Effect Of Molecular Structure Research Articles

Wettability of a Polymethylmethacrylate Surface by Fluorocarbon Surfactant Solutions

To clarify the adsorption behavior of fluorocarbon surfactants on PMMA surfaces, the contact angles of two nonionic fluorocarbon surfactants (FNS-1 and FNS-2) and an anionic fluorocarbon surfactant (FAS) on polymethylmethacrylate (PMMA) surface were determined using the sessile drop method. Moreover, the effects of molecular structures on the surface tension, adhesion tension, solid–liquid interfacial tension, and adhesion work of the three fluorocarbon surfactants were investigated. The results demonstrate that the adsorption amounts for three fluorocarbon surfactants at the air–water interface are 4~5 times higher than those at the PMMA–solution interface. The three fluorocarbon surfactants adsorb on the PMMA surface by polar groups before CMC and by hydrophobic chains after CMC. Before CMC, FNS-2 with the smallest molecular size owns the highest adsorption amount, while FAS with large-branched chains and electrostatic repulsion has the smallest adsorption amount. After CMC, the three fluorocarbon surfactants form aggregates at the PMMA-liquid interface. FAS possesses the smallest adsorption amount after CMC. Besides, FNS-1 possesses a higher adsorption amount than FNS-2 due to the longer fluorocarbon chain and the lower CMC value of FNS-1. The adsorption behaviors of nonionic and anionic fluorocarbon surfactants on the PMMA surface are different. FAS forms interfacial aggregates before CMC, which may be attributed to the electrostatic interaction between the anionic head of FAS and the PMMA surface.

High-Pressure CO2 and CH4 Transport in Smooth Crystalline Silica Mesopores: A Molecular Dynamics Study.

In this study, we use molecular dynamics (MD) simulation to study pressure-driven CO2 and CH4 flows and their slippage behaviors in β-cristobalite mesopores. The result illustrates that both CO2 and CH4 have an apparent adsorption layer on pore surface. However, significant differences in gas slippage are observed: CH4 flow shows considerable slippage, while it is negligible for CO2 flow. This disparity is attributed to the collective effect of gas molecular configurations and surface structure. The linear molecular structure of CO2 allows it to align perpendicular to the surface, even penetrating into the surface. Notably, the perpendicular orientation of CO2 molecules is energetically favored near the center of the equilateral triangle formed by adjacent oxygen atoms on β-cristobalite surface. Conversely, the symmetric molecular structure of CH4, coupled with its larger size, prevents its penetration into pore surfaces. Therefore, despite smooth crystalline surfaces, CO2 topological accessible plane is much more curved than that of CH4. Consequently, CO2 displays hesitating motions undergoing rotational movements, which significantly hinders its slippage. This study highlights the collective influences of gas molecular characteristics and surface structure on gas slippage, affording important insights into gas sequestration and the development of functional materials for gas separation.

Synthesis and characterization of new perylenediimide derivatives: Promising low-cost electron transport materials for perovskite solar cells

In organic-inorganic perovskite solar cells (PSCs), the electron transport layer (ETL) plays a crucial role providing efficient electron extraction and transport required for achieving high device performance. Compared to traditional fullerene-based electron-transport materials (ETMs), non-fullerene small molecules have attracted much attention due to their tunable optoelectronic properties, lower cost, and much higher stability. In this work, we synthesized and characterized four perylenediimide (PDI) derivatives and investigated their optoelectronic properties in the context of application as ETMs for PSCs. To establish the compatibility of PDI films with perovskite absorber material, the surface properties of Cs0.12FA0.88PbI3/PDI bilayer stacks were studied using contact angle and infrared scattering scanning near-field microscopy methods. A study of the photochemical stability of these bilayer stacks showed that coating the perovskite film with a layer of PDI improves its tolerance with respect to light. Utilizing these molecules as ETMs in the inverted p-i-n PSCs delivered light power conversion efficiencies ranging from 11.1 % to 15.4 %, thus indicating the considerable effect of the PDI derivative molecular structure on the photovoltaic properties. Further development of this research direction may lead to the rational design of advanced PDI-based electron transport materials for efficient and stable PSCs.

Effects of molecular structure and temperature field on the crystallization behavior of poly(tetrafluoroethylene-co-perfluoroalkylvinyl ether)

Despite the wide industrial application of poly(tetrafluoroethylene-co-perfluoroalkylvinyl ether) (PFA) in semiconductor processing, its crystallization behavior has little been studied. In this work, three PFA resins with similar molecular weight but different comonomer content and distribution were synthetized. Then the non-isothermal crystallization kinetics and crystalline structures were studied by differential scanning calorimetry, polarizing optical microscopy, and X-ray diffraction systematically. It is found that the incorporation of comonomers destroys the chain regularity and reduces the crystallizability of PFA thermodynamically, while the comonomer insertion improves the chain flexibility to accelerate the crystal growth dynamically. When the comonomer content of PFA is low, both the nucleation and growth rates are quite fast, which is favorable for the formation of spherulite. As the comonomer content increases or distribute uniformly in the chain, the nucleation rate declines notably and the side groups distort the crystal cell to increase the spacing of [100] plane. Moreover, two-dimensional growth mode is dominant to form bundle-like structure when crystallizing at slow cooling, where nucleation is suppressed by growth. But three-dimensional symmetrical spherulite can be activated and perfected at high cooling rate due to the initiation of substantial nucleation sites. This unique crystallization behavior is opposite to that of conventional polymers, providing a guidance for the polymerization and processing of PFA.

Effects of Oxygen Concentration on Soot Formation in Ethylene and Ethane Fuel Laminar Diffusion Flames

In studying the effects of oxygen concentration and molecular structure on the morphologies of the soot particles produced by hydrocarbon fuels, ethylene and ethane were chosen as experimental fuels. With a Gülde laminar coaxial diffusion flame device, a soot particle device was used to sample soot particles at different oxygen concentrations (21%, 24%, 26%, 28%, and 31%) and at different heights above a burner (HABs = 10 mm, 20 mm, 30 mm, 40 mm, and 50 mm). High-resolution transmission electron microscopy (HRTEM) was used to scrutinize and analyze the soot particles at varying oxygen concentrations. The findings suggest that at the same oxygen concentration, ethylene produces brighter and taller flames. With an increase in the oxygen concentration, ethylene flames and ethane flames gradually decrease in height and become brighter. With an increase in the HAB, the average primary soot particle diameter (Dp) increases initially and then decreases, the fractal dimension (Df) increases, and the aggregates transition from strips and chains to clusters. At the same flame height (HAB = 30 mm), the Dp decreases, the Df increases, the carbon layer torsion resistance (Tf) and the carbon layer spacing (Ds) increase, and the carbon layer changes from a parallel arrangement to a curved arrangement to form denser network aggregations.

Effect of molecular weight and chemical structure of plasticizer on suspension property, binder removal, and sintered performance for zirconia toughened alumina ceramics fabricated by vat photopolymerization

Adding plasticizer is an appealing strategy to optimize binder removal for ceramic components fabricated by vat photopolymerization (VPP). However, so far the studies for effect mechanism of plasticizer on whole technological process of VPP are comparatively very limited, especially through analysis of physical and chemical properties of plasticizers. Herein, the effect of molecular weight and chemical structure of plasticizer on suspension property, binder removal, and sintered performance of zirconia toughened alumina (ZTA) ceramics was comprehensively investigated. Two types of plasticizers, namely, polyethylene glycol (PEG) and polypropylene glycol (PPG), with various molecular weights from 200 to 600 were used. Interestingly, only after adding PEG200 or PPG200, the suspensions still exhibited desired rheological and photocuring behavior, and the superior surface quality was still observed. More importantly, PPG200 proved to be the most effective plasticizer to achieve the most excellent and stable mechanical performances, as well as the highest debinding efficiency.

Effect of molecular structure on the dynamics and viscoelasticity of vitrimers

Vitrimers are a class of dynamic polymer networks that perform bond-exchange reactions (BERs) under environmental stimuli while preserving network connectivity. The viscoelastic properties of vitrimers are not only dependent on the kinetics of BERs, but also the architectures of polymer matrix. Here, we investigate the influence of polymer architectures on the dynamics and linear viscoelasticity of vitrimers through varying the sticker (reactive bead) distribution in the precursor chain and the BERs energy barrier (Ub) by performing hybrid molecular dynamics-Monte Carlo simulations. Increasing Ub, vitrimers with block and gradient distributions exhibit considerably faster relaxations of chain ends, Rouse mode, and stress and lower zero-shear viscosity than the analogs with random and uniform distributions, in qualitative agreement with the predictions of the sticky Rouse model. In contrast, the distribution of stickers has a small influence on the relaxation of dynamic bonds regardless of the Ub value. By comparing the molecular structures of vitrimers with different distributions of stickers, we find that the molecular defects, especially the relatively longer dangling end in block and gradient distributions, impair the effect of dynamic bonds on the dynamics and viscoelasticity of vitrimers. This suggests that the dangling defects can be leveraged for further development of recyclable and healable materials with fast stress relaxation and improved flowability.

The effect of molecular structure of imidazole-based compounds on corrosion inhibition of Cu, Zn, and Cu-Zn alloys

Three imidazole-based compounds (imidazole, 2-mercaptobenzimidazole, and 2-mercapto-1-methylbenzimidazole) were studied as corrosion inhibitors of Cu, Zn, and a family of Cu-xZn brass alloys (x = 10−40wt.%) in 3wt.% NaCl solution. The composition of inhibitor layers on the surface was studied using X-ray photoelectron and infrared spectroscopies. The molecular adsorption modes on Cu and Zn were modelled using density-functional theory (DFT) calculations. Mercapto-based inhibitors act as efficient inhibitors on all materials studied due to the formation of inhibitor layer through bonding with nitrogen and sulphur atoms. In contrast, imidazole is a moderate inhibitor for Zn, while it is much less efficient for Cu.

Retention mechanisms of dipeptides on superficially porous particle vancomycin- and teicoplanin-based chiral stationary phases

Chromatographic behavior of new chiral stationary phases (CSPs) Chiral-T and Chiral-V with teicoplanin and vancomycin antibiotics grafted onto superficially porous silica particles was studied in relation to dipeptide (DP) stereoisomers. The unbuffered water–methanol solutions were used as mobile phases (MPs). The effects of physical properties and molecular structure of analytes and selectors on retention and separation of DP stereoisomers are discussed herein. Chiral-T was evinced to exhibit high enantioselectivity, with highest α values attaining 16.5, 18.8 and 20.4 for Gly-Leu, dd/ll-Phe-Leu and ld/dl-Ala-Ala. At this point, Chiral-V did not exhibit enantioselectivity towards DP stereoisomers. The effect of MP composition on retention and enantioseparation of DPs was investigated. Lipophilicity of DPs was found to be an essential factor in the dependence of their retention vs. methanol concentration in МPs. Lipophobic DPs were eluted more quickly by water-rich solvents, with lipophilic DPs exhibiting an asymmetric U-shaped, or a descending dependence of retention factor vs. the methanol percentage on Chiral-T or Chiral-V, respectively. A theoretical model taking into account interaction of both solvents of a binary MP with both an analyte and adsorption sites was successfully applied so as to approximate and interpret the dependences of DP retention (monotonic and U-shaped) vs. a modifier content in MP. Water molecules were evinced to predominantly participate in competitive adsorption with DP molecules. The model predicted better solvation of lipophilic DPs by methanol and better solvation of lipophobic DPs by water. An attempt was made to verify the possibility of modeling by molecular docking the processes occurring during interaction between DP stereoisomers and CSPs, including consideration of the influence of competitive binding of eluent molecules in selector cavity.

Differences and Mechanism of Waxy Corn Starch and Normal Corn Starch in the Preparation of Recrystallized Resistant Starch (RS3).

This study prepared resistant starch (RS) from waxy corn starch and normal corn starch and analyzed the effects of its molecular and microstructural characteristics on RS content. The RS content of waxy corn resistant starch (RS-WCS) was highest at 57.8%, whereas that of normal corn resistant starch (RS-NCS) was 41.46%. The short-chain amylose contents of RS-WCS and RS-NCS were 47.08% and 37.24%, respectively, proportional to their RS content. Additionally, RS content positively correlated with crystallinity, short-range order degree, and degree of polymerization (DP), exceeding 25. Electron microscopic images, before and after enzymolysis, revealed that RS-WCS was hydrolyzed from the surface to the center by pancreatic α-amylase, while RS-NCS underwent simultaneous hydrolysis at the surface and center. These results indicate that the higher RS content in RS-WCS, compared to RS-NCS, is attributable to the synergistic effects of molecular structure and microstructure.

New insights into the effect of molecular structure on stable intermediate formation during the pyrolysis of normal and branched alkanes – I: Multi-species time history measurements

Decarbonization of energy systems that drive the transportation industry is imperative for effectively mitigating global greenhouse gas emissions. In this pursuit, the transition towards scalable and sustainable fuels will play a key role. These fuels are predominantly composed of a diverse array of hydrocarbons spanning various molecular classes. To better understand the complex chemistry of such fuels, we studied the impact of molecular structure on the distribution of pyrolysis products of C6-C12 hydrocarbons, encompassing both normal and branched alkanes, in a shock tube at combustion-relevant temperatures. An extensive suite of laser absorption spectroscopy-based diagnostics was used to simultaneously measure the time histories of key intermediates (methane, ethylene, and larger alkenes) and fuel during the pyrolysis of ten neat hydrocarbons: n-hexane, n-heptane, n-octane, n-decane, n-dodecane, 2-methylhexane, 2-methylheptane, 2-methylnonane, triptane (or 2,2,3-trimethylbutane), and iso-octane (or 2,2,4-trimethylpentane). These experiments were conducted behind reflected shock waves using 2% Fuel/Argon test mixtures at a nominal pressure of 2 atm over the temperature range of 1100–1500 K. Conducting these experiments under similar test conditions facilitated the observation of clear trends in the distribution of intermediates formed during the pyrolysis of these fuels. The current paper delineates the experimental strategy and presents the measured mole fraction time histories of the stable intermediates. A companion paper [1] delves into the observed trends and effects of molecular structure, in particular, the impact of increasing carbon number and the impact of varying degree of branching on the yields of these pyrolysis products. We also investigate the impact of fuel blending and provide insights into the role of inter-coupling on the distribution of stable intermediates. The authors anticipate that the trends and findings presented in these two papers will guide the design of sustainable fuels and play a pivotal role in modeling the combustion chemistry of the next generation of fuels. To the best of our knowledge, this work presents the first systematic, detailed pyrolysis study of several transportation-relevant hydrocarbon fuels, involving simultaneous measurements of multiple species in a shock tube using laser absorption spectroscopy.

New insights into the effect of molecular structure on stable intermediate formation during the pyrolysis of normal and branched alkanes − II: Impact of carbon number and degree of branching

Transitioning to scalable and sustainable fuels produced from renewable feedstocks will be essential for decarbonizing the transportation sector. As these fuels typically encompass a wide range of molecular classes, it is important to understand the impact of varying molecular structure on their overall combustion behavior. To that end, experiments were conducted to investigate the thermal decomposition of ten neat hydrocarbons with varying carbon numbers and degree of branching in a shock tube at engine-relevant temperatures. A multi-wavelength, laser absorption spectroscopy-based approach was used to measure key stable intermediates formed during the pyrolysis process. The experiments revealed clear trends in intermediate formation and distribution, influenced by the molecular structure of each fuel. Additional experiments were conducted with a 2% composite fuel (consisting of a 50% n-heptane/50% iso-octane mixture)/Ar mixture to assess the impact of fuel blending on the pyrolysis process. A companion paper (Boddapati et al., 2024) delineates the experimental strategy and provides comprehensive mole fraction time histories of the major products, along with thorough analysis of carbon atom recovery. This paper establishes empirical trends in the measured intermediate yields with varying carbon number and degree of branching, and provides a discussion on the chemical phenomena governing the thermal decomposition of these fuels. In addition, this paper also lays the foundation for developing compact, robust chemical kinetic models for conventional and alternative fuels based on compositional information obtained through infrared spectra. The insights gained from these studies have the potential to guide sustainable fuel design and contribute to modeling the combustion chemistry of next-generation fuels.

Modulating lipid bilayer permeability and structure: Impact of hydrophobic chain length, C-3 hydroxyl group, and double bond in sphingosine

Sphingosine, an amphiphilic molecule, plays a pivotal role as the core structure of sphingolipids, essential constituents of cell membranes. Its unique capability to enhance the permeability of lipid membranes profoundly influences crucial life processes. The molecular structure of sphingosine dictates its mode of entry into lipid bilayers and governs its interactions with lipids, thereby determining membrane permeability. However, the incomplete elucidation of the relationship between the molecular structure of sphingosine and the permeability of lipid membranes persists due to challenges associated with synthesizing sphingosine molecules. A series of sphingosine-derived molecules, featuring diverse hydrophobic chain lengths and distinct headgroup structure, were meticulously designed and successfully synthesized. These molecules were employed to investigate the permeability of large unilamellar vesicles, functioning as model lipid bilayers. With a decrease in the hydrophobic chain length of sphingosine from C15 to C11, the transient leakage ratio of vesicle contents escalated from ∼ 13 % to ∼ 28 %. Although the presence of double bond did not exert a pronounced influence on transient leakage, it significantly affected the continuous leakage ratio. Conversely, modifying the chirality of the C-3 hydroxyl group gives the opposite result. Notably, methylation at the C-3 hydroxyl significantly elevates transient leakage while suppressing the continuous leakage ratio. Additionally, sphingosines that significantly affect vesicle permeability tend to have a more pronounced impact on cell viability. Throughout this leakage process, the charge state of sphingosine-derived molecule aggregates in the solution emerged as a pivotal factor influencing vesicle permeability. Fluorescence lifetime experiments further revealed discernible variations in the effect of sphingosine molecular structure on the mobility of hydrophobic regions within lipid bilayers. These observed distinctions emphasize the impact of molecular structure on intermolecular interactions, extending to the microscopic architecture of membranes, and underscore the significance of subtle alterations in molecular structure and their associated aggregation behaviors in governing membrane permeability.

In-situ formation of hydrophobic deep eutectic solvents to separate lactic acid: Lactam as hydrogen bond acceptor and lactic acid as hydrogen bond donor

Lactic acid (LA) is a typical high added-value chemical and platform molecule derived from renewable biomass. To realize high efficiency and green separation of LA is of both scientific and practical significance. In this work, we proposed a novel mechanism of in-situ formation of hydrophobic deep eutectic solvents (HDES) to couple the separation of LA and synthesis of HDES. Due to the high solubility of LA as hydrogen bond donor in water, three hydrophobic lactams (N-Octyl-2-pyrrolidone (NOP), N-Dodecyl-2-pyrrolidone (NDP) and 2-Octyl-4-isothiazolin-3-one (OIT)) were optioned as hydrogen bond acceptors. The effect of lactam molecular structure on separation efficiency was discussed and compared in detail. The compositions of HDES forming in-situ were found to be 1.50 for NOP and NDP to LA while 1.20 for OIT to LA using experiments of slope method and continuous variations method. The key evidence of formation of HDES was confirmed by FT-IR, frontier molecular orbital analysis and interaction region indicator analysis. The multistage counter-current extraction experiment results showed the in-situ formation of HDESs can transfer 99% of LA from fermentation broth to the HDES, and LA was separated completely from the impurities. This work provided a new perspective on lactic acid separation and its potential industrial applications.

Novel bio-based polyurethane elastomers for adjustable room-temperature damping property

The distinctive viscoelastic behavior of elastomeres can be exploited for reducing vibrations and noise. However, the utility of conventional rubber-based elastomers is limited by low glass transition temperature (Tg) and narrow adjustable damping range, which constrain the room-temperature damping property. Moreover, the majority of rubber-based elastomers are sourced from unsustainable petroleum-based resources. Therefore, designing bio-based materials with room-temperature high-damping property to replace conventional rubber-based elastomers is crucial. Herein, a novel bio-based polyurethane (bio-PU) elastomer with an adjustable damping-temperature range and room-temperature high-damping property is successfully synthesized from bio-based poly (trimethylene ether) glycol. The effects of molecular chain structure on the thermal properties, mechanical properties, and adjustable damping-temperature range of the bio-PU elastomers, along with the mechanisms underlying these effects, are elucidated in detail. As the content of hard segment increasing, the Tg of bio-PU elastomers significantly increases from −13.0 to 29.9 °C, effectively encompassing the damping temperature range within the room-temperature working range. This promising strategy for formulating bio-based elastomers with adjustable damping-temperature range can advance the sustainable growth of PU industry and broaden the scope of PU damping applications.

Self-Assembled Micelles Based on Ginsenoside Rg5 for the Targeted Treatment of PTX-Resistant Tumors.

Paclitaxel (PTX) is one of the first-line drugs for prostate cancer (PC) treatment. However, the poor water solubility, inadequate specific targeting ability, multidrug resistance, and severe neurotoxicity are far from being fully resolved, despite diverse PTX formulations in the market, such as the gold-standard PTX albumin nanoparticle (Abraxane) and polymer micelles (Genexol-PM). Some studies attempting to solve the multiple problems of chemotherapy delivery fall into the trap of an extremely complicated formulation design and sacrifice druggability. To better address these issues, this study designed an efficient, toxicity-reduced paclitaxel-ginsenoside polymeric micelle (RPM). With the aid of the inherent amphiphilic molecular structure and pharmacological effects of ginsenoside Rg5, the prepared RPM enhances the water solubility and active targeting of PTX, inhibiting chemotherapy resistance in cancer cells. Moreover, the polymeric micelles demonstrated favorable anti-inflammatory and neuroprotective effects, providing ideas for the development of new clinical anti-PC preparations.

Evaluation of adsorption behaviour of benzylidene chitosan derivatives at mild steel/ 0.5 M H2SO4 solution interface

Four green benzylidene chitosan derivatives (BCs) were synthesized and evaluated as anti-corrosive substances for the first time against mild steel corrosion in 0.5 M H2SO4 solution. The synthesized BCs were laid to infrared spectroscopy and proton resonance spectroscopy for structural confirmation. Gravimetric and electrochemical experiments were accustomed to appraise the effectiveness of inhibitors, however, Scanning Electron Microscopy-Electron Dispersive Spectroscopy (SEM-EDS), Atomic Force Microscopy (AFM), and X-ray Photoelectron Spectroscopy (XPS) were exploited to evaluate the protective mechanism offered by benzylidene chitosan derivatives. Experimental results demarcate the synthesized inhibitors; Anisaldehyde modified Chitosan (CMB), 2-Hydroxy-4-methoxybenzaldehyde modified Chitosan (CHMB), 2,4-Dimethoxybenzaldehyde modified Chitosan (CDMB) and 2-Bromo-4-methoxybenzaldehyde modified Chitosan (CBMB) exhibiting praising inhibitory properties for mild steel corrosion and CDMB was seen possessed preferable inhibition potential at the finest concentration of 500 mgL-1 owing to the proximity of two electron-donating OCH3 groups. Furthermore, the inhibitors have been recorded to behave mixed type with pronounced impact on hydrogen evolution kinetics. The order of inhibition efficacy obtained was CDMB (98.8 %) > CHMB (95.4 %) > CMB (92.8 %) > CBMB (89.2 %) which was further validated by quantum chemical calculations which later opened up about the mechanistic approach involved in electron transfer from inhibitors to metallic vacant orbitals. Additionally, the effect of molecular structure possessed by synthesized inhibitors has been correlated with observed variation in their corrosion inhibition efficiency.

Rheology of polyborazanes with various molecular structures and dynamic transformation process

AbstractThe molecular structure of polymer precursors significantly affects their rheological properties, thermal stability, and ceramic conversion rates. For the first time, we revealed the effects of polyborazane molecular structure on rheology and molecular configuration dynamic transformation process. The systems studied are polyborazane precursors with rigid six‐membered ring structures. We synthesized precursors with different molecular structures, including polyborazanes with varying degrees of branching and molecular chain flexibility, and investigated how molecular structure affects viscosity under different conditions of temperature, time, and shear rates. The results indicate that decreasing the branching degree enhances thermal stability and reduces both zero‐shear viscosity and infinite‐shear viscosity. Increasing the flexibility of molecular chains notably reduces infinite‐shear viscosity, while having minimal impact on zero‐shear viscosity and thermal stability. In conclusion, the ideal molecular structure should aim to increase the flexibility of the molecular chains while maintaining a certain degree of branching, such as a dendritic molecular configuration. By correlating viscosity data with molecular structure, we constructed a dynamic transition process of molecular chain entanglement, disentanglement, and crosslinking. This research is essential for understanding polymer rheology and its applications in industry, particularly in designing and synthesizing precursor structures for producing various ceramic fibers through Polymer‐Derived Ceramics.

Deasphalting of crude oils: A molecule-based model to explore an optimization approach and alternative solvents

Actual motivation to reduce environmental impact leads to an increase in the study of green technologies, even those used in processes with fossil fuels. However, far from the proposed reduction of such energies, heavier crude oils are being processed to fulfill the energy demand. Heavy crude oils require an upgrading process to mitigate the effect of noxious components or contaminants such as asphaltenes and heavy metals. In this work, a deasphalting process was studied by simulation as a pretreatment to eliminate the heavy compounds of crude oil. The simulation of such a deasphalting process was carried out by Aspen Plus® software by combining a model for crude oil, formed by 33 molecules and able to describe its complex composition, mainly in the asphaltene fraction, and a model for the phase equilibria that use liquid-liquid equilibrium equations and the modified UNIFAC (Dortmund) model.A new objective function, including extraction yield, asphaltene reduction, and the ratio solvent/crude oil, was proposed and used to optimize extraction conditions and compare the performance of several solvents. Up to 12 pure solvents of different nature (tert-butanol, n-butanol, iso-propanol, methanol, ethylene glycol, acetone, methyl-isobutyl ketone, per-fluoro heptane, anisole, 1-metil-2-pyrrolidone, sulfolane, and n-heptane) were checked as well as some binary mixtures of them to explore more sustainable alternatives against conventional paraffin as precipitating agents. Satisfactory results were obtained when alcohols or ketones were used. A deeper study was developed to understand the effects of the alcohols' molecular structure (branching, chain length, and molecular weight) as solvents. Higher branching reduces the solvent/oil ratio, while higher molecular weight leads to higher extraction yield but poorer asphaltene reduction.

Effects of molecular structure and charge state on the foaming and emulsifying properties of Spirulina protein isolates

Microalgae protein holds great potential for various applications in the food industry. However, the current knowledge regarding microalgae protein remains limited, with little information available on its functional properties. Furthermore, the relationship between its molecular structure and functional properties is not well defined, which limits its application in food processing. This study aims to addresses these gaps though an analysis of the emulsibility and foamability of various soluble protein isolates from two species of Spirulina (Arthospira platensis and Spirulina platensis), and the functional properties of Spirulina protein isolates in relation to its molecular structure and charge state. Results revealed that the degree of cross-linking and aggregation or folding and curling of protein tertiary structures was higher in the highly soluble Spirulina protein isolates (AP50% and SP50%) than in the low-solubility isolates (AP30% and SP30%). The foaming capacity (FC) of AP50% and SP50% was found to be lower than that of AP30% and SP30%. Spirulina protein isolates can stably adsorb at the air-water interface for at least 20 min and possessed good interfacial activity. A high pH value was found to promote cross-linking of protein particles at the oil-water interface, thereby reinforcing the internal network structure of emulsions and increasing viscosity. These findings provide preliminary insights for potential applications of Spirulina protein isolates in food production, especially towards quality improvement.