Screening the Optimal Probe by Expounding the ESIPT Mechanism and Photophysical Properties in Bis-HBX with Multimodal Substitutions.

DFT and TD-DFT were used in this article to investigate the effects of different substitutions at multiple sites on the photophysical mechanism of bis-HBX in the gas phase. Four different substitution modes were selected, denoted as A1 (X=Me, Y=S), A2 (X=OMe, Y=S), B1 (X=Me, Y=NH), and C1 (X=Me, Y=O). The geometric parameters proved that the IHBs enhanced after photoexcitation, which was conducive to promote the ESIPT process. Combining the analysis of the PECs, it was revealed that the bis-HBX molecule underwent the ESIPT process, and the ease of the ESIPT process was in the order of A1 > A2> B1 > C1. In particular, the TICT process in A1 and B1 promoted the occurrence of the ESIPT process. In addition, the IC process was identified, particularly in C1. Meanwhile, the calculation of fluorescence lifetime and fluorescence rate further confirmed that A1 was the most effective fluorescent probe molecule. This theoretical research provides an innovative theoretical reference for regulating ESIPT reactions and optimizing fluorescent probe molecules.

Concerning for the solvent-polarity-dependent conformational equilibrium and ESIPT mechanism in Pz3HC system: A novel insight.

In this report, we propose a new insight into the interaction between the solvent-polarity-dependent conformational equilibrium and excited state intramolecular proton transfer (ESIPT) behavior of Pz3HC system in four different polar solvents (polarity order: ACN > THF > TOL > CYC). Using quantum chemistry method, we first announce a coexistence mechanism between Pz3HC-1 and Pz3HC-3 in the ground state in four solvents based on the Boltzmann distribution. In particular, Pz3HC-1 is the principal configuration in non-polar solvent, but Pz3HC-3 is the principal configuration in polar solvent. In addition, the simulated fluorescence spectra interprets the negative solvatochromism effect of Pz3HC-1 and Pz3HC-3 in four solvents. The evidence from intramolecular hydrogen bonding (IHB) parameters and electronic perspective collectively confirms the light-induced IHB enhancement and intramolecular charge transfer (ICT) properties in Pz3HC-1 and Pz3HC-3, which raises the likelihood of the ESIPT process. Combining the calculation of potential energy curve (PEC) and intrinsic reaction coordinate (IRC), we demonstrate that the ESIPT ease of Pz3HC-1 in different polar solvents obeys the order of CYC > TOL > THF > ACN, while the order of ESIPT ease in Pz3HC-3 is opposite. Notably, the ESIPT process of Pz3HC-3 in CYC solvent is accompanied by the twisted intramolecular charge transfer (TICT) process. In addition, we also reveal that the enol* and keto* fluorescence peaks of Pz3HC-3 in CYC solvent are quenched by ISC and TICT process, respectively. Our work not only provides a satisfactory explanation of the novel dynamics mechanism for Pz3HC system, but also brings light to the design and application of new sensing molecules in the future.

Modulating the ESIPT Mechanism and Luminescence Characteristics of Two Reversible Fluorescent Probes by Solvent Polarity: A Novel Perspective.

As reversible fluorescent probes, HTP-1 and HTP-2 have favourable applications for the detection of Zn2+ and H2S. Herein, the impact of solvent on the excited-state intramolecular proton transfer (ESIPT) of HTP-1 and HTP-2 was comprehensively investigated. The obtained geometric parameters and infrared (IR) vibrational analysis associated with the intramolecular hydrogen bond (IHB) indicated that the strength of IHB for HTP-1 was weakened in the excited state. Moreover, structural torsion and almost no ICT behaviour indicated that the ESIPT process did not occur in HTP-1. Nevertheless, when the 7-nitro-1,2,3-benzoxadiazole (NBD) group replaced the H atom, the IHB strength of HTP-2 was enhanced after photoexcitation, which inhibited the twisting of tetraphenylethylene, thereby opening the ESIPT channel. Notably, hole-electron analysis and frontier molecular orbitals revealed that the charge decoupling effect was the reason for the fluorescence quenching of HTP-2. Furthermore, the potential energy curves (PECs) revealed that HTP-2 was more inclined to the ESIPT process in polar solvents than in nonpolar solvents. With a decrease in solvent polarity, it was more conducive to the ESIPT process. Our study systematically presents the ESIPT process and different detection mechanisms of the two reversible probe molecules regulated by solvent polarity, providing new insights into the design and development of novel fluorescent probes.

Euphohelioscopin A enhances NK cell antitumor immunity through GSDME-triggered pyroptosis.

Immune evasion by cancer cells poses a significant challenge for natural killer (NK) cell-based immunotherapy. Pyroptosis, a newly discovered form of programmed cell death, has shown great potential for enhancing the antitumor immunity of NK cells. Consequently, targeting pyroptosis has become an attractive strategy for boosting NK cell activity against cancer. In this study, various assays were conducted, including NK cell cytotoxicity assays, flow cytometry, xenograft tumor models, real-time PCR, and ELISA to assess NK cell-mediated cell killing, as well as gene and protein expressions. The results indicated that Euphohelioscopin A (Eupho-A), a potential pyroptosis activator, enhances NK cell-mediated lysis of tumor cells, resulting in inhibiting tumor growth that could be reversed by NK cell depletion. Furthermore, we found that Eupho-A significantly enhanced IFN-γ production in NK cells and synergistically up-regulated GSDME with IFN-γ in cancer cells. Eupho-A also increased the cleavage of GSDME, promoting GZMB-induced pyroptosis, which could be reversed by GSDME knockdown and IFN-γ blockade. Overall, the findings suggested that Eupho-A enhanced NK cell-mediated killing of cancer cells by triggering pyroptosis, making Eupho-A a promising pyroptosis activator with great potential for using in NK cell-based cancer immunotherapy.

Macrolide sesquiterpene pyridine alkaloids from Celastrus monospermus and evaluation of their immunosuppressive and anti-osteoclastogenesis activities.

Phytochemical investigation of the stems of Celastrus monospermus Roxb enabled isolation and identification of fifteen new macrolide sesquiterpene pyridine alkaloids (1-15) along with five known analogues. Their structures were elucidated by comprehensive spectroscopic analysis (NMR, HRESIMS, IR, UV), chemical hydrolysis, and single crystal X-ray diffraction analysis. Bioassay of the abundant isolates revealed that seven compounds inhibited the proliferation of B lymphocytes with IC50 values ranging between 1.4 and 19.9 µM. Among them, celasmondine C (3) could significantly promote the apoptosis of activated B lymphocyte, especially late-stage apoptosis. Besides, compounds 3, 16, and 20 exhibited potent suppression of osteoclast formation at a concentration of 1.0 µM. This investigation enriched the chemical diversity of macrolide sesquiterpene pyridine alkaloids, and supported evidence for the development of new immunosuppressive and anti-osteoclastogenesis agents.

Photophysical Properties of (E)-1-(4-(Diethyla-mino)-2-hydroxybenzylidene)-4,4-dimethylthiosemicarbazide Compound and Its Triple Fluorescence Emission Mechanism: A Theoretical Perspective.

In view of the application prospects in biomedicine of (E)-1-(4-(diethyla-mino)-2-hydroxybenzylidene)-4,4-dimethylthiosemicarbazide (DAHTS), the behavior of excited-state dynamics and photophysical properties were studied using the density functional theory/time-dependent density functional theory method. A series of studies indicated that the intramolecular hydrogen-bond (IHB) intensity of DAHTS was enhanced after photoexcitation. This was conducive to promoting the excited-state intramolecular proton-transfer (ESIPT) process. Combining the analysis of the IHB and hole-electron, it revealed that the molecule underwent both the ESIPT process and the twisted charge-transfer (TICT) process. Relying on exploration of the potential energy surface, it was proposed that the different competitive mechanisms between the ESIPT and TICT processes were regulated by solvent polarity. In acetonitrile (ACN) solvent, the ESIPT process occurred first, and the TICT process occurred later. In contrast, in the CYH solvent, the molecule first underwent the TICT process and then the ESIPT process. Furthermore, we raised the possibility that the TICT behavior was the cause of weak fluorescence emission for the DAHTS in CYH and ACN solvents. By the dimer correlation analysis, the corresponding components of triple fluorescence emission were clearly assigned, corresponding to the monomer, dimer, and ESIPT isomer in turn. Our work precisely elucidated the photophysical mechanism of DAHTS and the attribution of the triple fluorescence emission components, which provided valuable guidance for the development and regulation of bioactive fluorescence probes with multiband and multicolor emission characteristics.

Composite formation of whey protein isolate and OSA starch for fabricating high internal phase emulsion: A comparative study at different pH and their application in biscuits.

The composites formed by whey protein isolate (WPI) and octenyl succinate anhydride (OSA)-modified starch were characterized with a focus on the effect of pH, and their potential in fabricating high internal phase emulsions (HIPEs) as fat substitutes was evaluated. The particles obtained at pH 3.0, 6.0, 7.0, and 8.0 presented a nanosized distribution (122.04 ± 0.84 nm-163.24 ± 4.12 nm) while those prepared at pH 4.0 and 5.0 were remarkably larger. Results from the shielding agent reaction and Fourier transform infrared spectroscopy (FT-IR) showed that the interaction between WPI and OSA starch was mainly hydrophobic at pH 3.0-5.0, while there was a strong electrostatic repulsion at pH 6.0-8.0. A quartz crystal microbalance with dissipation (QCM-D) study showed that remarkably higher ΔD and lower Δf/n were observed at pH 3.0-5.0 after successive deposition of WPI and OSA starch, whereas slight changes were noted for those made at higher pH values. The WPI-OSA starch (W-O) composite-based HIPEs made at pH 3.0 and 6.0-8.0 were physically stable after long-term storage, thermal treatment, or centrifugation. Incorporation of HIPE into the biscuit formula yielded products with a desirable sensory quality.

Effects of wheat protein on hot-extrusion 3D-printing performance and the release behaviours of caffeic acid-loaded wheat starch.

In this study, the effects of wheat protein (WP) on the hot-extrusion 3D-printing (HE-3DP) performance of wheat starch (WS) gels, as well as effects of such gels on the encapsulation of caffeic acid, were investigated for the first time. The HE-3DP results show that the addition of WP can reduce print-line width and improve printing accuracy and fidelity, and the best printing results were achieved when using gels with 10 % WP. The rheological results show that WP reduced the gels' linear viscoelastic region (LVR), yield stress (τy), flow stress (τf) and consistency factor (K) but increased their structural recovery rate, which facilitated smooth extrusion during 3D printing and, thus, improved printing accuracy. The analysis of X-ray diffraction and small-angle X-ray scattering indicates that adding WP to WS could increase the mass fractal dimension and lead to denser gel network structures. The results regarding release kinetics demonstrate that the maximum release of caffeic acid from gels decreased by 28 % with the addition of WP, indicating slow-release behaviour. This study provided valuable information about processing wheat products via 3D printing.

Dihydro-ß-agarofuran-type sesquiterpenoids from the seeds of Tripterygium wilfordii (Thunder God Vine) and evaluation of their anti-osteoclastogenesis and immunosuppressive activities.

Extensive phytochemical investigation of the seeds of Tripterygium wilfordii led to the identification of 54 polyesterified dihydro-ß-agarofuran-type sesquiterpenoids, including 27 previously undescribed ones, named Tripwilin I-XXVII (1-27). Comprehensive spectroscopic and single-crystal X-ray diffraction analyses, along with electronic circular dichroism (ECD) calculations were used for the structural elucidation of the new compounds. Biological assay revealed that 37 compounds among the isolates exhibited significant inhibition against osteoclastogenesis induced by receptor activator of nuclear factor-κB ligand (RANKL) at 10 µM. Further investigation indicated that Triptogelin C-3 (54), with the most potent osteoclastogenesis inhibitory activity, regulated the osteoclast marker genes (MMP-9, c-Fos, CTSK, and TRAP) and proteins in a dose-dependent manner in vitro. Besides, celaforin D-1 (28), 1α,6ß,15-triacetoxy-8α,9α-dibenzoyloxy-2α-hydroxydihydro-ß-agarofuran (34), triptogelin A-2 (37), and chiapen D (49) showed moderate suppressive effects on the proliferation of T and B lymphocytes with IC50 values ranging between 8.1 ± 0.8 and 19.0 ± 0.9 µM.

Paying Comprehensive Attention to the Temperature-Dependent Dual-Channel Excited-State Intramolecular Proton Transfer Mechanism of Fluorescence Ratio Probe BZ-DAM.

The mechanism of fluorescence detection of diethyl chlorophosphate (DCP) based on 2-substituted benzothiazole (BZ-DAM) was studied by a theoretical calculation method. It should not be ignored that both the BZ-DAM and the detection product BZ-CHO have two excited-state intramolecular proton transfer (ESIPT) channels. Density functional theory (DFT) and time-dependent DFT (TDDFT) theory were used to study the photophysical mechanism of two compounds in two channels in (acetonitrile) ACN solvent, and the temperature dependence of the two channels was given. Channel 1 is more likely to exist at low temperatures and channel 2 is more likely to exist at high temperatures. By theoretical analysis of the constructed potential energy curve, the hydrogen bond energy and electron-hole analysis, we confirmed that both molecules undergo ESIPT and intramolecular charge transfer (ICT) processes in channel 1 and ESIPT and twisted intramolecular charge transfer (TICT) coupling processes in channel 2. The formation of product BZ-CHO molecules led to a significant fluorescence blue-shift phenomenon and inhibited the ICT process, which confirmed that BZ-DAM could be used as a fluorescence probe for fluorescence detection. We sincerely hope that this work will not only help to clarify the excited-state dynamics behavior of the BZ-DAM probe but also provide a new idea for designing and optimizing a new chemical dosimeter.

Research Progress of Quinoa Seeds (Chenopodium quinoa Wild.): Nutritional Components, Technological Treatment, and Application.

Quinoa (Chenopodium quinoa Wild.) is a pseudo-grain that belongs to the amaranth family and has gained attention due to its exceptional nutritional properties. Compared to other grains, quinoa has a higher protein content, a more balanced amino acid profile, unique starch features, higher levels of dietary fiber, and a variety of phytochemicals. In this review, the physicochemical and functional properties of the major nutritional components in quinoa are summarized and compared to those of other grains. Our review also highlights the technological approaches used to improve the quality of quinoa-based products. The challenges of formulating quinoa into food products are addressed, and strategies for overcoming these challenges through technological innovation are discussed. This review also provides examples of common applications of quinoa seeds. Overall, the review underscores the potential benefits of incorporating quinoa into the diet and the importance of developing innovative approaches to enhance the nutritional quality and functionality of quinoa-based products.

Preparation and characterization of debranched starches: Influence of botanical source and debranching time.

The influence of botanical source (waxy corn, glutinous rice, tapioca and potato), either based on crystallization or morphology, and the debranching time (6-48 h) on the physicochemical properties of debranched starches (DBSs) were systematically investigated. The divergence of depolymerization among different botanical sources within same hydrolysis time suggested that the debranching treatment was not only depending on the molecular profile and crystalline structure, but also related with the granular size and morphology of native starches. Fourier transformation infrared spectroscopy (FT-IR), X-ray diffraction (XRD), differential scanning calorimetry (DSC) suggested that long-term debranching reaction produced DBSs with improved degree of crystallization and reduced iodine binding capacity. Simulated in-vitro digestion assay showed that the proportion of digestive fractions from different botanical originated DBSs differed greatly. Additionally, prolonging the debranching time yielded increased level of resistant starch. The study may provide guidance for exploring DBSs with various molecular weight to fulfill their tailored applications.

Formation of Starch-Lipid Complexes during the Deep-Frying Process and Its Effects on Lipid Oxidation.

In the present study, maize starch (MS), potato starch (PS), high-amylose maize starch (HAMS), and wheat starch (WS) were deep-fried in soybean oil that was continuously heated for 40 h under 180 °C. The thermodynamic and pasting properties of deep-fried starch samples were determined. The results suggested that starch−lipid complexes formed with the extension of frying oils' usage; however, their number was not dependent on the frying oils' life cycle. Importantly, the results of pasting properties revealed the following strength of intermolecular force in deep-fried starch samples: PS > MS > HAMS > WS. The results of XRD and FTIR analysis confirmed the formation of starch−lipid complexes during the deep-frying process. Furthermore, the results of the in vitro digestibility of deep-fried starch revealed that the formation of starch−lipid complexes inhibited the swelling of starch granules and prevented the entrance of amylase into the interior. Additionally, the results of the oxidation stability of deep-frying oil indicated that the formation of starch−lipid complexes did not alter the trend of lipid oxidation as an effect of the limited number of starch−lipid complexes. These results could have critical implications for the development of healthier deep-fried foods.

Effects of temperature and ferric ion on the formation of glycerol core aldehydes during simulated frying.

Glycerol core aldehydes (GCAs) are toxins widely formed in oils at high temperature. This study investigated the effects of frying time, temperature, and Fe3+ content on the GCAs formation in high-oleic sunflower oil. The results showed that the GCAs (8-oxo, 9-oxo, 10-oxo-8, 11-oxo-9) concentrations increased with time following the pseudo-first-order kinetics. Frying at 160 °C without Fe3+ and at 180 °C with 0.0005 mol·L-1 Fe3+ yielded the lowest and highest total GCA content. The concentrations of GCAs (8-oxo) and GCAs (9-oxo) or GCAs (10-oxo-8) and GCAs (11-oxo-9) changed similarly with different frying temperature and Fe3+ concentration. The major GCAs was GCAs (9-oxo) (40-70%), which also had the highest formation rate (5.42 × 10-4 mg·g-1·h-1). However, GCA (10-oxo-8) and GCAs (11-oxo-9) with similar proportion (ca. 10-20%) and GCAs (8-oxo) made up the least proportions (<10%).

Dihydro-ß-agarofuran-type sesquiterpenoids from the seeds of Celastrus virens with lifespan-extending effect on the nematode Caenorhabditis elegans.

Twelve dihydro-ß-agarofuran-type sesquiterpenoids, including five new ones (1-5), were purified from the seeds of Celastrus virens (Wang et Tang) C. Y. Chent et T. C. Kao. Their chemical structures were characterized via comprehensive spectroscopic analysis, single-crystal X-ray diffraction analysis, and computational prediction of ECD, as well as comparison of observed and reported NMR spectral data. Among the isolates, nine abundant dihydro-ß-agarofuran-type sesquiterpenoids were evaluated for their lifespan-extending activity using the nematode Caenorhabditis elegans model. As a result, compounds 1, 2, 5, 6, 8, and 9 (50 µM) significantly extended the mean survival time of C. elegans, respectively, compared with the blank control group (p < 0.05). Further Quantitative RT-PCR showed that the prolonging of lifespan mediated by compounds 1, 6, 8, and 9 were dependent on the transcription factors skn-1 and hsf-1.

Formation of protein corona on interaction of pepsin with chitin nanowhiskers in simulated gastric fluid.

Protein corona (PC) usually changes the physicochemical properties of nanoparticles (NPs) and determines their ultimate fate in the physiological environment. As NPs are widely used in food, it is important to obtain a deep understanding of PC formation in the gastrointestinal fluid. Herein, we explored the adsorption of pepsin to chitin nanowhiskers (CNWs) and their interactions in simulated gastric fluid. Results suggest that the binding of pepsin reduced the surface potential of CNWs from 22.4 ± 0.15 to 12.9 ± 0.51 mV and caused their aggregation. CNWs quenched the fluorescence of pepsin and induced slightly changes in its secondary structure containing a reduction in the ß-sheet content (∼ 3%) and an increase in the random coils (∼ 2%). The isothermal titration calorimetry (ITC) data suggested that the interaction forces between CNWs and pepsin were mainly hydrogen bonds and van der Waals forces.

First Report on Inhibitory Effect against Osteoclastogenesis of Dihydro-ß-agarofuran-Type Sesquiterpenoids.

Dihydro-ß-agarofuran-type sesquiterpenoids are characteristic metabolites of Celastraceae plants, and the extracts of these plants have been developed into botanical pesticides. In the course of our efforts to find novel natural biologically active products, eight new dihydro-ß-agarofuran-type sesquiterpenoids (1-8) were identified from the stems of Celastrus monospermus Roxb. Their structures were elucidated by extensive spectroscopic analysis, single crystal X-ray crystallography, and electronic circular dichroism (ECD) calculations. In consideration of the efficacy of certain Celastrus plants for the treatment of arthritis and arthralgia in folk medicine, the isolates were evaluated for their inhibitory activities against osteoclastogenesis. As a result, compounds 4, 6, and 7 were found to restrain osteoclastogenesis induced by receptor activator of nuclear factor-κB ligand (RANKL) with IC50 values of 0.58, 1.2, and 6.1 µM, respectively. Furthermore, compound 4 was found to inhibit osteoclastogenesis-related gene (c-Fos, MMP-9, CTSK, TRAP) expression and block c-Fos protein expression and inhibited bone resorption of mature osteoclasts induced by M-CSF and RANKL in a dose dependent manner. This is the first report of dihydro-ß-agarofuran-type sesquiterpenoid for their potential medical applications in bone metabolic diseases.

Microencapsulation of algae oil by complex coacervation of chitosan and modified starch: Characterization and oxidative stability.

The formation of complex coacervation using chitosan and octenyl succinic anhydride modified starch (OSA starch) and microencapsulation of algae oil were investigated in this study. The zeta-potential, turbidity and coacervate yield were evaluated as a function of pH and the chitosan- OSA starch mass ratio. The highest coacervate yield was achieved at pH 6.0 with a chitosan to OSA starch ratio of 1:3 (w/w). Isothermal titration calorimetry (ITC) indicated favorable affinity (Ka = 1.51 × 105 M-1) between chitosan and OSA starch. The microcapsules yielded an encapsulation efficiency (EE) in the range of 42.8 ± 0.8%- 93.1 ± 1.2%, the loading capacity ranged between 30.4 ± 2.7% and 58.3 ± 1.3%. Fourier transform infrared spectroscopy (FT-IR) spectra and scanning electron microscopy (SEM) further confirmed the microencapsulation. In comparison with the bulk oil, the microencapsulated algae oil exhibited improved oxidative stability during storage.

Diterpenoids from Euphorbia helioscopia and their enhancement of NK cell-mediated killing of NSCLC cells.

Fourteen previously undescribed diterpenoids, including an unusual diterpenoid (1) with a 9,10-seco-jatrophane skeleton, ten jatrophane-type diterpenoids (2-11), two lathyrane-type diterpenoids (12, 13), and an abietane-type diterpenoid (14), together with thirty-six known ones (15-50), were isolated from the whole plants of Euphorbia helioscopia L. The structures of the new isolates were characterized by spectroscopic methods, single-crystal X-ray diffraction analysis, and computational prediction of ECD and chemical shifts. Thirty-nine abundant diterpenoids were evaluated for their enhancement of NK cell-mediated killing of NSCLC cells. As a result, compounds 24, 33, and 41 were found to significantly enhance the killing activity of NK cells towards H1299-luci cells and A549-luci cells at the concentration of 2.5 µM.

Pilot-Scale Airlift Bioreactor with Function-Enhanced Microbes for the Reduction of Refinery Excess Sludge.

A pilot-scale airlift bioreactor (ALBR) system was built and operated continuously for refinery excess sludge (RES) reduction. Combined ALBR and function-enhanced microbes (composed of photosynthetic bacteria and yeast) were integrated into the system. The pilot-scale ALBR was operated for 62 days, and the start-up time was 7 d. Continuous operation showed that the sludge reduction efficiency was more than 56.22%, and the water quality of the effluent was satisfactory. This study focused on investigating the effects of hydraulic retention time (HRT) on the stability of the system and the effect of sludge reduction. Under different HRT conditions of 40, 26.7, 20, and 16 h, the sludge reduction rates reached 56.22%, 73.24%, 74.09%, and 69.64%, respectively. The removal rates of chemical oxygen demand (COD) and total nitrogen (TN) decreased with decreasing HRT, whereas the removal rate of NH4+-N increased. The removal rate of total phosphorus (TP) was approximately 30%. Results indicate that the ALBR and function-enhanced microbe system can reduce sludge and treat sewage simultaneously, and the effluent is up to the national emission standard. Addition of function-enhanced microbes can promote the degradation of petroleum hydrocarbon substances in the sludge, especially alkanes with low carbon numbers. This study suggests that the optimal HRT for the system is 16 h. The total operation cost of the ALBR combined with the function-enhanced microbe system can be reduced by 50% compared with the cost of direct treatment of the RES system.