Molecular motion behaviors of starch affect starch-polyphenol inclusion complex and digestibility among different stilbenes polyphenol structures.

Starch-polyphenol V-type inclusion complex has become a hot topic due to its anti-digestibility and nutritional function. This paper aimed to explore the molecular motion behavior of starch affects starch-polyphenol inclusion complex and digestibility among different stilbene polyphenol structures (resveratrol (RA), pterostilbene (PB) and polydatin (PD) via the high-pressure homogenization (HPH) and heat moisture treatment (HMT) processes), which represented the fully extended and limited molecular motion behavior of starch, respectively. These results revealed distinct trends in complex formation among different stilbenes polyphenol structures, highlighting RA as particularly conducive to increasing single helix and V-type crystalline structures with the highest resistant starch (RS) content of 28.11 % due to its smaller steric hindrance. Novelty, in HPH environments with extended molecular motion behavior, the steric hindrance and hydrophobicity/CH-π interactions of polyphenols influence complex formation in the order of RA > PB > PD. Conversely, in HMT systems with limited molecular motion behavior, the limited movement of molecules emphasized the importance of hydrogen bond interactions between polyphenols and starch. Thus, the glucoside in PD enhanced its interaction with starch compared to methoxy-modified PB, leading to increased formation of inclusion complex with RS content of 18.61 %. Overall, these findings deepen the understanding of starch-polyphenol interactions.

Effect of active carbonyl-carboxyl ratio on dynamic Schiff base crosslinking and its modulation of high-performance oxidized starch-chitosan hydrogel by hot extrusion 3D printing.

The quest to develop 3D starch-based printing hydrogels for the controlled release of active substances with excellent mechanical and printing properties has gained significant attention. This work introduced a facile method based on crosslinking via Schiff base reaction for preparing bicomponent hydrogels. The method involved the utilization of customizable oxidized starch (OS) and chitosan (CS), enabling superior printing performance through the precise control of various active carbonyl-carboxyl ratios (ACR, 2:1, 1:1, and 2:3, respectively) of OS. OS-CS hydrogel (OSC) with an ACR level of 2:1 (OS-2-y%CS) underwent rearrangement during printing environment, fostering increased Schiff base reaction with a higher crosslinking degree and robust high structural recovery (>95 %). However, with decreasing ACR levels (from 2:1 to 2:3), the printing performance and mechanical strength of printed OSC (POSC) declined due to lower Schiff base bonds and increased phase separation. Compared with printed OS, POS-2-2%CS exhibited a remarkable 1250.52 % increase in tensile strength and a substantial 2424.71 % boost in compressive strength, enhanced shape fidelity and notable self-healing properties. Moreover, POS-2-2%CS exhibited stable diffusive drug release, showing potential application in the pH-responsive release of active substances. Overall, controlling the active carbonyl-carboxyl ratios provided an efficient and manageable approach for preparing high-performance 3D-printed hydrogels.

A mathematical model for HIV dynamics with multiple infections: implications for immune escape.

Multiple infections enable the recombination of different strains, which may contribute to viral diversity. How multiple infections affect the competition dynamics between the two types of strains, the wild and the immune escape mutant, remains poorly understood. This study develops a novel mathematical model that includes the two strains, two modes of viral infection, and multiple infections. For the representative double-infection case, the reproductive numbers are derived and global stabilities of equilibria are obtained via the Lyapunov direct method and theory of limiting systems. Numerical simulations indicate similar viral dynamics regardless of multiplicities of infections though the competition between the two strains would be the fiercest in the case of quadruple infections. Through sensitivity analysis, we evaluate the effect of parameters on the set-point viral loads in the presence and absence of multiple infections. The model with multiple infections predict that there exists a threshold for cytotoxic T lymphocytes (CTLs) to minimize the overall viral load. Weak or strong CTLs immune response can result in high overall viral load. If the strength of CTLs maintains at an intermediate level, the fitness cost of the mutant is likely to have a significant impact on the evolutionary dynamics of mutant viruses. We further investigate how multiple infections alter the viral dynamics during the combination antiretroviral therapy (cART). The results show that viral loads may be underestimated during cART if multiple-infection is not taken into account.

Pre-dry heat treatment alters the structure and ultimate in vitro digestibility of wheat starch-lipids complex in hot-extrusion 3D printing.

Herein, we proposed dry heat treatment (DHT) as a pre-treatment method for modifying printed materials, with a particular focus on its application in the control of starch-lipid interactions during hot-extrusion 3D printing (HE-3DP). The results showed that pre-DHT could promote the complexation of wheat starch (WS) and oleic acid (OA)/corn oil (CO) during HE-3DP and thus increase the resistant starch (RS) content. From the structural perspectives, pre-DHT could break starch molecular chains into lower relative molecular weight which enhanced the starch-lipids hydrophobic interactions to form the V-type crystalline structure during HE-3DP. Notably, pre-DHT could also induce the formation of complexed structure which was maintained during HE-3DP. Compared with CO, OA with linear hydrophobic chains was easier to enter the spiral cavity of starch to form more ordered structures, resulting in higher RS content of 27.48 %. Overall, the results could provide basic data for designing nutritional starchy food systems by HE-3DP.

Introduction of chlorogenic acid into thermal processed starch- oleic acid system controls the ordered structure and inhibits oleic acid oxidation through molecular interactions.

In this study, the effects of starch- oleic acid (OA)- chlorogenic acid (CA) molecular interaction on OA oxidation during thermal processing were investigated based on structural analysis, oxidation characteristics and quantum calculations. The results showed that in the ternary system, on the one hand, OA could enter the spiral cavity of starch through hydrophobic forces and form V-type crystalline structure, which delayed its oxidation. On the other hand, CA could further inhibit the oxidation of OA through free radical reaction and did not affect the molecular interactions between OA and starch due to the steric hindrance and hydrophily. Notably, starch-OA-CA interactions could effectively decrease total oxidation value (19.07), prolong the induction time of oxidation (114.6 min) and reduce the abundance of oxidation products through hydrogen atom transfer reactions with active phenolic hydroxyl to protect the α-methylene groups at C=C. Overall, these results provided insights into functional property regulation by the interaction of starch-based multi-component systems.

3D printing-mediated microporous starch hydrogels for wound hemostasis.

Starch hydrogels with biodegradability and cytocompatibility are good alternatives to traditional dressings. Herein, oxidized starch hydrogel loaded with coagulation factor Ca2+ ions (CaOMS) is successfully constructed by green hot-extrusion 3D printing technology (HE-3DP). In vitro study demonstrated the good water absorbing capacity (845.15-1194.20%) and blood cell and platelet adhesion of CaOMS to assist hemostasis owing to the boosted network structure density, gel strength, and the release of activated Ca2+ ions. More importantly, in vivo experiments further demonstrated CaOMS could maintain the weight loss caused by blood loss from wounds and has excellent hemostatic (65 s) and wound healing properties by promoting the secretion of epidermal growth factor (EGF) and vascular endothelial growth factor (VEGF) expression. The advantages of CaOMS, including rapid and effective hemostasis, effective wound healing, low cost, easy usage, and adaptability to fit various wound shapes, make it a promising biomaterial for achieving fast hemostasis and wound healing.

Metal-organic framework-mediated construction of confined ultrafine nickel phosphide immobilized in reduced graphene oxide with excellent cycle stability for asymmetric supercapacitors.

Transition metal phosphides (TMPs) with unique metalloid features have been promised great application potential in developing high-efficiency electrode materials for electrochemical energy storage. Nevertheless, sluggish ion transportation and poor cycling stability are the critical hurdles limiting their application prospects. Herein, we presented the metal-organic framework-mediated construction of ultrafine Ni2P immobilized in reduced graphene oxide (rGO). Nano-porous two-dimensional (2D) Ni-metal-organic framework (Ni-MOF) was grown on holey graphene oxide (Ni(BDC)-HGO), followed by MOF-mediated tandem pyrolysis (carbonization and phosphidation; Ni(BDC)-HGO-X-P, X denoted carbonization temperature and P represented phosphidation). Structural analysis revealed that the open-framework structure in Ni(BDC)-HGO-X-Ps had endowed them with excellent ion conductivity. The Ni2P wrapped by carbon shells and the PO bonds linking between Ni2P and rGO ensured the better structural stability of Ni(BDC)-HGO-X-Ps. The resulting Ni(BDC)-HGO-400-P delivered a capacitance of 2333.3 F g-1 at 1 A g-1 in a 6 M KOH aqueous electrolyte. More importantly, Ni(BDC)-HGO-400-P//activated carbon, the assembled asymmetric supercapacitor with an energy density of 64.5 Wh kg-1 and a power density of 31.7 kW kg-1, almost maintained its initial capacitance after 10,000 cycles. Furthermore, in situ electrochemical-Raman measurements were exploited to demonstrate the electrochemical changes of Ni(BDC)-HGO-400-P throughout the charging and discharging processes. This study has further shed light on the design rationality of TMPs for optimizing supercapacitor performance.

Bioinspired design of Na-ion conduction channels in covalent organic frameworks for quasi-solid-state sodium batteries.

Solid polymer electrolytes are considered among the most promising candidates for developing practical solid-state sodium batteries. However, moderate ionic conductivity and narrow electrochemical windows hinder their further application. Herein, inspired by the Na+/K+ conduction in biological membranes, we report a (-COO-)-modified covalent organic framework (COF) as a Na-ion quasi-solid-state electrolyte with sub-nanometre-sized Na+ transport zones (6.7-11.6 Å) created by adjacent -COO- groups and COF inwalls. The quasi-solid-state electrolyte enables selective Na+ transport along specific areas that are electronegative with sub-nanometre dimensions, resulting in a Na+ conductivity of 1.30×10-4 S cm-1 and oxidative stability of up to 5.32 V (versus Na+/Na) at 25 ± 1 °C. Testing the quasi-solid-state electrolyte in Na||Na3V2(PO4)3 coin cell configuration demonstrates fast reaction dynamics, low polarization voltages, and a stable cycling performance over 1000 cycles at 60 mA g-1 and 25 ± 1 °C with a 0.0048% capacity decay per cycle and a final discharge capacity of 83.5 mAh g-1.

HIV infection dynamics and viral rebound: Modeling results from humanized mice.

Despite years of combined antiretroviral therapy (cART), HIV persists in infected individuals. The virus also rebounds after the cessation of cART. The sources contributing to viral persistence and rebound are not fully understood. When viral rebound occurs, what affects the time to rebound and how to delay the rebound remain unclear. In this paper, we started with the data fitting of an HIV infection model to the viral load data in treated and untreated humanized myeloid-only mice (MoM) in which macrophages serve as the target of HIV infection. By fixing the parameter values for macrophages from the MoM fitting, we fit a mathematical model including the infection of two target cell populations to the viral load data from humanized bone marrow/liver/thymus (BLT) mice, in which both CD4+ T cells and macrophages are the target of HIV infection. Data fitting suggests that the viral load decay in BLT mice under treatment has three phases. The loss of infected CD4+ T cells and macrophages is a major contributor to the first two phases of viral decay, and the last phase may be due to the latent infection of CD4+ T cells. Numerical simulations using parameter estimates from the data fitting show that the pre-ART viral load and the latent reservoir size at treatment cessation can affect viral growth rate and predict the time to viral rebound. Model simulations further reveal that early and prolonged cART can delay the viral rebound after cessation of treatment, which may have implications in the search for functional control of HIV infection.

Dual Molecules Cooperatively Confined In-Between Edge-oxygen-rich Graphene Sheets as Ultrahigh Rate and Stable Electrodes for Supercapacitors.

Noncovalent modification of carbon materials with redox-active organic molecules has been considered as an effective strategy to improve the electrochemical performance of supercapacitors. However, their low loading mass, slow electron transfer rate, and easy dissolution into the electrolyte greatly limit further practical applications. Herein, this work reports dual molecules (1,5-dihydroxyanthraquinone (DHAQ) and 2,6-diamino anthraquinone (DAQ)) cooperatively confined in-between edge-oxygen-rich graphene sheets as high-performance electrodes for supercapacitors. Cooperative electrostatic-interaction on the edge-oxygen sites and π-π interaction in-between graphene sheets lead to the increased loading mass and structural stability of dual molecules. Moreover, the electron tunneling paths constructed between edge-oxygen groups and dual molecules can effectively boost the electron transfer rate and redox reaction kinetics, especially at ultrahigh current densities. As a result, the as-obtained electrode exhibits a high capacitance of 507 F g-1 at 0.5 A g-1 , and an unprecedented rate capability (203 F g-1 at 200 A g-1 ). Moreover, the assembled symmetrical supercapacitor achieves a high energy density of 17.1 Wh kg-1 and an ultrahigh power density of 140 kW kg-1 , as well as remarkable stability with a retention of 86% after 50 000 cycles. This work may open a new avenue for the efficient utilization of organic materials in energy storage and conversion.

Starch-guar gum-ferulic acid molecular interactions alter the ordered structure and ultimate retrogradation properties and in vitro digestibility of chestnut starch under extrusion treatment.

Molecular interactions among starch and multiple-components during food processing determine the retrogradation properties and digestibility of starch. Here, the effects of starch-guar gum (GG)-ferulic acid (FA) molecular interactions on retrogradation properties, digestibility and ordered structural changes of chestnut starch (CS) under extrusion treatment (ET) were investigated by structural analysis and quantum chemistry. Due to the entanglement behaviors and hydrogen bond interactions, GG could inhibit the formation of helical and crystalline structures of CS. When FA was introduced simultaneously, FA could weaken the interactions between GG and CS as well as enter the spiral cavity of starch to increase the single/double helix and V-type crystalline structures while reducing A-type crystalline. Based on the above structural changes, ET with starch-GG-FA molecular interactions resulted in resistant starch content of 20.31% and anti-retrogradation rate of 42.98% for 21-day storage. Overall, the results could provide basic data for creation of chestnut-based food with higher value.

A biophotonic device based on a conjugated polymer and a macrophage-laden hydrogel for triggering immunotherapy.

A biophotonic device is fabricated by a 3D printing technique for tumor immunotherapy utilizing a flexible organic light-emitting diode (OLED) with deep blue emission and a gelatin-alginate hydrogel that contains a poly(phenylene vinylene) (PPV) derivative and live immune cells of macrophages (M0-RAW264.7). PPV is excited by the OLED to generate reactive oxygen species (ROS), enabling the macrophages to polarize to the M1 phenotype and secrete cytotoxic cytokines to induce the apoptosis of tumor cells. This strategy provides a new method for fabricating cell-involved biophotonic devices for immunotherapy.

Weighted Gene Co-Expression Network Analysis to Explore Hub Genes of Resveratrol Biosynthesis in Exocarp and Mesocarp of 'Summer Black' Grape.

Resveratrol is a polyphenol compound beneficial to human health, and its main source is grapes. In the present study, the molecular regulation of resveratrol biosynthesis in developing grape berries was investigated using weighted gene co-expression network analysis (WGCNA). At the same time, the reason for the resveratrol content difference between grape exocarp (skin) and mesocarp (flesh) was explored. Hub genes (CHS, STS, F3'5'H, PAL, HCT) related to resveratrol biosynthesis were screened with Cytoscape software. The expression level of hub genes in the exocarp was significantly higher than that in the mesocarp, and the expressions of the hub genes and the content of resveratrol in exocarp peaked at the maturity stage. While the expression levels of PAL, CHS and STS in the mesocarp, reached the maximum at the maturity stage, and F3'5'H and HCT decreased. These hub genes likely play a key role in resveratrol biosynthesis. Kyoto Encyclopedia of Genes and Genomes (KEGG) pathway analysis further indicated that resveratrol biosynthesis was related to flavonoid biosynthesis, phenylalanine metabolism, phenylpropanoid biosynthesis, and stilbene biosynthesis pathways. This study has theoretical significance for exploring genes related to resveratrol biosynthesis in the exocarp and mesocarp of grapes, and provides a theoretical basis for the subsequent function and regulatory mechanism of hub genes.

Threshold behaviour of a stochastic SIRS Le´vy jump model with saturated incidence and vaccination.

A stochastic SIRS system with $ \mathrm {L\acute{e}vy} $ process is formulated in this paper, and the model incorporates the saturated incidence and vaccination strategies. Due to the introduction of $ \mathrm {L\acute{e}vy} $ jump, the jump stochastic integral process is a discontinuous martingale. Then the Kunita's inequality is used to estimate the asymptotic pathwise of the solution for the proposed model, instead of Burkholder-Davis-Gundy inequality which is suitable for continuous martingales. The basic reproduction number $ R_{0}^{s} $ of the system is also derived, and the sufficient conditions are provided for the persistence and extinction of SIRS disease. In addition, the numerical simulations are carried out to illustrate the theoretical results. Theoretical and numerical results both show that $ \mathrm {L\acute{e}vy} $ process can suppress the outbreak of the disease.

Evaluation of Copper Levels in Dental Calculus of OSF Patients with Chewing Dried Areca-Nut Quids in Hunan Province of Mainland China.

Dental calculus is a potential material that can be used for assessing chronic exposure to trace heavy metals in oral cavity as it is a long-term reservoir. The aim of this study was to investigate the correlation between dental calculus copper levels and risk of oral submucous fibrosis (OSF) due to chewing dried areca-nut quids in Mainland China. This study included 34 OSF (grade 1) sufferers with dried areca-nut quids chewing as the patient group and 23 healthy individuals without areca-nut chewing as the control group. The dental calculus sample was obtained from all 57 participants and evaluated by inductively coupled plasma mass spectrometry (ICP-MS) for dental calculus level of copper. This work revealed that the mean copper level of dental calculus was significantly higher in OSF (grade 1) sufferers with areca-nut chewing than those in healthy individuals without areca-nut chewing (p < 0.001). This work provided an evidence to support that there may be a positive correlation between elevated levels of copper in dental calculus caused by chewing dried areca-nut quids and an increased risk of developing OSF in Mainland China.

Towards a new combination therapy with vectored immunoprophylaxis for HIV: Modeling "shock and kill" strategy.

Latently infected cells are considered as a major barrier to curing Human Immunodeficiency Virus (HIV) infection. Reactivation of latently infected cells followed by killing the actively infected cells may be a potential strategy ("shock and kill") to purge the latent reservoir. Based on vectored immunoprophylaxis (VIP) experiment that can elicit bNAbs, in this paper a mathematical model is formulated to explore the efficacy of "shock and kill" strategy with VIP. We derive the basic reproduction number R0 of the model and show that R0 completely determines the dynamics of the model: if R0<1, the disease-free equilibrium is globally asymptotically stable; if R0>1, the system is uniformly persistent. Numerical simulations suggest that the "shock and kill" strategy with VIP can effectively control HIV infection while this strategy cannot eradicate the reservoir without VIP although it can alleviate the HIV infection. To model the administration of drugs and vaccine more realistically, pharmacokinetics and pulse vaccination are incorporated into the model of ordinary differential equations. The resultants are described by impulsive differential equations. The thresholds are obtained for the frequency and strength of the vaccination to eliminate the viruses. Furthermore, the most appropriate times are numerically investigated for starting a short-term latency-reversing agents (LRAs) treatment relative to ART considering the toxicity of LRAs. The results show that LRAs treatment at the beginning of ART might be a better option. These results have important implications for the design of HIV cure-related clinical trials.

A cell model about symmetric and asymmetric stem cell division.

We construct a multi-stage cell lineage model including self-renewal, apoptosis, cell movement and the symmetrical/asymmetrical division of stem cells. The evolution of cell populations can be described by coupled reaction-diffusion partial differential equations, and the propagating wavefront speeds can be obtained analytically and verified by numerical solutions of the equations. The emphasis is on the effect of symmetric/asymmetric division of stem cells on the population and propagating dynamics of cell lineage. It is found that stem cells' asymmetric cell division (ACD) can move the phase boundary of the homogenous solution of the system. The population of the cell lineage will be promoted in presence of ACD. The concentration of stem cells increases with ACD but that of differentiated daughter cells decreases with ACD. In addition, it is found that the propagating speed of the stem cells can be evaluated with ACD. When the daughter cells move fast to a new space, stem cells can catch them up through increasing ACD. Our results may suggest a mechanism of collective migration of cell lineage through cooperation between ACD of stem cells and fast diffusion of the daughter cells.

Impacts of demographic and environmental stochasticity on population dynamics with cooperative effects.

Different types of stochasticity play essential roles in shaping complex population dynamics. This paper presents a novel approach to model demographic and environmental stochasticity in a single-species model with cooperative components that are measured by component Allee effects. Our work provides rigorous mathematical proof on stochastic persistence and extinction, ergodicity (i.e., the existence of a unique stationary distribution) and the existence of a nontrivial periodic solution to study the impacts of demographic and environmental stochasticity on population dynamics. The theoretical and numerical results suggest that stochasticity may affect the population system in a variety of ways, specifically: (i) In the weak Allee effects case (e.g., strong cooperative efforts), the demographic stochasticity from the attack rate contributes to the expansion of the population size, while the demographic stochasticity from the handling rate and the environmental stochasticity have the opposite role, and may even lead to population extinction; (ii) In the strong Allee effects case (cooperative efforts not strong enough), both demographic and environmental stochasticity play a similar role in the survival of population, and are related to the initial population level: if the initial population level is large enough, demographic stochasticity and environmental stochasticity may be detrimental to the survival of population, otherwise if the initial population level is small enough, demographic stochasticity and environmental stochasticity may bring survival opportunities for the population that deterministically would extinct indefinitely; (iii) In the extinction case, demographic and environmental stochasticity cannot change the trend of population extinction, but they can delay or promote population extinction.

Effect of starch-catechin interaction on regulation of starch digestibility during hot-extrusion 3D printing: Structural analysis and simulation study.

Recent developments of hot-extrusion 3D printing (HE-3DP) have made it possible to manipulate starch digestibility. This work investigated the regulating mechanism of starch-catechin (EC) interactions on rice starch digestibility during HE-3DP by using modern analytical techniques and computational models. The results showed that the HE-3DP processing with starch-EC interactions could significantly decrease the starch digestibility (p < 0.05) due to the formation of ordered structures including short-range ordered structure, nano-aggregates and V-type crystalline structure. Meanwhile, molecular dynamics simulations were performed to reveal the mechanism of EC as an enzyme inhibitor to enhance the resistant starch contents of rice starch to 46.1%. Results showed that EC could loosely attach to starch chains, thereby facilitating binding to Trp59 of pancreatic α-amylase and preventing starch from binding to its active pocket. These findings provide useful structural information for EC to reduce starch digestibility in the HE-3DP environment.

3D-printing of oxidized starch-based hydrogels with superior hydration properties.

High-hydration hydrogels based on carbohydrate polymers and green preparation methods have attracted intensive research focus recently. Driven by the attractive functions of starch, oxidized maize starch (OMS) was chosen and the related hydrogel (3D-OMS) was constructed by hot-extrusion 3D printing (HE-3DP). Meanwhile, the effect of different OMS concentrations (11 %-19 %) on its printability, structure and hydration properties were systematically investigated. The results showed that the formation of porous structure during HE-3DP environment contributed to rapid water absorption and well water holding capacity of 3D-OMS. Interestingly, as the OMS concentration increased from 11 % to 19 %, the 3D-OMS presented great hydration properties, with its maximum water absorption capacity and water holding capacity reaching 3013.43 % (11-OMS) and 93.53 % (19-OMS), respectively. Among them, 13 % was the best concentration for HE-3DP. Besides, 3D-OMS also exhibited good biodegradability and cytocompatibility. These results demonstrated potential for developing new starch-based biomedical hydrogel with great hydration properties through HE-3DP technology.