Endothermic Events Research Articles

Novel Cu1+xMn1-xSeTe nanostructure fabrication by simple microwave synthesis for potential photodetection and dielectric applications

Chalcogenide compounds featuring transition metals have garnered significant interest due to their remarkable properties in various optoelectronic and dielectric applications. This study utilized a straightforward microwave synthesis technique to fabricate Cu1+xMn1-xSeTe (CMST) nanomaterials by varying the concentrations of Cu and Mn. Structural analysis confirmed the presence of two distinct ternary crystalline phases: Cu2MnSe2 and Cu (SeTe)2. Further examination through Raman spectroscopy revealed unique vibrational modes within the CMST nanostructure, characterized by a shift of active modes towards lower wave numbers. Surface morphology investigations indicated a nanoparticle-like structure, while optical measurements displayed a notable blue shift in the absorption edge, leading to an enhancement of the optical bandgap. Additionally, theoretical calculations suggested that the refractive index decreased as the bandgap increased. Thermal analysis identified multiple endothermic and exothermic events, indicating structural modifications and changes in thermal properties associated with mass disintegration. Dielectric studies showed promising results, with improved performance observed at elevated temperatures and higher frequency ranges. A photo-response evaluation demonstrated that the Cu-rich CMST-1 material exhibited a higher current response under illumination. In contrast, reducing the Cu content while increasing the Mn concentration resulted in a slight decrease in the current value for the CMST material. ​These findings point to the potential applicability of CMST nanomaterials in optoelectronic devices, photodetectors, and dielectric applications.

Different Magnitudes of Second-Order Jahn-Teller Effect in Isostructural NaMO2F2 (M = Nb5+, Ta5+) Oxyfluorides

The structures of the ordered and isotype oxyfluorides NaMO2F2 (M = Nb, Ta) were thoroughly investigated by combining powder X-Ray Diffraction (PXRD), 19F and high-field 23Na and 93Nb solid-state NMR, and DFT calculations. The structures, derived from Rietveld refinement of the PXRD data, exclusively consist of cis-[MO4F2]5– octahedra, in which cations are displaced from their ideal centered positions toward an oxide face. The NMR parameters were calculated for both the experimental (ES) and the atomic positions optimized (APO) structures, the latter exhibiting, as is often the case, the best agreement with the experimental data. Nb5+ and Ta5+ cations having the same size, niobium and tantalum isotypes have usually very close cell parameters. However, those of NaNbO2F2 and NaTaO2F2, particularly c, differ in unusual proportions. This difference in c parameters is due to stronger second-order Jahn-Teller effect (SOJTE) for the cis-[NbO4F2]5– than for the cis-[TaO4F2]5– octahedra, further confirmed by band structure and projected density of states calculations. Furthermore, by optimizing the synthesis conditions of these compounds using thermal analysis, a very low amplitude endothermic event, upon heating, was observed only for NaNbO2F2. An extensive analysis of the variable temperature (VT) PXRD data revealed that this event is related to a deviation from linearity of the cell parameters evolution and that structural features of these two isotypes evolve differently with temperature.

Tutton salt (NH4)2Zn(SO4)2(H2O)6: thermostructural, spectroscopic, Hirshfeld surface, and DFT investigations

ContextAmmonium Tutton salts have been widely studied in recent years due to their thermostructural properties, which make them promising compounds for application in thermochemical energy storage devices. In this work, a detailed experimental study of the Tutton salt with the formula (NH4)2Zn(SO4)2(H2O)6 is carried out. Its structural, vibrational, and thermal properties are analyzed and discussed. Powder X-ray diffraction (PXRD) studies confirm that the compound crystallizes in a structure of a Tutton salt, with monoclinic symmetry and P21/a space group. The Hirshfeld surface analysis results indicate that the main contacts stabilizing the material crystal lattice are H···O/O···H, H···H, and O···O. In addition, a typical behavior of an insulating material is confirmed based on the electronic bandgap calculated from the band structure and experimental absorption coefficient. The Raman and infrared spectra calculated using DFT are in a good agreement with the respective experimental spectroscopic results. Thermal analysis in the range from 300 to 773 K reveals one exothermic and several endothermic events that are investigated using PXRD measurements as a function of temperature. With increasing temperature, two new structural phases are identified, one of which is resolved using the Le Bail method. Our findings suggest that the salt (NH4)2Zn(SO4)2(H2O)6 is a promising thermochemical material suitable for the development of heat storage systems, due to its low dehydration temperature (≈ 330 K), high enthalpy of dehydration (122.43 kJ/mol of H2O), and hydration after 24 h.MethodsComputational studies using Hirshfeld surfaces and void analysis are conducted to identify and quantify the intermolecular contacts occurring in the crystal structure. Furthermore, geometry optimization calculations are performed based on density functional theory (DFT) using the PBE functional and norm-conserving pseudopotentials implemented in the Cambridge Serial Total Energy Package (CASTEP). The primitive unit cell optimization was conducted using the Broyden–Fletcher–Goldfarb–Shanno (BFGS) algorithm. The electronic properties of band structure and density of states, and vibrational modes of the optimized crystal lattice are calculated and analyzed.Graphical abstract

Effect of carboxymethyl cellulose binder on physical, thermal, and rheological properties of milk protein isolate/guar gum mixture powder

This study examined the effect of fluidized-bed agglomeration with a carboxymethyl cellulose (CMC) binder on the physical, thermal, and rheological properties of agglomerated milk protein isolate (MPI)-guar gum (GG) mixtures (AMGs). The agglomeration process produced larger and more porous particles, improving solubility and powder flowability. An exothermic event followed by an endothermic event was observed in DSC thermograms. These thermal events tended to occur at a higher temperature with lower enthalpy values as the binder concentration increased. All samples exhibited shear-thinning behavior, with apparent viscosity at 100 s−1 values (0.27–0.29 Pa s) for AMGs being lower than for non-agglomerated MPI-GG mixture (NAMG; 0.34 Pa s). Viscoelastic moduli values showed similar trends. Additionally, compared to NAMG, larger and more guar gum lumps occurred in the AMGs. These findings suggest that the agglomeration process with CMC promoted depletion interactions between the protein and polysaccharide components in the mixture system.

Characterization of Carbamide Peroxide: Stability Studies, and Degradation Kinetics under Isothermal Conditions for Industrial Application

Background: Carbamide peroxide (CP) is a hydrogen peroxide derivative bonded with urea. It is a solid substitute for liquid hydrogen peroxide in the chemical, cosmetics, and pharmaceutical industries, mainly as a disinfectant and bleaching application. However, it has an unstable nature, and there are scant studies on CP thermal analysis. Objective: This study focuses on CP thermal analysis and degradation behavior. Methods: CP was characterized by differential scanning calorimetry, thermogravimetric analysis, Fourier-transformed infrared, diffraction by X-ray, as well as, thermal and photodegradation was determined by ultraviolet spectrophotometer. Results: CP was characterized with a sharp endothermic event (88.50 oC; ΔH= -643.20 J.g-1), and a thermal decomposition behavior in a four-steps process. The pattern diffraction presented sharp peaks at 2θ: 15.2, 25.1 and 26.0o. The Arrhenius plot obtained by isothermal thermogravimetric analysis showed a linear relation with temperature in two steps. The first step the activation energy values was Ea = 45.73 J.mol-1.K-1. The thermal degradation recovery was 3.29% after 5 days, and 11.31% against 97.4% under the dark control to photostability. Conclusion: The study contributed to characterizing the CP and the results suggest that degradation depends on the surface transition state and the ternary formed system (CP-urea-water) and that the temperature influenced this system. The data were obtained through quick and easy techniques, which use wispy raw material and presented a significant result that can be used by the entire industry in the development of new formulations.

Preliminary Study on the Chemical and Biological Properties of Propolis Extract from Stingless Bees from the Northern Region of Brazil

Natural products are historically regarded as the main sources of bioactive compounds to fight the most diverse diseases; among them, propolis deserves to be highlighted due to several biological activities, such as antioxidant, anti-inflammatory, healing, antibacterial and antileishmanial activity. In this study, the antioxidant and antipromastigote activities and the cytotoxicity of propolis of the Scaptotrigona aff. postica stingless bee were evaluated. Propolis extract was analyzed by infrared spectroscopy, thermogravimetry and spectrophotometry for total polyphenols and flavonoid contents. Antioxidant activity was assessed spectrophotometrically by the DPPH, ABTS and FRAP methods, while antipromastigote activity and cytotoxicity were assessed by the MTT assay. The infrared spectra showed the characteristic bands of both phenols and alcohols. The thermogravimetry study revealed two events and thermal stability around 370 °C, while differential scanning calorimetry showed two endothermic events and an exothermic event. Total polyphenol and flavonoid contents were 21.29 ± 0.003 mg/g and 8.17 ± 0.00 mg/g, respectively, and the antioxidant activities identified by the DPPH, ABTS and FRAP methods were 910.09 ± 0.0264 µM Trolox (IC50 18.9 ± 0.01 µg/mL), 859.97 ± 0.0854 µM Trolox (IC50 692 ± 0.01 µg/mL) and 1613.67 ± 0.2610 µM Trolox (IC50 80 ± 0.1 µg/mL), respectively. The satisfactory antioxidant activity of propolis can be related to the high content of phenolic compounds, which adds value to this product and can contribute to the development of meliponiculture in the Brazilian state of Pará. The propolis extract caused a toxic effect on promastigote forms of Leishmania amazonensis at all concentrations tested, with an IC50 value of 1.50 µg/mL and a statistically significant difference compared to the negative control (p < 0.001). These results show that the propolis extract from S. postica bees may be a promising alternative for treatment against promastigote forms of L. amazonensis.

Determining early marine survival and predation by endothermic predators on acoustically tagged Atlantic salmon (Salmo salar) post-smolts

Many Atlantic salmon ( Salmo salar) populations have experienced significant declines for decades throughout North America and Europe. Mortality due to marine mammal predation during their early marine life could be an important factor contributing to these declines and limiting their population recoveries. However, quantifying predation events, and particularly the extent of marine mammal predation on Atlantic salmon, remains a challenge. In this study, we estimated the contribution of mesothermic and endothermic species predation to the mortality of Atlantic salmon post-smolts during their early marine life using acoustic telemetry. Predation events were inferred from changes in temperatures and depths experienced by acoustically tagged hatchery-reared Atlantic salmon smolts. No salmon were consumed by mesothermic predators, with most endothermic predation events being classified as marine mammals. Post-smolt mortality during the study period was low overall in both years (13.1%–16.7%), with endothermic predation accounting for 33.1%–42.9% of all marine mortality events (5.2%–5.6% mortality). Our results suggest that the current low return of adult Atlantic salmon observed in this area in recent years was not heavily influenced by endothermic predation on post-smolts in the first weeks at sea.

Synthesis, crystal structure and thermal properties of poly[[μ-1,2-bis-(pyridin-4-yl)ethene-κ2N:N'-μ-bromido-copper(I)] 1,2-bis-(pyridin-4-yl)ethene 0.25-solvate

The reaction of copper(I) bromide with 1,2-bis-(pyridin-4-yl)ethene in aceto-nitrile leads to the formation of the title compound, {[CuBr(C12H10N2)]·0.25C12H10N2}n or CuBr(4-bpe)·0.25(4-bpe) [4-bpe = 1,2-bis-(pyridin-4-yl)ethene]. The asymmetric unit consists of one copper(I) cation and one bromide anion in general positions as well as two crystallographically independent half 4-bpe ligands and a quarter of a disordered 4-bpe solvate mol-ecule that are completed by centers of inversion. The copper(I) cations are tetra-hededrally coordinated as CuBr2N2 and linked by pairs of μ-1,1-bridging bromide anions into centrosymmetric dinuclear units that are further connected into layers by the 4-bpe coligands. Between the layers, inter-layer C-H⋯Br hydrogen bonding is observed. The layers are arranged in such a way that cavities are formed in which the disordered 4-bpe solvate mol-ecules are located. Powder X-ray (PXRD) investigations reveal that a pure sample has been obtained. Thermogravimetric (TG) and differential thermoanalysis (DTA) measurements show two mass losses that are accompanied by endothermic events in the DTA curve. The first mass loss correspond to the removal of 0.75 4-bpe mol-ecules, leading to the formation of (CuBr)2(4-bpe), already reported in the literature as proven by PXRD.

Cytotoxicity and bioavailability assessment from thiamin-phospholipid complexation loaded Ajwain oil based self nanoemulsifying system

Poor bioavailability (<5%) of thiamin hydrochloride (TH) primarily relates to its impaired permeability across gut mucosa. To modulate its permeability, a dual system based approach consisting of phospholipid complexation embedded into a self nanoemulsifying system was investigated. Thiamin-Phospholipid Complex (TPC) was developed and its Ajwain oil (AJO)-based self nanoemulsifying formulations (SNFs) were evaluated. Formation of TPC complexation was resulted from molecular interactions held between free bases of thiamin and phospholipid (PL). FTIR characterization reveals that the amino group (-NH2) in the free base of thiamin was physically interacted to phosphate linkage in PL. Single endothermic event in TPC & TH, reveals complexation between PL & free bases as interpreted from DSC data. Their corresponding melting point was 127 °C and 258 °C, respectively. Heat of fusion (ΔHf) in TPC was higher than TH or PL. TPC exhibits a poor conductive environment over TH when diluted with ethanol/Tween20 (T2) medium. Lipophilic character of TPC was confirmed from partition coefficient (log P). Exact combination where ternary components produced fully dilutable nanoemulsion system, was identified using ternary diagram drawn between AJO (incorporated with TPC) as oil phase, and Tween20/Polyethylene glycol 600 (PEG600) as Surfactant/co-surfactant (Smix) at ratios 1:1; 1:2 & 2:1. Seven TPC-loaded self nanoemulsifying formulations (SNFs) were designed which, upon subjected to aqueous phase dilution yielded nanoemulsion with droplet size range 95–190 nm with zeta potential −1.78 ± 0.10 mV. Conductivity and Refractive index (RI) data of SNFs were in the range of 98 ± 7.0 to 231 ± 27 μS/cm and 1.458 to 1.463 units, respectively. In vitro TH release from SNF was determined in hydrochloric (HCl) buffer at pH 1.2, and in phosphate buffer solution (PB) at pH 6.8, data interpretation reveals that TPC delayed the release pattern compared to TH and could be attributed to lipophilic behavior of TPC. Intestinal permeability of drug was assessed from optimized SNF (F1) vs. TH across intestinal gut sac model (Apical to basolateral A→B) resulted in a significant difference in permeability coefficient (1.09 × 10−5cm/h). Antioxidant potential of SNF was demonstrated in the DPPH method. MTT assay of TPC formulation conducted on MCF-7 and MDA-MB-231 (Breast cancer) cell lines showed the developed system from AJO possessed cytotoxicity effect. Pharmacokinetic assessment showed that optimized SNFs produced more than four-fold enhancement in bioavailability over control (TH solution) in the Wistar rat model. Meanwhile Area under curve (AUC) data obtained from TPC (in coarse emulsion) vs.TH produced a significant difference (p < 0.001). It can be concluded that developed SNFs via phospholipid complexation produced lipophilic transformation of TH and its SNFs modulated permeability as well as bioavailability enhancement of thiamin.

Biotechnological investigation of Pediastrum boryanum and Desmodesmus subspicatus microalgae species for a potential application in bioenergy

The production of photosynthetic microalgae is a promising ecological advantage for obtaining carbon credits. This paper addresses cultivation and preparation, growth analysis, physicochemical characterization (X-ray diffraction-XRD, Fourier transform infrared-FTIR, scanning electron microscopy-SEM, and energy dispersive spectroscopy-EDS), and thermal behavior (thermogravimetry-TG, derivative thermogravimetry-DTG, and differential scanning calorimetry-DSC) of two microalgae, namely Pediastrum boryanum-PB (CH007) and Desmodesmus subspicatus-DS (AEE431E) for a potential application as an energy resource. Regarding the former, the literature reports no specific study on the species, which shows high lipid productivity and fast growth. A synthetic culture medium (Walter culture-WC) was subjected to variations in pH, luminosity, and maximum growth reached in 12 and 13 days for PB and DS, respectively. TG/DTG curves identified the main thermal degradation stages, i.e., dehydration (DS (24.68–158.68 °C) and PB (20.06–116.18 °C)), devolatilization (DS (166.34–543.00 °C) and PB (128.22–493.93 °C)), and gasification or carbonization (DS (>550 °C) and PB (>500 °C)), and DSC curves revealed two endothermic events, an exothermic one for DS, and only one endothermic event and an exothermic one for PB. XRD patterns showed a cellulose crystallinity index (CI) for DS (22.54 %) and PB (28.82 %), confirming the predominance of amorphous regions. SEM images detected external epidermis for DS and some interconnected pores for PB. The FTIR spectra identified functional groups (lipids, proteins, and carbohydrates) and CO, CO, OH, CH, and C-O-C linkages, and EDS and ICP-OES identified the main organic, inorganic, and metallic elements. The microalgae species displayed characteristics similar to those of the other biomasses in the bioenergy industry, enabling their use in thermoconversion processes for biofuel production and considering some socioenvironmental aspects.

Calorimetric analysis of AdcR and its interactions with zinc(II) and DNA

Zinc(II) ions play critical roles in all known life as structurally important stabilizing ions in proteins, catalytically active metals in enzymes, and signaling agents impacting physiological changes. To maintain homeostasis, the intracellular concentration of zinc(II) is strictly controlled by a family of metal-regulatory proteins in both prokaryotic and eukaryotic organisms. In S. pneumoniae, there are two proteins that share responsibility for Zn2+ homeostasis, one of them is the Adhesin Competence Repressor (AdcR) and it binds to a specific double-stranded DNA binding domain (dsDNA). AdcR has been structurally characterized containing two zinc(II) metal centers per monomeric unit. Here we report data collected from differential scanning calorimetry (DSC) experiments aimed to measure the structural stability of AdcR, the fully complimented Zn2AdcR complex, and the protein/DNA complex Zn2AdcR/dsDNA. Thermograms collected from DSC experiments yielded endothermic unfolding events for AdcR, Zn2AdcR, and Zn2AdcR/dsDNA complex at 55.6, 70.2, and 56.6 °C, respectively. A non-two state unfolding model best fits the data, giving ΔH terms associated with these thermal unfolding events of 5.1, 7.1, and 4.9 kcal/mol. These data allow for the development of a thermodynamic cycle connecting both zinc(II) and DNA binding to AdcR. Furthermore, pairing this newly reported data with known association constants for zinc(II) and DNA binding allowed for the generation of thermodynamic profiles for both zinc(II) binding to AdcR and Zn2AdcR binding to DNA, which show both are decisively entropy-driven processes.

Diversity of Solid Forms Promoted by Ball Milling: Characterization and Intrinsic Dissolution Studies of Pioglitazone Hydrochloride and Fluvastatin Sodium Drug-Drug Systems.

Coamorphous salt in a 1:1 ratio prepared by ball milling from Fluvastatin sodium (FLV) and Pioglitazone hydrochloride (PGZ·HCl) can be selectively formed by neat grinding (NG). Furthermore, the salt-cocrystal continuum was preferably formed by employing liquid-assisted grinding (LAG) using ethanol (EtOH). Attempts to prepare the coamorphous salt starting from the salt-cocrystal continuum by NG were unsuccessful. Interestingly, through ball milling by NG or LAG, a great diversity of solid forms (PGZ·HCl-FLV 1:1) could be accessed: NG and hexane (coamorphous); ethyl acetate (physical mixture); EtOH (salt-cocrystal continuum); and water (which presents two Tg, indicating immiscibility of the components). An exploration was performed at different drug-to-drug ratios by NG. By differential scanning calorimetry (DSC), the presence of two endothermic events was observed in this screening: incongruous melting point (solidus) and excess of one of the components (liquidus), except in the 1:1 solid form. From these results, eutectic behavior was observed. Through the construction of a binary phase diagram, it was determined that the 1:1 molar ratio gives rise to the formation of the most stable coamorphous composition. Dissolution profile studies of these solid forms were carried out, specifically on pure FLV and the solid forms of PGZ⋅HCl-FLV (1:2; 1:4; and 1:6), together with the coamorphous 1:1 salt. By itself, pure FLV presented the highest Kint (13.6270 ± 0.8127 mg/cm2⋅min). On the other hand, the coamorphous 1:1 showed a very low Kint (0.0220 ± 0.0014 mg/cm2·min), indicating very fast recrystallization by the FLV, which avoids observing a sudden release of this drug in the solution. This same behavior was observed in the eutectic composition 1:2. In the other solid forms, the value of Kint increases along with the %w of FLV. From the mechanochemical point of view, ball milling by NG or LAG became an important synthetic tool since it allows obtaining a great variety of solid forms to explore the solid-state reactivity of the drug-drug solid-form PGZ HCl-FLV.

Polypropylene Nanocomposites Attained by In Situ Polymerization Using SBA-15 Particles as Support for Metallocene Catalysts: Effect of Molecular Weight and Tacticity on Crystalline Details, Phase Transitions and Rheological Behavior.

In this study, nanocomposites based on polypropylene are synthesized by the in situ polymerization of propene in the presence of mesoporous SBA-15 silica, which acts as a carrier of the catalytic system (zirconocene as catalyst and methylaluminoxane as cocatalyst). The protocol for the immobilization and attainment of hybrid SBA-15 particles involves a pre-stage of contact between the catalyst with cocatalyst before their final functionalization. Two zirconocene catalysts are tested in order to attain materials with different microstructural characteristics, molar masses and regioregularities of chains. Some polypropylene chains are able to be accommodated within the silica mesostructure of these composites. Thus, an endothermic event of small intensity appears during heating calorimetric experiments at approximately 105 °C. The existence of these polypropylene crystals, confined within the nanometric channels of silica, is corroborated by SAXS measurements obtained via the change in the intensity and position of the first-order diffraction of SBA-15. The incorporation of silica also has a very significant effect on the rheological response of the resultant materials, leading to important variations in various magnitudes, such as the shear storage modulus, viscosity and δ angle, when a comparison is established with the corresponding neat iPP matrices. Rheological percolation is reached, thus demonstrating the role of SBA-15 particles as filler, in addition to the supporting role that they exert during the polymerizations.

Studies on the nature and pressure evolution of phase transitions in 1-adamantylamine and 1-adamantanol

In this paper, several experimental techniques, i.e., differential scanning calorimetry, X-ray diffraction, Fourier transform infrared, Raman, and broadband dielectric spectroscopy were applied to study the nature of the phase transitions in 1-adamantylamine (1-NH2-ADM, C10H17N) and 1-adamantanol (1-OH-ADM, C10H16O). Calorimetric measurements showed one and three endothermic peaks in thermograms for the latter and the former substance, respectively. Indeed, results of spectroscopic investigations indicated that the observed thermal events in 1-NH2-ADM correspond to transitions between various plastic crystal (PC) phases (I, II, III, IV), while the endothermic process in 1-OH-ADM can be assigned to a phase transition between the PC and the ordinary crystal (OC). Especially interesting were the outcomes of dielectric studies carried out both at ambient and high-pressure conditions, during heating and cooling cycles. They showed: i) noticeable changes in the frequency dependencies of the imaginary (ε'') and real (ε') parts of the complex dielectric permittivity that occurred around temperatures of the characteristic endothermic events detected by the calorimetry, and ii) significant fluctuations of ε'' and ε' at pressures attributed to the respective phase transitions. Moreover, the pressure coefficients of the phase transition temperatures were estimated to be approximately equal to 0.2 K/MPa for both compounds. In turn, volume variation (ΔV) at the PC (II)-PC (III) and PC (III)-PC (IV) transition temperatures for 1-NH2-ADM was essentially different than ΔV for the PC-OC transition in 1-OH-ADM.

Study of the Crystal Architecture, Optoelectronic Characteristics, and Nonlinear Optical Properties of 4-Amino Antipyrine Schiff Bases.

Two Schiff bases, (E)-4-((2-chlorobenzylidene)amino)-1,5-dimethyl-2-phenyl-1,2-dihydro-3H-pyrazol-3-one (4AAPOCB) and (E)-4-((4-chlorobenzylidene)amino)-1,5-dimethyl-2-phenyl-1,2-dihydro-3H-pyrazol-3-one (4AAPPCB), have been synthesized and grown as single crystals. Single-crystal X-ray diffraction analysis was employed to determine the crystal structure of the compounds, and the results suggest that the compounds crystallized into an orthorhombic crystal system having P212121 and Pbca space groups, respectively. Further, the crystallinity of the compounds was analyzed by the PXRD technique. The UV-vis-NIR spectra of the compounds demonstrate excellent transmittance in the entire visible region. The lower cutoff wavelengths of the compounds were determined to be 338 and 333 nm, respectively; additionally, optical band gaps of the compounds found were 4.60 and 4.35 eV. FTIR and NMR (1H and 13C) spectral techniques were utilized to analyze the molecular structure of the compounds. The compounds emit photoluminescence with broad emission bands with centers at 401 and 418 nm. The thermal stability and phase transitions were assessed through thermogravimetric methods. The phase transition prior to melting was indicated by the endothermic event at around 190 °C in the DTA curves of both crystals, and the same was observed in the DSC curves. The second harmonic efficiencies of the powdered compounds I and II were found to be 3.52 and 1.13 times better than that of the standard reference KDP. The 4AAPOCB and 4AAPPCB compounds showed isotropic polarizability amplitudes of 46.02 × 10-24 and 46.52 × 10-24 esu, respectively. The calculation of linear polarizability and NLO second-order polarizability (β) along with other optical parameters was performed for optimized geometries. The nonzero amplitudes of the average β values for compounds 4AAPOCB and 4AAPPCB were found to be 14.74 × 10-30 and 8.10 × 10-30 esu, respectively, which show a decent potential of the synthesized molecules for NLO applications. The calculated β amplitudes were further explained based on calculated electronic parameters like molecular electrostatic potentials, frontier molecular orbitals, molecular orbital energies, transition energies, oscillator strengths, and unit spherical representation of NLO polarizability. The current analysis emphasizes the significance of synthesized compounds as prospective candidates for optical and NLO applications through the use of experiments and quantum computations.

Enhancing the Mechanical Properties of Corn Starch Films for Sustainable Food Packaging by Optimizing Enzymatic Hydrolysis.

The objective of this study was to investigate the effects of enzymatic hydrolysis using α-amylase from Bacillus amyloliquefaciens on the mechanical properties of starch-based films. The process parameters of enzymatic hydrolysis and the degree of hydrolysis (DH) were optimized using a Box-Behnken design (BBD) and response surface methodology (RSM). The mechanical properties of the resulting hydrolyzed corn starch films (tensile strain at break, tensile stress at break, and Young's modulus) were evaluated. The results showed that the optimum DH for hydrolyzed corn starch films to achieve improved mechanical properties of the film-forming solutions was achieved at a corn starch to water ratio of 1:2.8, an enzyme to substrate ratio of 357 U/g, and an incubation temperature of 48 °C. Under the optimized conditions, the hydrolyzed corn starch film had a higher water absorption index of 2.32 ± 0.112% compared to the native corn starch film (control) of 0.81 ± 0.352%. The hydrolyzed corn starch films were more transparent than the control sample, with a light transmission of 78.5 ± 0.121% per mm. Fourier-transformed infrared spectroscopy (FTIR) analysis showed that the enzymatically hydrolyzed corn starch films had a more compact and solid structure in terms of molecular bonds, and the contact angle was also higher, at 79.21 ± 0.171° for this sample. The control sample had a higher melting point than the hydrolyzed corn starch film, as indicated by the significant difference in the temperature of the first endothermic event between the two films. The atomic force microscopy (AFM) characterization of the hydrolyzed corn starch film showed intermediate surface roughness. A comparison of the data from the two samples showed that the hydrolyzed corn starch film had better mechanical properties than the control sample, with a greater change in the storage modulus over a wider temperature range and higher values for the loss modulus and tan delta, indicating that the hydrolyzed corn starch film had better energy dissipation properties, as shown by thermal analysis. The improved mechanical properties of the resulting film of hydrolyzed corn starch were attributed to the enzymatic hydrolysis process, which breaks the starch molecules into smaller units, resulting in increased chain flexibility, improved film-forming ability, and stronger intermolecular bonds.

Polyisoprenes obtained from jackfruit latex (Artocarpus heterophyllus L.): Extraction and characterization

AbstractJackfruit latex is a residue from the agricultural production of this fruit, which does not have an application in the food or pharmaceutical industry. The objectives of the study were to (1) extract the polyisoprenes from jackfruit latex using the surfactant sodium lauryl sulfate, and (2) characterize their physicochemical and techno‐functional properties. The chemical composition, foaming and emulsifying capacity, and thermal behavior. According to the proximal chemical analysis of the extracts, the major content were lipophilic compounds (89%), including polyisoprenes. Regarding the emulsifying properties, the concentrates extracts showed intermediate values for the emulsifying activity index (32–59 m2/g) and stability times from 15 to 95 min. The thermal analysis showed endothermic events (50–65°C) associated with the melting of the concentrate, as well as exothermic events related to the crystallization of the polyisoprenes. The FTIR spectra indicates the presence of the polyisoprenes in the extracts, the stretching of the C═C bonds in 1704 at 1712 cm−1 are characteristic of cis‐1,4 polyisoprene bonds, and at 980 cm−1 the CH bending. The physicochemical and techno‐functional properties of polyisoprene extracts indicate that they could be used in emulsions or electrohydrodynamic encapsulation processes.

Kinetically facilitated liquid-liquid transition in a metallic liquid

The subtle existence of a liquid-liquid transition in ‘homogeneous’ equilibrium metallic liquids is difficult to detect. An exothermic peak with the onset temperature above the equilibrium liquidus temperature is detected by in-situ ultrafast calorimetry in Yb-Zn liquid. The thermal event emerges on cooling, only. The exothermic event maintains a constant reversible part of the specific heat during modulated cooling, and it does not appear to be reversed on heating as no corresponding endothermic event is detected. The transition temperature lies about 6% above the equilibrium liquidus temperature and the detected enthalpy change of the transition is about 10−12% of the enthalpy of fusion for the highest cooling rates ∼104 K s−1 applied. The critical quenching temperature, below which the exotherm disappears on cooling, coincides with a liquid-liquid transition studied in the literature by other techniques. A phase diagram inclusive of the transition in the liquid is constructed by using calorimetry signals.

Particle filled protein-starch composites as the basis for plant-based meat analogues

Rapid swelling, high amylopectin starches including Thermally Inhibited (TI), Chemically Modified (CM), and Granular Cold- Swelling (GCS) were assessed for their supporting matrix forming potential and properties. Starches displayed identical calorimetric profiles with no endothermic events, and completely amorphous structure as judged by powder X-ray diffraction. However, they each provided different textural attributes. The starches were combined with pea protein isolate at a total concentration of 47%w/w (d.b.) to create a proteinacious supporting matrix. The starch protein matrix was then tested in a non-cold-set dough state as well as in a cold-set state after storage for 24h at 5oC. In the non-cold-set state, hardness increased with the addition of protein. CM was the softest dough and was difficult to work with, while TI and GCS were harder, with TI having the greatest resilience. Once cold-set, the textural properties changed, and GCS was not able to form a solid structure, instead remaining a viscoelastic dough. The hardness and storage modulus (G’) of TI and CM displayed a negative correlation with the addition of protein due to matrix disruption. However, the combination of TI starch and pea protein at a ratio of 70% starch and 30% protein in the dry fraction displayed a synergistic effect, with increased resilience, chewiness, and ductility. FTIR of TI starch and protein at the same 70:30 ratio provided further evidence for the existence of an interaction between pea protein and TI starch. The results support the use of TI rapid swelling starch and pea protein isolate as a supporting matrix for application in meat analogue systems.

Confinement in Extruded Nanocomposites Based on PCL and Mesoporous Silicas: Effect of Pore Sizes and Their Influence in Ultimate Mechanical Response

In this study, nanocomposites based on polycaprolactone (PCL) and two types of mesoporous silicas, MCM-41 and SBA-15, were attained by melt extrusion. The effect of the silica incorporated within the PCL matrix was observed, firstly, in the morphological characteristics and degradation behavior of the resultant composites. DSC experiments provided information on the existence of confinement in the PCL–SBA-15 materials through the appearance of an additional small endotherm, located at about 25–50 °C, and attributed to the melting of constrained crystallites. Displacement to a slightly lower temperature of this endothermic event was observed in the first heating run of PCL–MCM-41 composites, attributed to the inferior pore size in the MCM-41 particles. Thus, this indicates variations in the inclusion of PCL chains within these two mesostructures with different pore sizes. Real-time variable-temperature small-angle X-ray scattering (SAXS) experiments with synchrotron radiation were crucial to confirm the presence of PCL within MCM-41 and SBA-15 pores. Accurate information was also deduced from these measurements regarding the influence of these two mesoporous MCM-41 and SBA-15 silicas on PCL long spacing. The differences found in these morphological and structural features were responsible for the ultimate mechanical response exhibited by the two sets of PCL nanocomposites, with a considerably higher increase of mechanical parameters in the SBA-15 family.