonomers. In aqueous solution, the polymer particles reached nanosizes, i.e. 190–328 nm for AMP systems and 200–235 nm for AMP/PAS systems. In the release process, the pharmaceutical anions were released through exchange by phosphate anions in PBS at pH 7.4 at 37 °C. Depending on the copolymer composition the release of AMP was attained in 72–100 % (11.1–19.5 µg/mL) within 26 h by the single drug systems, while the dual drug systems released 61–100 % of AMP (14.8–24.7 µg/mL) and 82–100 % of PAS (3.1–4.8 µg/mL) within 72 h. The effectiveness in the drug delivery of the designed TMAMA polymers seems to be promising for future applications in antibiotic therapy and the combined therapy.

Cerium(III)phosphotungstate: an efficient catalyst in esterification of fatty acids

In this report, a known heteropolyacid salt (HPAs) cerium (Ⅲ) phosphotungstate was synthesized in a volume ratio of 2:1:2 with a molar ratio of 1:1:1 of each ingredient. These HPAs are further utilized in form of a catalyst to generate biodiesel through the esterification of variable carbon chain length alcohols (methanol, ethanol, n-propanol, isopropanol, n-butanol) and stearic acid at different conditions of reaction. FTIR of the produced biodiesel was also done for the assurance of ester peaks in it. Analysis of some important biodiesel properties (density, dynamic viscosity, acid value, aniline point, boiling point, cloud and pour point, and flash and fire point) etc., to differentiate and validate the results. A large surface area of the catalyst i.e. 121.427 m2/g determined using the BET surface area analyser, supports the fact of outrageous catalytic action in the esterification reaction. The effect of additives was also studied on the properties of resultant biodiesel. The calorific value of the samples was measured at 7320 Kcal/kg without additive and 7512 Kcal/kg after adding toluene (as an additive) in the biodiesel generated in the study. The pour point temperature of the biodiesel with additives was observed even < 20℃.

Biobased polyesteramides derived from bisfuranic diamine and aliphatic diesters of varied chain lengths: synthesis and chemical stability

This study presents the development of a series of biobased polyesteramides, labeled as PEAF1–3, via a greener approach, from bisfuranic diamine and commercially available aliphatic diesters of varied chain lengths. The resulting polymers showed reasonable molar masses, in accordance with inherent viscosities ranging between 0.19 and 0.35 dL/g. Evaluation of their thermal properties by thermogravimetric analysis and differential scanning calorimetry showcased excellent thermal stability (Td ,max ≥ 335 °C), amorphous character and low glass transition temperature (Tg ) decreased with the increasing chain length. Moreover, notable finding was the exceptional stability of these polyesteramides against both hydrolytic and oxidative degradation processes. This resistance underscores their potential as highly stable materials, making them promising for various applications where durability and resistance to degradation are crucial.

Analysis of enzyme activity and substrate specificity of dolichyl-phosphate β-glucosyltransferase

Protein folding and quality control processes primarily occur in the endoplasmic reticulum (ER). ER-resident molecular chaperones play a crucial role in guiding nascent polypeptides towards their correct tertiary structures. Some of these chaperones specifically recognize glucosylated N-glycan moieties on peptide. It is of great significance to study the N-glycan biosynthetic pathway and glycoprotein quality control system by analyzing the sugar donor of ER luminal glucosyltransferases, known as dolichol phosphate glucose (Dol-P-Glc), or its analogues in vitro. In this study, we investigated a range of dolichol analogues to synthesize lipid phosphate glucose, which served as substrates for dolichyl-phosphate β-glucosyltransferase E (Alg5E) derived from Trichomonas vaginalis. The results demonstrated that the recombinant Alg5E, expressed in Escherichia coli, exhibited strong catalytic activity and the ability to recognize lipid phosphate glucose with varying chain lengths. Interestingly, the enzyme's catalytic reaction was found to be faster with longer carbon chains in the substrate. Additionally, Alg5E showed a preference for branched chain methyl groups in the lipid structure. Furthermore, our study confirmed the importance of divalent metal ions in the binding of the crucial DXD motif, which is essential for the enzyme's catalytic function. These findings lay the groundwork for future research on glucosyltransferases Alg6, Alg8, and Alg10 in the synthesis pathway of dolichol-linked oligosaccharide (DLO).

Penetration of oils into hair.

The objective of this work was to understand how triglyceride plant oils can deliver strength and softness benefits to hair by their penetration. These plant oils are complex mixtures of TAGs, so the initial studies performed were with pure TAGs and then these data compared to plant oils and their measured TAG compositions. LC-MS was used to identify the di and triglycerides in coconut oil, Camellia oleifera oil and safflower seed oil. Penetration of these plant oils and pure individual triglycerides was measured by a differential extraction method. Cross-sections of oils treated with 13C-labelled triolein were studied by NanoSIMS to visualize location of triglyceride inside hair. Fatigue strength was measured using constant stress to generate a survival distribution. Models of the lipid-rich cell membrane complex (CMC) were created with the equimolar ratio of 18-methyl-eicosanoic acid (MEAS), palmitic acid (C16:0) and oleic acid (C18:1). Penetration of the individual pure TAGs was confirmed for all chain lengths and degree of unsaturation tested with higher penetration for shorter chain lengths and unsaturated fatty acids. Detailed compositional analysis of selected plant oils showed a wide variety of TAGs and penetration was also demonstrated for these oils. NanoSIMS and modelling confirmed these TAGs are penetrating the lipid-rich CMC of hair and are interacting with the fatty acids that make up the CMC. All plant oils delivered a fatigue strength improvement by penetration into the CMC and it is proposed that these oils prevent formation and/or propagation of flaws in the CMC network that leads to breakage. Many plant oils with a wide range of triglyceride compositions can penetrate into hair and NanoSIMS data confirmed these oils partition into the lipid-rich cell membrane complex. Penetration studies of individual TAGs shown to be present in these oils confirmed TAGs of varying chain length can penetrate and there is a correlation between increased penetration efficacy and shorter chain lengths and presence of unsaturation in the fatty acid chains. All the oils studied delivered single fibre fatigue strength benefits.

Fe/Mn-MOFs with monocarboxylic acid-induced defects enhances the catalytic oxidation of calcium sulfite in desulfurization ash

The application of catalysis is an effective way to enhance calcium sulfite oxidation reactions, which is essential to the calcium-based wet flue gas desulfurization and the handle and/or utilization of the solid by-product from semi-dry desulfurization process, i.e., desulfurization ash. In this report, we present a method for constructing Fe/Mn(BDC)(DMF,OA) bimetallic catalysts with defect engineering by using monocarboxylic acids with varying chain lengths as regulators. After removing the monocarboxylic acid, the unsaturated coordinated iron and manganese active sites in Fe/Mn(BDC)(DMF,OA) become more abundant. This makes it easier to adsorb O2 and activate it into reactive oxygen species (O2–), which in turn activates the radical chain reaction and promotes the production of sulfur-oxygen free radicals(SO5−). Density functional theory (DFT) calculations show that the synergistic effect of Fe-Mn bimetallic catalysts reduces the energy barrier for SO42− formation, thereby accelerating the oxidation of sulfite. Upon addition of Fe/Mn(BDC)(DMF,OA), the oxidation rate of calcium sulfite within 3 h increased from 2.76 % to 96.09 %, compared to non-catalytic oxidation. After five cycles, the 3 h oxidation rate of calcium sulfite decreased by 10.42 % compared to the first cycle, and the higher leaching rate of Mn element was the main reason for the decrease in catalytic performance. The catalyst is non-toxic and economical, showing significant potential for resource utilization of CaSO3-containing desulfurization ash.

Nanoscale surface defects of goethite governing DNA adsorption process and formation of the Goethite-DNA conjugates

In urbanized areas, extracellular DNA (exDNA) is suspected of carrying genes with undesirable traits like virulence genes (VGs) or antibiotic resistance genes (ARGs), which can spread through horizontal gene transfer (HGT). Hence, it is crucial to develop novel approaches for the mitigation of exDNA in the environment. Our research explores the role of goethite, a common iron mineral with high adsorption capabilities, in exDNA adsorption processes. We compare well-crystalline, semi-crystalline, and nano goethites with varying particle sizes to achieve various specific surface areas (SSAs) (18.7–161.6 m2/g) and porosities. We conducted batch adsorption experiments using DNA molecules of varying chain lengths (DNA sizes: <11 Kb, <6 Kb, and <3 Kb) and assessed the impact of Ca2+ and biomacromolecules on the adsorption efficacy and mechanisms. Results show that porosity and pore structure significantly influence DNA adsorption capacity. Goethite with well-developed meso- and macroporosity demonstrated enhanced DNA adsorption. The accumulation of DNA on the goethite interface led to substantial aggregation in the system, thus the formation of DNA-goethite conjugates, indicating the bridging between mineral particles. DNA chain length, the presence of Ca2+, and the biomacromolecule matrix also affected the adsorption capacity and mechanism. Interactions between DNA and positively charged biomacromolecules or Ca2+ led to DNA compaction, allowing greater DNA accumulation in pores. However, a high concentration of biomacromolecules led to the saturation of the goethite surface, inhibiting DNA adsorption. AFM imaging of goethite particles after adsorption suggested the formation of the DNA multilayer. The study advances understanding of the environmental behavior of exDNA and its interaction with iron oxyhydroxides, offering insights into developing more effective methods for ARGs removal in wastewater treatment plants. By manipulating the textural properties of goethite, it's possible to enhance exDNA removal, potentially reducing the spread of biocontamination in urban and industrial environments.

Molecular insights into the self-assembly of Janus nanoparticles obtained from coarse-grained molecular dynamics simulations

Abstract Grafting polymeric chains onto surfaces of nanoparticles generates amphiphilic Janus nanoparticles (JNPs) that can self-assemble into a variety of well-ordered and/or functional nanostructures. The self-assembly structures of JNPs can be designed by the manipulation of grafting schemes, but only if the self-assembly rule can be well understood. By using coarse-grained molecular dynamics (CGMD) simulations, we investigated the self-assembly process and morphology of triblock JNPs with varying chain lengths, chain ratios, and grafting topology. The HTH type of JNPs which possesses a middle hydrophobic block and two terminal hydrophilic blocks tends to aggregate into film structures via a shoulder-by-shoulder packing mode. The THT (Hydrophobic-Hydrophilic-Hydrophobic) type of JNPs is likely to form string structures via a head-to-head packing mode. The self-assembled film structures and string structures can be further regulated by the hydrophilic-hydrophobic chain ratio and length, forming rigid flakes, vesicles, porous structures, and so forth. Based on the molecular insights revealed by the example models, some plausible rules and strategies for tuning the self-assembly of nanoparticles are discussed in this paper. They are expected to facilitate future studies on the application of chemical self-assembly in materials science.

Molecular Dynamics Investigation into CerENP's Effect on the Lipid Matrix of Stratum Corneum.

The extracellular lipid matrix in the stratum corneum (SC) plays a critical role in skin barrier functionality, comprising three primary components: ceramides, cholesterol, and free fatty acids. The diverse ceramides, differentiated by molecular structures such as hydroxylations and varying chain lengths, are essential for the lipid matrix's structural integrity. Recently, a new subclass of ceramide, 1-O-acylceramide NP (CerENP), has been identified; however, its precise role in the lipid matrix of the SC is still elusive. Herein, we investigate the role of CerENP on the structure and permeability of the SC using molecular dynamics simulations. Our findings indicate that CerENP contributes to a compact lipid matrix in the lateral dimension of our SC model with a repeat distance of about 13 nm. Additionally, ethanol permeability assessments show that CerENP effectively reduces molecular penetration through the lipid matrix. This study provides an insight into the role of a new subclass of ceramide in the SC, enhancing our understanding of skin structure and the mechanisms behind barrier dysfunction in skin diseases.

Effect of the surface coating of carbonyl iron particles on the dispersion stability of magnetorheological fluid

The dispersion stability of carbonyl iron particle (CIP)-based magnetorheological fluid (MRF) is improved by CIP, which particle is etched with hydrochloric acid (HCl) to form porous structure with many hydroxyl groups and subsequently coated with silane coupling agents that have varying chain lengths. The microstructures, coating effect and magnetism of the CIPs were examined using the Scanning Electron Microscopy, Automatic Surface and Porosity Analyzer (BET), Fourier-Transform Infrared Spectroscopy, Thermogravimetric Analysis and Vibrating Sample Magnetometer. Furthermore, the rheological properties and dispersion stability of the MRFs were assessed using a Rotating Rheometer and Turbiscan-lab. The results revealed that the nanoporous structure appeared on the CIPs and the specific surface area increased remarkably after being etched by hydrochloric acid. Additionally, as the chain length of the silane coupling agent increases, the coated mass on the particles increases, the the density and the saturation magnetization of particles decreased, and the coated particles with different shell thicknesses were obtained; without a magnetic field, the viscosity of MRF prepared by coated particles increase slightly, due to the enhancement of special three-dimensional network structure; under a magnetic field, the viscosity of the MRF decreased distinctly; the sedimentation rate of MRF decreased from 58 to 3.5% after 100 days of sedimentation, and the migration distances of the MRFs were 22.4, 3.7, 2.4, and 0 mm, with particle sedimentation rates of 0.149, 0.019, 0.017, and 0 mm/h, respectively. The MRF with high dispersion stability was obtained, and the etching of CIP by HCl and the proper chain length of the coating of silane coupling agent were proved effective manners to improve the dispersion stability of MRF.

Dimerization enhances cytotoxicity and tumor/non-tumor cell selectivity of juglone

&lt;span lang="DE"&gt;The study investigates the biological activity of spaced juglone dimers derived from the reaction of juglone with dicarboxylic acid dichlorides of varying chain lengths. It builds upon the observation that dimeric structures can exhibit enhanced biological activity compared to their monomeric counterparts. The cytotoxic effects of the synthesized compounds were assessed against a range of human cancer cell lines and non-malignant fibroblasts. Results indicate that the cytotoxicity varied depending on the length of the spacer, with specific dimers showing significantly improved activity. Furthermore, these compounds demonstrated a higher selectivity towards cancer cell lines than non-malignant fibroblasts, suggesting potential for targeted anticancer therapy&lt;/span&gt;&lt;span lang="EN-US"&gt;. &lt;/span&gt;

Viscosity effects on the dynamics of diols and diol-based deep eutectic solvents.

Diols, characterized by the presence of two hydroxyl groups, form extended hydrogen-bonded networks. Increasing hydrocarbon chain length is known to elevate the viscosity of diols. Given the established influence of viscosity on solvent dynamics, it becomes imperative to comprehend the impact of viscosity on the fluctuation dynamics within diols and establish connections with hydrogen bond formation and breaking dynamics. In this study, we employ two-dimensional infrared spectroscopy to investigate the viscosity dependence of the structural evolution dynamics in three diols with varying chain lengths. Complementing our experimental approach, molecular dynamics simulations are conducted to extract hydrogen bond lifetimes. Our findings reveal a linear correlation between bulk viscosity, solvent fluctuation timescales, and hydrogen bond lifetimes. Notably, the selected diols exhibit the capability to form deep eutectic solvents upon mixing with choline chloride at specific molar ratios. In contrast to molecular solvents like diols, deep eutectic solvents are characterized by the formation of heterogeneous nanodomains, comprising various intercomponent hydrogen-bonded networks. Interestingly, our observations indicate that while the fluctuation dynamics decelerate with increasing bulk viscosity in diol-based deep eutectic solvents, the relationship between viscosity and dynamics is not linear, in contrast to the observed linearity in diols. This nuanced understanding contributes to the broader comprehension of the interplay between viscosity and dynamics in both molecular and deep eutectic solvents.

Coumarin Schiff base derivatives with 4′-alkoxy biphenyl-4-carboxaldehyde: Synthesis, mesomorphic studies and DFT calculations

Two homologous series of coumarin Schiff base derivatives with 4′-alkoxy biphenyl-4-carboxaldehyde have been designed and synthesized. All the compounds were analyzed IR, 1H NMR, 13C NMR, ESI-MS and CHN analysis followed by mesomorphic properties polarizing optical microscopy (POM) and differential scanning calorimetry (DSC) analysis. In the first homologous series BPS(6–16), Schiff base of 7-alkoxy-3-aminocoumarin with 4′-alkoxy biphenyl-4-carboxaldehyde, alkoxy chain length was varied systematically at both end of the molecules such as n = 6,8,10,12,14,16. In this series, BPS(6–10) (n = 6,8,10) exhibited enantiotropic nematic(N) and smectic C (SmC) mesophase and turned to monophasic on increasing the chain length n = 12,14,16 in BPS(12–16) with stable SmC mesophase. While in the second homologous series 10BPU(2–16), systemic variation of alkoxy chain length was carried out at coumarin end only (n = 2–18) and 4′-decyloxy-biphenyl-4-carboxaldehyde was used for Schiff base formation. In the this series, early member of the series with n = 2,3 showed enantiotropic very stable (∼ 145 °C) nematic mesophase, while N as well as SmC mesophase were observed for n = 4–8 at, whereas with increase of chain length stability of nematic mesophase was decreased and that of SmC was increased. Higher membered analogous 10BPU(12–16) exhibited SmC mesophase with stability in the rage of 130–160 °C. VT-XRD analysis was also confirmed the tilted SmC mesophase in this class of compounds. For both the series, all compounds were studied for the DFT calculations as well as literature molecules with similar variations. Based on the calculated structural (length, aspect ratio) and electronic (dipole moment, polarizability) parameters were correlated with mesomorphic behaviour observed for literature compounds and compounds from both the series followed by the detailed discussion.

Functionalization and Structural Evolution of Conducting Quasi-One-Dimensional Chevrel-Type Telluride Nanocrystals.

Interfacing organic molecular groups with well-defined inorganic lattices, especially in low dimensions, enables synthetic routes for the rational manipulation of both their local or extended lattice structures and physical properties. While appreciably studied in two-dimensional systems, the influence of surface organic substituents on many known and emergent one-dimensional (1D) and quasi-1D (q-1D) crystals has remained underexplored. Herein, we demonstrate the surface functionalization of bulk and nanoscale Chevrel-like q-1D ionic crystals using In2Mo6Te6, a predicted q-1D Dirac semimetal, as the model phase. Using a series of alkyl ammonium (-NR4+; R = H, methyl, ethyl, butyl, and octyl) substituents with varying chain lengths, we demonstrate the systematic expansion of the intrachain c-axis direction and the contraction of the interchain a/b-axis direction with longer chain substituents. Additionally, we demonstrate the systematic expansion of the intrachain c-axis direction and the contraction of the interchain a/b-axis direction as the alkyl chain substituents become longer using a combination of powder X-ray diffraction and Raman experiments. Beyond the structural modulation that the substituted groups can impose on the lattice, we also found that the substitution of ammonium-based groups on the surface of the nanocrystals resulted in selective suspension in aqueous (NH4+-functionalized) or organic solvents (NOc4+-functionalized), imparted fluorescent character (Rhodamine B-functionalized), and modulated the electrical conductivity of the nanocrystal ensemble. Altogether, our results underscore the potential of organic-inorganic interfacing strategies to tune the structural and physical properties of rediscovered Chevrel-type q-1D ionic solids and open opportunities for the development of surface-addressable building blocks for hybrid electronic and optoelectronic devices at the nanoscale.

Small-Angle X-ray Scattering Study of the Amphiphilic Bulk Nanostructure of Tetraalkylammonium Deep Eutectic Solvents.

Deep eutectic solvents (DESs) are low-melting mixtures, often prepared from a salt and a molecular hydrogen bond donor. Like ionic liquids, DESs that contain at least one sufficiently amphiphilic component can form bicontinuous nanostructures consisting of polar and nonpolar domains, although this has not been widely explored for many DES combinations. Here, the bulk nanostructures of DESs comprising tetraalkylammonium bromide salts (tetrabutylammonium bromide, tetraoctylammonium bromide, and methyltrioctylammonium bromide) with alkanols and alkanoic acids of systematically varied chain lengths (C2, C6, C8, and C10) as hydrogen bond donors have been studied. Small-angle X-ray scattering techniques were used to identify the relationship between the alkyl chain length and functionality of the hydrogen bond donor on the nature of the amphiphilic nanostructures formed. These findings demonstrated that the amphiphilic nanostructures of the DESs were not affected by the functional group on the hydrogen bond donor, with these nanostructures influenced primarily by both the absolute and relative alkyl chain lengths of the salt and hydrogen bond donor.

Functionalization of 2-Mercapto-5-methyl-1,3,4-thiadiazole: 2-(ω-Haloalkylthio) Thiadiazoles vs. Symmetrical Bis-Thiadiazoles.

A study on the functionalisation of 2-mercapto-5-methyl-1,3,4-thiadiazole has been conducted, yielding two series of products: 2-(ω-haloalkylthio)thiadiazoles and symmetrical bis-thiadiazoles, with variable chain lengths. The experimental conditions were optimised for each class of compounds by altering the base used and the reagents' proportions, leading to the development of separate protocols tailored to their specific reactivity and purification needs. The target halogenide reagents and bis-thiadiazole ligands were obtained either as single products or as mixtures easily separable by chromatography. Characterisation of the products was performed using 1D and 2D NMR spectra in solution, complemented by single crystal X-ray diffraction (XRD) for selected samples, to elucidate their structural properties.

Internal Factors Affecting the Crystallization of the Lipid System: Triacylglycerol Structure, Composition, and Minor Components.

The process of lipid crystallization influences the characteristics of lipid. By changing the chemical composition of the lipid system, the crystallization behavior could be controlled. This review elucidates the internal factors affecting lipid crystallization, including triacylglycerol (TAG) structure, TAG composition, and minor components. The influence of these factors on the TAG crystal polymorphic form, nanostructure, microstructure, and physical properties is discussed. The interplay of these factors collectively influences crystallization across various scales. Variations in fatty acid chain length, double bonds, and branching, along with their arrangement on the glycerol backbone, dictate molecular interactions within and between TAG molecules. High-melting-point TAG dominates crystallization, while liquid oil hinders the process but facilitates polymorphic transitions. Unique molecular interactions arise from specific TAG combinations, yielding molecular compounds with distinctive properties. Nanoscale crystallization is significantly impacted by liquid oil and minor components. The interaction between the TAG and minor components determines the influence of minor components on the crystallization process. In addition, future perspectives on better design and control of lipid crystallization are also presented.

Biphenyl based schiff base derivatives of 6-aminocoumarin: Design, synthesis, mesomorphic properties and DFT studies

The study focused on synthesizing two series of coumarin Schiff base liquid crystals. These series involved molecules with variations in alkoxy chains at aldehyde ends: one being the Schiff base with 4′‑hydroxy-[1,1′]-biphenyl-4-carbaldehyde (ASBP series) and the other being alkyl 4-formyl-[1,1′]-biphenyl-4-carboxylate (AEBP series). The compounds were characterized using FTIR, NMR, and Mass spectral analyses. All the compounds were studied for their mesomorphic properties, differential scanning calorimetry (DSC) and polarized optical microscopy (POM). In both the homologous series, variation of alkyl chain length showed intriguing phase transitions. In the first homologous series ASBP, compound with hexyloxy chain displayed an enantiotropic nematic (N) phase, while those with chain lengths n = 8–16 exhibited enantiotropic smectic A (SmA) mesophase. Similarly, in the AEBP series, compounds with n = 6,8 chain length showed an enantiotropic nematic (N) phase, while those with higher chain lengths n = 10–16 exhibited enantiotropic smectic A (SmA) phases. SmA mesophase was further confirmed by powdered XRD analysis. The study included DFT theoretical calculations to comprehend the compounds' mesomorphic behavior, comparing them with analogous reported compounds. Additionally, the investigation correlated experimental findings of individual compounds with calculated parameters like polarizability, dipole moment, and aspect ratio. Molecular electrostatic potential projections and analysis of frontier molecular orbitals were also employed to elucidate how polarity variations in terminal chains and mesogenic cores influenced the energy gap of FMOs and the distribution of electrostatic charges on these compounds. It has been found that the ASBP series has lower energy gap and higher dipole moment than the AEBP series.

Autochthonous bioaugmentation strategies for the successful bioremediation of high-salt petrochemical wastewater using a biosurfactant-producing Enterobacter cloacae Z11

Petrochemical wastewater contains a high concentration of refractory aliphatic and aromatic hydrocarbons. Bioremediation of these hazardous materials using autochthonous bioaugmentation (ABA) strategy is attracting increasing interest. Herein, an indigenous biosurfactant-producing bacteria Z11 was isolated and identified as Enterobacter sp. The reintroduction of Z11 into petrochemical wastewater led to a substantial reduction (P < 0.01) in TPHs, decreasing from 8099 to 1723 mg/L, as well as a significant decrease in COD, decreasing from 8064.2 to 1689.2 mg/L. At a critical micelle concentration of 200 mg/L, the biosurfactant synthesized by Z11 exhibited an extraordinary decrease in surface tension from 67.5 to 29 mN/m. The biosurfactant demonstrated favorable surface activity over a wide pH, temperature, and salinity range. Based on a series of chemical analyses, the biosurfactant was classified as phospholipid. The autochthonous bioaugmentation technique developed by Z11 indicated a significant increase (P < 0.05) in the degradation of n-alkanes of varying chain lengths and polycyclic aromatic hydrocarbons. The analysis of the microbial composition demonstrated that the addition of Z11 caused a rise in bacterial populations capable of hydrocarbon decomposition, such as Pseudomonas sp. and Stenotrophomonas sp. The activities of two enzymes involved in degradation, alkane hydroxylase and alcohol dehydrogenase, increased dramatically and showed a significant (P < 0.05) correlation with Enterobacter sp. Z11. The proposed mechanism could be elucidated that functional genes regulate the secretion of biodegradation enzymes and biosurfactants to promote the deep degradation of petroleum hydrocarbons. This study provides technical support for the reintroduction of autochthonous microorganisms capable of producing biosurfactants in implementing in situ ABA strategies.