Molar Ratio Research Articles

Novel bioactive petrodispersing agents based on cationic polymeric surfactant: Design, synthesis, and surface indices

Novel bioactive cationic polymeric surfactants based on fatty acid derived from natural wastes were developed with different hydrophilic head groups, which were employed for collecting the thin petroleum film from water surface and dispersing it. The preparation procedures pass through three steps, in first step lauryl methacrylate (LMA) was copolymerized with methacrylic acid (MAA) with different feed from the two monomers to obtain five copolymers of poly(LMA-co-MAA) (P1-5) of different molar ratio. In second step, carboxylic groups in copolymers (P1-5) were esterified with N,N‘-dimethyl-ethanol amine and finally the modified copolymers (PE1-5) were quaternized with Butyl-2-chloroacetate and Hexyl-2-chloroacetate to afford the bioactive PSB1-5 and PSH1-5, respectively. The structure of synthetic compounds was confirmed by FT-IR and 1H NMR. Upon examination, the surface-active characteristics of the bioactive petrodispersing agents that were synthesized exhibited significant defoaming capacity, good wettability, and foaming qualities. The synthesized PSB1-5 and PSH1-5 were applied for petro-collecting and dispersing in solid state and diluted form on three water sources. In sea water and diluted form, the results showed that PSB1-5 showed better effects than PSH1-5. Also, the antimicrobial efficiency of the synthesized PSB(1-5) and PSH(1-5) were tested. The data obtained from FT-IR and 1H NMR spectra proved the esterification of carboxylic group in copolymers due to the appearing of peak at 1738 cm−1 for carbonyl group of formed esters and the disappearing for proton of carboxylic group in 1H NMR. Also, data obtained from antimicrobial studies showed that the highest inhibition zone diameter against C. albicans, L. monocytogenes, S. aureus, Salmonella sp. and E. coli were observed for PSH(1-5). Which PSH-2 gives the highest value of inhibition zone diameter of 3.2 mm against L. monocytogenes. The results exhibited that PSH(1-5) showed the stronger antimicrobial functions than PSB(1-5).

High-Efficiency Ag-Modified ZnO/g-C3N4 Photocatalyst with 1D-0D-2D Morphology for Methylene Blue Degradation

Photocatalysts with different molar ratios of Ag-modified ZnO to g-C3N4 were prepared through an electrostatic self-assembly method and characterized through techniques such as X-ray diffraction, Fourier transform infrared spectroscopy, and scanning electron microscopy. The resulting Ag-ZnO/g-C3N4 photocatalysts exhibited a unique 1D-0D-2D morphology and Z-type heterojunction. Moreover, g-C3N4 nanosheets with large layer spacing were prepared using acid treatment and thermal stripping methods. The Z-type heterostructure and localized surface plasmon resonance effect of Ag nanowires enabled high-speed electron transfer between the materials, while retaining large amounts of active substances, and broadened the light response range. Because of these features, the response current of the materials improved, and their impedance and photoluminescence reduced. Among the synthesized photocatalysts, 0.05Ag-ZnO/g-C3N4 (molar ratio of g-C3N4/ZnO: 0.05) exhibited the highest photocatalytic performance under UV–visible light. It degraded 98% of methylene blue in just 30 min, outperforming both g-C3N4 (21% degradation in 30 min) and Ag-ZnO (84% degradation in 30 min). In addition, 0.05Ag-ZnO/g-C3N4 demonstrated high cycling stability.

Salt stimulates sulfide−driven autotrophic denitrification: Microbial network and metagenomics analyses

Sulfur autotrophic denitrification (SADN) is a promising biological wastewater treatment technology for nitrogen removal, and its performance highly relies on the collective activities of the microbial community. However, the effect of salt (a prevailing characteristic of some nitrogen−containing industrial wastewaters) on the microbial community of SADN is still unclear. In this study, the response of the sulfide−SADN process to different salinities (i.e., 1.5 % salinity, 0.5 % salinity, and without salinity) as well as the involved microbial mechanisms were investigated by molecular ecological network and metagenomics analyses. Results showed that the satisfactory nitrogen removal efficiency (>97 %) was achieved in the sulfide−SADN process (S/N molar ratio of 0.88) with 1.5 % salinity. In salinity scenarios, the genus Thiobacillus significantly proliferated and was detected as the dominant sulfur−oxidizing bacteria in the sulfide−SADN system, occupying a relative abundance of 29.4 %. Network analysis further elucidated that 1.5 % salinity had enabled the microbial community to form a more densely clustered network, which intensified the interactions between microorganisms and effectively improved the nitrogen removal performance of the sulfide−SADN. Metagenomics sequencing revealed that the abundance of functional genes encoding for key enzymes involved in SADN, dissimilatory nitrate reduction to ammonium, and nitrification was up−regulated in the 1.5 % salinity scenario compared to that without salinity, stimulating the occurrence of multiple nitrogen transformation pathways. These multi−paths contributed to a robust SADN process (i.e., nitrogen removal efficiency >97 %, effluent nitrogen <2.5 mg N/L). This study deepens our understanding of the effect of salt on the SADN system at the community and functional level, and favors to advance the application of this sustainable bioprocess in saline wastewater treatment.

Fine-tuning porosity of In-MOFs with ncb topology based on reticular chemistry for one-step purification C2H4 from ternary C2H6/C2H4/C2H2 mixtures

One-step purification of C2H4 from ternary C2H6/C2H4/C2H2 mixtures by single adsorbent is of great industrial significance, but few adsorbents can achieve this purpose. Herein, four isoreticular In-MOFs, In-BDC-AINA, In-ATC-INA, In-Fum-INA, and In-Fum-AINA (H2BDC, H2ATC, H2Fum, HINA, and HAINA are 1,4-benzenedicarboxylic acid, 2-amino-terephthalic acid, fumaric acid, isonicotinic acid and 3-amino-isonicotinic acid, respectively), were designed and synthesized by the guidance of reticular chemistry, using the known In-BDC-INA as the platform, through amino modification and ligand shortening approaches. In-ATC-INA and In-BDC-AINA were aminations of H2BDC and HINA, respectively. In-Fum-INA is replacing H2BDC to shorter H2Fum. In-Fum-AINA is obtained by further amination of In-Fum-INA. Due to the molar ratio of isoniacic and dicarboxylic ligands in this series structure is 2/1, they exhibit different site numbers, site distributions, pore sizes and pore volumes after regulation. These frameworks without open metal sites provided the ability of C2H6/C2H4 inversion adsorption. The amino modification and ligand shortening approaches successfully improved the selectivity of C2H2/C2H4, and the equimolar C2H2/C2H4 selectivities of In-ATC-INA (1.82) and In-Fum-INA (2.81) were higher than that of In-BDC-INA (1.73) calculated by IAST method. The breakthrough results show that In-BDC-INA, In-ATC-INA and In-Fum-INA can achieve one-step separation of the ternary C2 mixtures and the C2H4 yields are 0.08, 0.13 and 0.09 mmol/g, respectively, demonstrating that the two approaches have successfully improved the gas separation performance. In addition, these materials possess exceptional thermal and chemical stability, the low-cost ligand used in In-Fum-INA synthesis further enhances its potential application for industrial gas separation.

Constructing Self-Healing Polydimethylsiloxane through Molecular Structure Design and Metal Ion Bonding

Self-healing polydimethylsiloxane (PDMS) has garnered significant attention due to its potential applications across various fields. In this study, a functionalized modification of PDMS containing di-aminos was initially conducted using 2,6-pyridinedicarbonyl chloride to synthesize pyridine-PDMS (Py-PDMS). Subsequently, rare earth metal europium ions (Eu3+) were incorporated into Py-PDMS. Due to the coordination interaction between Eu3+ and organic ligands, a coordination cross-linking network was created within the Py-PDMS matrix, resulting in the fabrication of Eu3+-Py-PDMS elastomer. At a molar ratio of Eu3+ to ligands of 1:1, the tensile strength of Eu3+-Py-PDMS reached 1.4 MPa, with a fracture elongation of 824%. Due to the dynamic reversibility of coordination bonds, Eu3+-Py-PDMS with a metal-to-ligand molar ratio of 1:2 exhibited varying self-healing efficiencies at different temperatures. Notably, after 4 h of repair at 60 °C, its self-healing efficiency reached nearly 100%. Furthermore, the gas barrier properties of Eu3+-Py-PDMS with a molar ratio of 1:1 was improved compared with that of Eu3+-Py-PDMS with a molar ratio of 1:1. This study provides an effective strategy for the design and fabrication of PDMS with high mechanical strength, high gas barrier properties, and exceptional self-healing efficiency.

Induced Diffusion Effect Realizes Heterogeneous Separation/Aggregation for In Situ Fabrication of Heterostructure with Enhanced Catalytic Activity

AbstractSpace charge transfer, which can be provided by heterogeneous structure, is the key to efficient electrocatalytic processes. However, difficulty in controlling the relative atomic diffusion rates due to different atomic radii and affinity makes heterogeneous nanostructures difficult to be accurately designed. Herein, an induced diffusion strategy based on affinity differences between elements is proposed to direct the separation/aggregation of different components in the precursor. The key to strategy in this study is the different affinity of Cu and Co to S/P in the precursor of CuCo Prussian blue analogue (PBA). By controlling the molar ratio of S and P during the phosphorization/vulcanization process, induced diffusion can be achieved and leads to directional separation/aggregation of Cu and Co species. As a result, a heterogeneous yolk‐shell Cu2S@CoP2‐C‐N‐S structure is successfully synthesized with a reticular CoP2‐C‐N‐Cu‐S as the shell and a Cu2S nanocrystal as the core. The space charge effect of the semiconductor heterojunction resulting from component separation/aggregation significantly promotes oxygen evolution reaction, resulting in an ultralow overpotential of 180 mV at 10 mA·cm−2. This work not only provides a simple method for efficient separation of key components in gas‐solid systems but also provides a method for fine‐tuning the active site in an active‐site‐engineering approach.

Migration of polydimethylsiloxane chain segments toward the surface of UV-cured waterborne poly(urethane-acrylate) films

Waterborne polyurethane (WPU) has poor water resistance and low surface hydrophobicity due to the incorporation of hydrophilic chain-extender. The water resistance and the surface hydrophobicity can be improved by incorporation of polydimethylsiloxane (PDMS), which is attributed to the migration of PDMS chain segments toward the surface of WPU film. However, whether the PDMS chain segments can migrate toward the surface of WPU film after UV-curing, resulting in higher hydrophobicity, needs further investigation? We prepared the different WPUA films by changing the molar ratio of aminopropyl-terminated polydimethylsiloxane (APT-PDMS) to hydroxyethyl acrylate (HEA), to deeply understand the migrating phenomenon of PDMS chain segments toward the surface of WPUA films. The migration cause of PDMS chain segments and the influence of chemical cross-linking on the migration were investigated by thermal annealing and solvent immersion of WPUA films. In addition, the migration activation energy and the relaxation time were studied by the migration rate of PDMS chain segments in the thermal annealing and the rheological behavior of WPUA film, aiming to elucidate the migration of PDMS chain segments depending on the chain motion and the fractional free volume. This investigation provides a simple and feasible strategy for improving the hydrophobicity of waterborne polyurethane.

The Design of a Novel Alkali-Activated Binder for Solidifying Silty Soft Clay and the Study of Its Solidification Mechanism

In order to overcome the problems of the high economic and environmental costs of a traditional ordinary portland cement-based binder, this study used self-combusted coal gangue (SCCG), granulated blast furnace slag (GBFS) and phosphorous slag (PS) to prepare a novel SCCG-GBFS-PS (SGP) ternary alkali-activated binder for solidifying silty soft clay (SC). Firstly, the parameters of the SGP ternary binder were optimized using orthogonal experiments. Then the effects of the SGP ternary binder content (mass ratio of the SGP ternary binder and the SGP-solidified soil), initial water content of SC (mass ratio of SC’ water and SC) and types of additives on the unconfined compressive strength (UCS) of the SGP-solidified soil were analyzed. Finally, the hydration products and microstructure of the SGP-solidified soil were analyzed to investigate the solidification mechanism of the SGP ternary binder. The results showed that the optimal mass ratio of GBFS and PS is 2:1, and the optimal alkali activator content (mass ratio of Na2O and the SGP ternary binder) and modulus of alkali activator (molar ratio of SiO2 and Na2O of alkali activator) were 13% and 1.3, respectively. When the SGP ternary binder content was 16% and the initial water content of SC was 35%, the SGP-solidified soil met the requirement of UCS for tertiary cured soil. The incorporation of triethanolamine and polyvinyl alcohol improved the UCS, while the incorporation of Na2SO4 significantly deteriorated the UCS of the SGP-solidified soil. The C-S-H gels and C(N)-A-S-H gels generated by hydration of the SGP-solidified soil were interspersed, interwoven and adhered to each other to form a network-like space structure that played the roles of skeleton, bonding soil particles and filling pores, which improved the macroscopic properties of the SGP-solidified soil. The results of this study provide a reference for the design and development of a solid waste-based binder for solidifying SC.

The role of hard and soft segments in the thermal and mechanical properties of non-isocyanate polyurethanes produced via polycondensation reaction

Plenty of research is being conducted on non-isocyanate polyurethanes (NIPUs) to replace harmful diisocyanates in traditional polyurethanes (PUs). In this research, the role of different types of hard and soft segments was investigated in the production of NIPUs via the polycondensation route. Hard segments comprised ethylene carbonate or propylene carbonate with hexane-1,6-diamine, while the soft segments consisted of polyethylene glycol (1000 g/mol or 400 g/mol) or polypropylene glycol (1000 g/mol) and were polymerized in different molar ratios. The NIPUs were characterized for their thermal and mechanical properties. FTIR and solvent resistance to tetrahydrofuran (THF) was used to evaluate the polycondensation reaction. Thermal analysis revealed mainly mixed hard and soft segments; the selection of the hard segment had an impact on the crystallinity of the mixed phase. Promising cohesive strength results as well as lap shear strengths were found on stainless steel and beech when the right selection of components was used. The best results were achieved when propylene carbonate was used as the hard segment, and polypropylene glycol (1000 g/mol) as the soft segment precursor in 1:30 M ratio.

Gamma-aminobutyric acid (GABA) improves salinity stress tolerance in soybean seedlings by modulating their mineral nutrition, osmolyte contents, and ascorbate-glutathione cycle

BackgroundIn plants, GABA plays a critical role in regulating salinity stress tolerance. However, the response of soybean seedlings (Glycine max L.) to exogenous gamma-aminobutyric acid (GABA) under saline stress conditions has not been fully elucidated.ResultsThis study investigated the effects of exogenous GABA (2 mM) on plant biomass and the physiological mechanism through which soybean plants are affected by saline stress conditions (0, 40, and 80 mM of NaCl and Na2SO4 at a 1:1 molar ratio). We noticed that increased salinity stress negatively impacted the growth and metabolism of soybean seedlings, compared to control. The root-stem-leaf biomass (27- and 33%, 20- and 58%, and 25- and 59% under 40- and 80 mM stress, respectively]) and the concentration of chlorophyll a and chlorophyll b significantly decreased. Moreover, the carotenoid content increased significantly (by 35%) following treatment with 40 mM stress. The results exhibited significant increase in the concentration of hydrogen peroxide (H2O2), malondialdehyde (MDA), dehydroascorbic acid (DHA) oxidized glutathione (GSSG), Na+, and Cl− under 40- and 80 mM stress levels, respectively. However, the concentration of mineral nutrients, soluble proteins, and soluble sugars reduced significantly under both salinity stress levels. In contrast, the proline and glycine betaine concentrations increased compared with those in the control group. Moreover, the enzymatic activities of ascorbate peroxidase, monodehydroascorbate reductase, glutathione reductase, and glutathione peroxidase decreased significantly, while those of superoxide dismutase, catalase, peroxidase, and dehydroascorbate reductase increased following saline stress, indicating the overall sensitivity of the ascorbate-glutathione cycle (AsA-GSH). However, exogenous GABA decreased Na+, Cl−, H2O2, and MDA concentration but enhanced photosynthetic pigments, mineral nutrients (K+, K+/Na+ ratio, Zn2+, Fe2+, Mg2+, and Ca2+); osmolytes (proline, glycine betaine, soluble sugar, and soluble protein); enzymatic antioxidant activities; and AsA-GSH pools, thus reducing salinity-associated stress damage and resulting in improved growth and biomass. The positive impact of exogenously applied GABA on soybean plants could be attributed to its ability to improve their physiological stress response mechanisms and reduce harmful substances.ConclusionApplying GABA to soybean plants could be an effective strategy for mitigating salinity stress. In the future, molecular studies may contribute to a better understanding of the mechanisms by which GABA regulates salt tolerance in soybeans.

Investigations on the Use of Deep Eutectic Solvents (DESs) as Promoters for the Conjugate Addition of α‐Nitroketones to Electron‐Poor Alkenes

AbstractDESs were profitably investigated as solvents and promoters of the conjugate reaction addition of cyclic and acyclic α‐nitroketones to a variety of electron‐poor alkenes. The best results were obtained conducing the reaction in betaine:1,2‐propanediol (1 : 5 molar ratio) DES at room temperature, and enones were demonstrated to be the most effective Michael acceptors. The same reaction conducted by using different molar ratios of the components in this DES showed the eutectic point to be the most effective in terms of the yields observed.

Synthesis of Cu-MOF-derived complex copper–chromium oxides and their catalytic study on the thermal decomposition of ammonium perchlorate

In this work, a series of complex copper-chromium oxides were prepared by adjusting the molar ratio of Cr3+/Cu2+ using MOF-199 as a template. X-ray diffraction (XRD), scanning electron microscopy (SEM), Transmission electron microscopy (TEM), and X-ray photoelectron spectroscopy (XPS) were used to characterize the structure, microscopic morphology and valence information of the samples. The specific surface area of the sample was estimated by the Brunauer-Emmett-Teller method (BET), and the pore size parameters of the sample were obtained by using the Barrett-Joyner-Halenda (BJH) model. The effect of the samples on the thermal decomposition process of ammonium perchlorate (AP) was investigated by differential scanning calorimetry-thermogravimetric analysis. The results show that the copper and chromium oxides in the complex exhibit good catalytic effects. Among them, CuCr(0.8) had the best catalytic effect, reducing the peak pyrolysis temperature of AP by 95.7 °C, increasing the heat release by 817 J/g, and reducing the reaction activation energy by 62.4 kJ/mol. Real-time FTIR was used to characterize the gas products during the thermal decomposition of AP, and the gas products of AP with CuCr(0.8) catalyst were different from those of pure AP, which may also be the reason for the increase of AP heat release after adding CuCr(0.8) catalyst.

New multi-parametrical pressurized WSGG model correlations for gaseous radiative heat transfer in high H2O/CO2 molar ratio conditions for sustainable fuel utilization

The utilization of H2 blended natural gas has great significance for advancing large-scale applications of hydrogen energy. Numerical simulation can provide valuable insights into the combustion characteristics of H2 blended natural gas. To calculate the radiative characteristics of H2O/CO2 mixed gas under complex conditions efficiently and accurately in CFD simulation, new multi-parametrical pressurized WSGG correlations were proposed in this study, which introduced a set of parameters that can simultaneously adapt to variations in temperature, pressure and H2O/CO2 molar ratio. The model coefficients are applicable across a wide range of conditions, including a total pressure range of 1∼10 bar, a temperature range of 400∼2500 K, H2O/CO2 molar ratio from 3–5 and partial pressure path lengths from 0.001 to 60 bar·m. The new correlations were validated under one- and two-dimensional cases. The average error of radiative heat flux was less than 3.92% and the average error of radiative heat source was less than 4.32%, while traditional WSGG models developed under standard pressure failed to comprehensively meet the demands. The calculation results indicated that the new multi-parametrical pressurized WSGG correlations can effectively simulate radiative calculations in combustion media under varying pressures and are suitable for the fuel with high H2 blending ratios, which is significant for hydrogen energy utilization.

Digital colorimetric detection of ammonium in water samples after microextraction procedure using deep eutectic solvent, based on DLLME method

In this study, we have presented a simple, cost-effective, and efficient method for quantifying ammonium ions based on digital colorimetry using a smartphone. Firstly, ammonium ions are converted into a yellow-colored derivative in an alkaline medium in the presence of acetylacetone and formaldehyde. Then, the colored compound is extracted using the dispersive liquid–liquid microextraction (DLLME) technique and its color intensity was measured using a smartphone as RGB Color Detector. For this purpose, a novel deep green eutectic solvent including tetrapropylammonium bromide (TPABr) and 3-methyl-1-butanol (isoamyl alcohol) was employed, with a molar ratio of 1:6. The impact of key variables on the derivatization and microextraction processes, including solution pH, concentration of acetylacetone and formaldehyde, temperature, reaction time, and extraction solvent volume, was thoroughly investigated and optimized. In the optimized conditions, the method was found to be linear in the range of 0.15–5.00 µg mL−1 with a limit of detection of 0.05 µg mL−1 (S/N = 3). Moreover, the proposed method was successfully applied for the determination of ammonium ions in environmental water samples, fish pond, and aquarium water samples, with recoveries ranging from 94.7 to 106.7 %.

Performance and mechanism of DL‐alanine ionic liquid shale inhibitor

AbstractShale hydration and expansion during drilling can lead to wellbore instability, sticking, and frequent leakage accidents. To prevent these issues, an ionic liquid (IL) inhibitor solution was synthesized using DL‐alanine and 98% concentrated sulphuric acid as raw materials. The optimum composition and effect of the synthesized inhibitor in oilfield water‐based drilling fluids were evaluated through anti‐expansion, linear expansion rate, water washing resistance, and clay hydration dispersion experiments. The inhibition mechanism was investigated by thermogravimetric analysis, infrared spectroscopy, zeta potential, contact angle, and X‐ray diffraction analysis. The results show that the optimum IL consists of a 1:1 molar ratio of DL‐alanine to concentrated sulphuric acid synthesized under a reaction temperature and time of 70°C and 18 h, respectively. The resulting DL‐alanine IL exhibited the best inhibitory effect on the hydration, dispersion, and expansion of clay at a concentration of 0.5% in aqueous solution, and its linear expansion rate was only 18.49%. After adding a quantitative amount of clay to different concentrations of DL‐alanine IL aqueous solution, the expansion volume of the clay decreased and the water washing resistance significantly improved. These results provide a theoretical basis for improving the safety and efficiency of shale horizontal well drilling operations.

Ring-Opening Polymerization of Cyclohexene Oxide and Cycloaddition with CO2 Catalyzed by Amine Triphenolate Iron(III) Complexes.

A series of novel amine triphenolate iron complexes were synthesized and characterized using UV, IR, elemental analysis, and high-resolution mass spectrometry. These complexes were applied to the ring-opening polymerization (ROP) of cyclohexene oxide (CHO), demonstrating excellent activity (TOF > 11050 h-1) in the absence of a co-catalyst. In addition, complex C1 maintained the dimer in the presence of the reaction substrate CHO, catalyzing the ring-opening polymerization of CHO to PCHO through bimetallic synergy. Furthermore, a two-component system consisting of iron complexes and TBAB displayed the ability to catalyze the reaction of CHO with CO2, resulting in the formation of cis-cyclic carbonate with high selectivity. Complex C4 exhibited the highest catalytic activity, achieving 80% conversion of CHO at a CHO/C4/TBAB molar ratio of 2000/1/8 and a CO2 pressure of 3 MPa for 16 h at 100 °C, while maintaining >99% selectivity of cis-cyclic carbonates, which demonstrated good conversion and selectivity.

Porphysome Engineered With Specific Protein Binding Sites as a Multimodal Theranostic Nanocarrier for Targeted Protein Delivery.

The immobilization of proteins on the surface of carriers is challenging due to the loss of protein structure and function in this process. Here, we report the development of the protein immobilization on the surface of the metallated-porphyrin complex in the porphysome nanocarrier. The conjugated Ni-porphyrin to fatty acid (as a tail) has been synthesized and independently placed at the depth of the bilayer center of Dipalmitoylphosphatidylcholine (DPPC) in which the Ni-porphyrin was at the polar region of the membrane and is thus superficial. This porphysome (DPPC: Ni-porphyrin, 4 : 1 mole ratio) was formed by supramolecular self-assembly with a diameter of 173±7 nm and zeta potential -8.5±3.4 mv, which exhibited no significant toxicity at the experimental concentrations and acceptable cellular uptake on MCF-7 cells. The physicochemical properties and specific protein binding sites of the firefly luciferase as a model protein into the porphysome (1 : 2 mole ratio) show the conjugation efficiency about 80 % and the conformation of protein was completely maintained. Furthermore, bioluminescence assay and SDS-PAGE confirmed the preservation of protein function. The stabilized platform of porphyrin-lipid structure can potentially improve the efficacy of protein functionality for a particular display, shifting porphysomes from a simple carrier to a therapeutic agent.

Circulating perturbation of phosphatidylcholine (PC) and phosphatidylethanolamine (PE) is associated to cardiac remodeling and NLRP3 inflammasome in cardiovascular patients with insulin resistance risk

Lipidome perturbation occurring during meta-inflammation is associated to left ventricle (LV) remodeling though the activation of the NLRP3 inflammasome, a key regulator of chronic inflammation in obesity-related disorders. Little is known about phosphatidylcholine (PC) and phosphatidylethanolamine (PE) as DAMP-induced NLRP3 inflammasome. Our study is aimed to evaluate if a systemic reduction of PC/PE molar ratio can affect NLRP3 plasma levels in cardiovascular disease (CVD) patients with insulin resistance (IR) risk.Forty patients from IRCCS Policlinico San Donato were enrolled, and their blood samples were drawn before heart surgery. LV geometry measurements were evaluated by echocardiography and clinical data associated to IR risk were collected. PC and PE were quantified by ESI-MS/MS. Circulating NLRP3 was quantified by an ELISA assay.Our results have shown that CVD patients with IR risk presented systemic lipid impairment of PC and PE species and their ratio in plasma was inversely associated to NLRP3 levels. Interestingly, CVD patients with IR risk presented LV changes directly associated to increased levels of NLRP3 and a decrease in PC/PE ratio in plasma, highlighting the systemic effect of meta-inflammation in cardiac response. In summary, PC and PE can be considered bioactive mediators associated to both the NLRP3 and LV changes in CVD patients with IR risk.

Recycling of fly ash to synthesize zeolites for efficient removal of dioxins

The large amount of fly ash (FA) produced by coal-fired power plants places tremendous pressure on the environment. Meanwhile, toxic dioxins emitted from municipal solid waste incineration plants are of great concern. To address these challenges, a win-win approach was proposed to re-utilize FA for synthesis of zeolite materials for dioxins adsorption. The results indicate that the Si/Al molar ratio in the liquid-phase precursor significantly influences the distribution of Si-Al 4-membered rings (Si/Al=1) and Si-Al 4-membered rings (Si/Al=3) in the system. These units are key secondary structures of the zeolite skeleton, determining the proportions of A-type and X-type zeolites in the product. With the increasing Si/Al molar ratio of precursor, the specific surface area and Si/Al molar ratio of zeolites derived from fly ash (ZFA) both increased, while they played a positive and negative role in dioxins adsorption, respectively. The adsorption of dioxins by ZFA peaked at a Si/Al molar ratio of precursor of 1.5, reaching 4.13×105 pg I-TEF/g, surpassing activated carbon by 1.46 times. This study not only elucidates the mechanism of Si/Al molar ratio of precursor on crystalline transformation of ZFA, but also confirms the potential of ZFA in dioxins adsorption.

[Ti{η5-1-(SiMe3)-3-(R)-C9H5}Cl2(OEt)] half-sandwich complexes: Synthesis, solid-state structure, hirshfeld surface analysis and theoretical studies

Indenyl-titanium trichloride complexes of type [Ti{η5-1-(SiMe3)-3-(R)-C9H5}Cl3] (R = SiMe3 (3a); R = tBu (3b)) were obtained by treatment of Li[1-(SiMe3)-3-(R)-C9H5] (R = SiMe3 (1a); R = tBu (1b)) with titanium tetrachloride (2) in a 1:1 molar ratio in the presence of isopropanol and SOCl2. Compounds [Ti{η5-1-(SiMe3)-3-(R)-C9H5}Cl2(OEt)] (R = SiMe3 (4a); R = tBu (4b)) are accessible by reacting 1a,b (R = SiMe3 (1a); R = tBu (1b)) with TiCl4 (2) in the presence of ethanol and SOCl2, or when 3a,b were treated with equimolar amounts of EtOH in refluxing benzene. Spectroscopic methods and single crystal X-ray diffraction analysis confirmed the piano-stool geometry of 3a and 4b in the solid state. Hirshfeld surface analysis using 2D fingerprint plots of 3a and 4b were conducted to elaborate non-covalent, intermolecular interactions existing in the solid state, which accounted for the strengthening of the crystal lattice. The molecular structures of the 3 and 4 were further investigated by quantum-chemical calculations. The geometries of the compounds were optimized at the B3LYP/6-31G(d)+LANL2DZ level of theory, and their related molecular parameters including frontier orbital energy gap and molecular electrostatic surface potential have also been calculated to better understand their properties.