Intense Circularly Polarized Luminescence Induced by Chiral Supramolecular Assembly: The Importance of Intermolecular Electronic Coupling.

Herein we report on circularly polarized luminescence (CPL) emission originating from supramolecular chirality of organic microcrystals with a |glum| value up to 0.11. The microcrystals were prepared from highly emissive difluoroboron ß-diketonate (BF2dbk) dyes R-1 or S-1 with chiral binaphthol (BINOL) skeletons. R-1 and S-1 exhibit undetectable CPL signals in solution but manifest intense CPL emission in their chiral microcrystals. The chiral superstructures induced by BINOL skeletons were confirmed by XRD analysis. Spectral analysis and theoretical calculations indicate that intermolecular electronic coupling, mediated by the asymmetric stacking in the chiral superstructures, effectively alters excited-state electronic structures and facilitates electron transitions perpendicular to BF2bdk planes. The coupling increases cosθµ,m from 0.05 (monomer) to 0.86 (tetramer) and triggers intense optical activity of BF2bdk. The results demonstrate that optical activity of chromophores within assemblies can be regulated by both orientation and extent of intermolecular electronic couplings.

Insights into "wheat aroma": Analysis of volatile components in wheat grains cultivated in saline-alkali soil.

The wheat grains that are cultivated in saline-alkali soil exhibit a richer "wheat aroma" compared to their counterparts. This study characterized the composition and content of volatiles in five wheat kernel varieties, harvested from two fields with varying pH levels and total salt content in the soil. The wheat grown in soil with high pH and total salt content had significantly lower levels (p < 0.05) of ethyl 3-methylbutanoate and 1-octen-3-one and significantly higher levels (p < 0.05) of 1-butanol and 1-octen-3-ol. Among all factors, plant site contributed the highest F-value contribution rate (more than 77 %) for these four volatile compounds. Six e-nose sensors responsive to these four compounds exhibited consistent trends. Therefore, the lower of ethyl 3-methylbutanoate and 1-octen-3-one, the higher of 1-butanol and 1-octen-3-ol in wheat, grown on saline-alkali soil, served as characteristic markers for "wheat aroma".

Wheat Protein Hydrolysates Improving the Stability of Purple Sweet Potato Anthocyanins under Neutral pH after Commercial Sterilization at 121 °C.

Anthocyanins are prone to degradation and color fading after sterilization. This work examined the potential of wheat protein hydrolysates (WPHs, 40 g/L) in improving the stability of purple sweet potato anthocyanins (PSPAs) under a pH of 6.8 after sterilization at 121 °C followed by storage. Results showed that WPHs increased the thermal degradation half-life of PSPAs 1.65 times after sterilization. Compared to PSPAs alone, after being stored at 37 °C and 45 °C for 7 days, the retention concentration of PSPAs with WPHs was 5.4 and 32.2 times higher, and the color change of PSPAs with WPHs decreased from 6.19 and 10.46 to 0.29 and 0.77, respectively. AFM data, fluorescence and UV spectrograms indicated the formation of complexes between PSPAs and WPHs by hydrophobic attraction confirmed by zeta-potential data. PSPAs with WPHs had stable particle size and zeta potential, which may also significantly increase the concentrations after digestion and antioxidant power of PSPAs. This work indicated that the assembled PSPAs composite structure by WPHs significantly reduced the degradation of PSPAs at a pH of 6.8 after sterilization at 121 °C followed by long-term storage.

Interfacial Polarization Control Engineering and Ferroelectric PZT/Graphene Heterostructure Integrated Application.

Integration and miniaturization are the inevitable trends in the development of electronic devices. PZT and graphene are typical ferroelectric and carbon-based materials, respectively, which have been widely used in various fields. Achieving high-quality PZT/graphene heterogeneous integration and systematically studying its electrical properties is of great significance. In this work, we reported the characterization of a PZT film based on the sol-gel method. Additionally, the thickness of the PZT film was pushed to the limit size (~100 nm) by optimizing the process. The test results, including the remnant and leakage current, show that the PZT film is a reliable and suitable platform for further graphene-integrated applications. The non-destructive regulation of the electrical properties of graphene has been studied based on a domain-polarized substrate and strain-polarized substrate. The domain structures in the PZT film exhibit different geometric structures with ~0.3 V surface potential. The I-V output curves of graphene integrated on the surface of the PZT film exhibited obvious rectification characteristics because of p/n-doping tuned by an interfacial polarized electric field. In contrast, a ~100 nm thick PZT film makes it easy to acquire a larger strain gradient for flexural potential. The tested results also show a rectification phenomenon, which is similar to domain polarization substrate regulation. Considering the difficulty of measuring the flexural potential, the work might provide a new approach to assessing the flexural polarized regulation effect. A thinner ferroelectric film/graphene heterojunction and the polarized regulation of graphene will provide a platform for promoting low-dimension film-integrated applications.

Reversible Dual Fluorescence-Lifetime Imaging of Mitochondrial GSH and Microviscosity: Real-Time Evaluation of Ferroptosis Status.

Ferroptosis, as a new form of regulated cell death, is implicated in various physiological and pathological processes. Developing a single probe for an independent analysis of multiple analytes related to ferroptosis can provide more accurate information and simplify the detection procedures, but it faces great challenges. In this work, we develop a fluorescent probe for the simultaneous detection of GSH through ratiometric fluorescence response and microviscosity via a fluorescence lifetime model. Based on the reversible Michael addition reaction between GSH and unsaturated C═C bond, the probe responds reversibly to GSH with a ratiometric fluorescence variation and a fast response time (t1/2 = 4.7 s). At the same time, the probe is sensitive to environmental viscosity by changing its fluorescence lifetimes. The probe was applied to monitor the drug-induced ferroptosis process through both the classical Xc-/GSH/GPX4- and DHODH-mediated defense mechanisms. We hope that the probe will provide a useful molecular tool for the real-time live-cell imaging of GSH dynamics, which is benefit to unveiling related physiological and pathological processes.

Spontaneous Symmetry Breaking of Achiral Molecules Leading to the Formation of Homochiral Superstructures that Exhibit Mechanoluminescence.

Chirality, with its intrinsic symmetry-breaking feature, is frequently utilized in the creation of acentric crystalline functional materials that exhibit intriguing optoelectronic properties. On the other hand, the development of chiral crystals from achiral molecules offers a solution that bypasses the need for enantiopure motifs, presenting a promising alternative and thereby expanding the possibilities of the self-assembly toolkit. Nevertheless, the rational design of achiral molecules that prefer spontaneous symmetry breaking during crystallization has so far been obscure. In this study, we present a series of six achiral molecules, demonstrating that when these conformationally flexible molecules adopt a cis-conformation and engage in multiple non-covalent interactions along a helical path, they collectively self-assemble into chiral superstructures consisting of single-handed supramolecular columns. When these homochiral supramolecular columns align in parallel, they form polar crystals that exhibit intense luminescence upon grinding or scraping. We therefore demonstrate our molecular design strategy could significantly increase the likelihood of symmetry breaking in achiral molecular synthons during self-assembly, offering a facile access to novel chiral crystalline materials with unique optoelectronic properties.

Photo-Induced Disproportionation-Mediated Photodynamic Therapy: Simultaneous Oxidation of Tetrahydrobiopterin and Generation of Superoxide Radicals.

We herein present an approach of photo-induced disproportionation for preparation of Type-I photodynamic agents. As a proof of concept, BODIPY-based photosensitizers were rationally designed and prepared. The photo-induced intermolecular electron transfer between homotypic chromophores leads to the disproportionation reaction, resulting in the formation of charged intermediates, cationic and anionic radicals. The cationic radicals efficiently oxidize the cellularimportant coenzyme, tetrahydrobiopterin (BH4 ), and the anionic radicals transfer electrons to oxygen to produce superoxide radicals (O2 - ⋅). One of our Type-I photodynamic agents not only self-assembles in water but also effectively targets the endoplasmic reticulum. It displayed excellent photocytotoxicity even in highly hypoxic environments (2 % O2 ), with a half-maximal inhibitory concentration (IC50 ) of 0.96 µM, and demonstrated outstanding antitumor efficacy in murine models bearing HeLa tumors.

Polyphenol-fortified extruded sweet potato starch vermicelli: Slow-releasing polyphenols is the main factor that reduces the starch digestibility.

To investigate the digestive behavior of extruded starch-polyphenols system, extruded sweet potato starch vermicelli (ESPSV) was used as a model. The multi-scale structure, starch digestibility, polyphenol release, digestive enzyme activity during digestion and their correlation of ESPSV supplemented with matcha (MT), green tea extract (GTE), tea polyphenols (TP) and epigallocatechin gallate (EGCG) (at 1% polyphenol level) were discussed. Results showed that tea products in whatever form could retard starch digestion, with EGCG working best. The predicted glycemic index (pGI) of ESPSV was decreased from 82.50 to 65.46 after adding EGCG. Starch formed larger molecular aggregates with tea products under extrusion, showing a "B + V" type pattern. The order of V-type crystals content was EGCG + ESPSV (1.41) > TP + ESPSV (1.50) > GTE + ESPSV (1.88) > MT + ESPSV (2.62) > ESPSV (3.20). Under external pressure, EGCG, as tea monomer, was more likely to enter the spiral cavity of amylose and form V-type inclusion complex. Notably, polyphenols released during digestion could still reduce digestive enzyme activity, with a 15.53% decrease in EGCG + ESPSV compared to ESPSV. This was verified by correlation analysis, where RDS content (0.961, p < 0.01) and pGI (0.966, p < 0.01) were highly significantly correlated with the enzyme activity. Furthermore, tea products did not break or even enhance the quality of ESPSV as the final product.

Comparison of in vitro starch digestibility and structure of matcha-fortified starch vermicelli from different botanical sources.

BACKGROUND: In a study to explore the utilization of polyphenols in complex digestive systems, starch-based vermicelli was employed as the carrier and matcha (MT) was used as the source of polyphenols. Four percent MT was extruded with A-, B-, and C-type starch of rice, sweet potato, and mung bean to prepared starch vermicelli rice starch vermicelli (RSV), sweet potato starch vermicelli (SPSV), and mung bean starch vermicelli (MBSV), respectively. The multi-scale structure of starch, the digestive kinetics of starch, and the bioaccessibility of polyphenols during in vitro digestion were monitored. RESULTS: Matcha did not change the crystal configuration of vermicelli, but increased the relative crystallinity of RSV. Vermicelli with MT possessed a more uniform structure, and the polydispersity index decreased from 3.85-4.89 to 2.56-3.69. However, these structural changes made only a limited contribution to delaying digestion. The detection of polyphenols during digestion revealed that the release of most polyphenols was accomplished in the first 20 min of digestion. The release amount was in the order RSV + MT > MBSV + MT > SPSV + MT, and reached 4.81-5.45 mg GAE g-1 . Correspondingly, the activity of digestive enzyme decreased in the order RSV + MT < MBSV + MT < SPSV + MT. Consequently, MT significantly (P < 0.05) reduced the digestive rate of vermicelli, and the rapidly digested starch and predicted glycemic index of RSV + MT decreased from 71.28% to 56.31% and from 74.68 to 62.86, respectively. The released polyphenols were also the main source of the strong antioxidant capacity of vermicelli with MT. CONCLUSIONS: These results provided a theoretical basis for using polyphenols to pursue healthy starch-based food. © 2023 Society of Chemical Industry.

An ultra-compact acoustofluidic device based on the narrow-path travelling surface acoustic wave (np-TSAW) for label-free isolation of living circulating tumor cells.

Obtaining highly purified intact living cells from complex environments has been a challenge, such as the isolation of circulating tumor cells (CTCs) from blood. In this work, we demonstrated an acoustic-based ultra-compact device for cell sorting, with a chip size of less than 2 × 1.5 cm2. This single actuator device allows non-invasive and label-free isolation of living cells, offering greater flexibility and applicability. The device performance was optimized with different-sized polystyrene (PS) particles and blood cells spiked with cancer cells. Using the narrow-path travelling surface acoustic wave (np-TSAW), precise isolation of 10 µm particles from a complex mixture of particles (5, 10, 20 µm) and separation of 8 µm and 10 µm particles was achieved. The purified collection of 10 µm particles with high separation efficiency (98.75%) and high purity (98.1%) was achieved by optimizing the input voltage. Further, we investigated the isolation and purification of CTCs (MCF-7, human breast cancer cells) from blood cells with isolation efficiency exceeding 98% and purity reaching 93%. Viabilities of the CTCs harvested from target-outlet were all higher than 97% after culturing for 24, 48, and 72 h, showing good proliferation ability. This novel ultra-miniaturized microfluidic chip demonstrates the ability to sorting cells with high-purity and label-free, providing an attractive miniaturized system alternative to traditional sorting methods.

Peptide photowrapping of gold-silica nanocomposites for constructing MMP-responsive drug capsules for chemo-photothermal therapy.

A multifunctional undecapeptide, YYDPLGLADYY, was designed and synthesized for the photowrapping of silica-coated gold nanorods. The obtained nanocapsules, bearing a well-defined core-shell structure, were able to encapsulate a therapeutic drug, respond to an MMP-upregulated tumor microenvironment, and achieve NIR-triggered anticancer chemo-photothermal therapy with favorable efficacy.

The alleviative effect of curdlan on the quality deterioration of konjac glucomannan thermo-irreversible gels after commercial sterilization at 121 °C.

This work employed different curdlan concentrations (0.00 %, 1.00 %, 1.50 %, 2.00 %, and 2.50 %) to alleviate the quality degradation of konjac glucomannan (KGM) gels after commercial sterilization at 121 °C for 15 min. The results showed that all levels of curdlan could retard the deterioration of KGM gels, with the best effect at 2.00 %. After commercial sterilization, incorporating curdlan into KGM gels greatly reduced the Tan σ (G"/ G'), total relaxation time and half-free water from 0.52, 89.85 ms and 98.26 % to 0.27, 38.48 ms and 21.42 %, respectively. Moreover, the addition of curdlan imparted a better texture to KGM gels, as reflected in the increase of hardness, springiness, water-holding capacity and whiteness value from 1400.85 g, 0.42, 87.92 % and 33.33 to 3461.68 g, 0.80, 96.50 % and 49.27, respectively. Furthermore, SEM images revealed that curdlan endowed KGM gels with a tighter structure and smaller pores, and the pore size distribution was reduced from 113.46 µm to17.91 µm, indicating a stronger interaction among molecules, as evidenced by XRD and FTIR results. KGM gels with curdlan possessed less proportion of complete crystallites and crystalline region. These findings suggested that curdlan can be the potently protectant for improving the quality of commercially sterilized KGM gel-based products.

Ultra-Small Nano-Assemblies as Tumor-Targeted and Renal Clearable Theranostic Agent for Photodynamic Therapy.

It is a challenge to design photosensitizers to balance between the tumor-targeting enrichment for precise treatment and efficient clearance within a reasonable timescale for reducing side effects. Herein, an ultra-small nano-photosensitizer 1a with excellent tumor-specific accumulation and renal clearance is reported. It is formed from the self-assembly of compound 1 bearing three triethylene glycol (TEG) arms and two pyridinium groups in water. The positively charged surface with neutral TEG coating enables 1a to efficiently target the tumor, with the signal-to-background ratio reaching as high as 11.5 after tail intravenous injection. The ultra-small size of 1a with an average diameter of 5.6 nm allows its fast clearance through kidney. Self-assembly also endows 1a with an 18.2-fold enhancement of reactive oxygygen species generation rate compared to compound 1 in organic solution. Nano-PS 1a manifests an excellent photodynamic therapy efficacy on tumor-bearing mouse models. This work provides a promising design strategy of photosensitizers with renal clearable and tumor-targeting ability.

Supramolecular Photosensitizer Enables Oxygen-Independent Generation of Hydroxyl Radicals for Photodynamic Therapy.

The highly oxygen-dependent nature of photodynamic therapy (PDT) limits its therapeutic efficacy against hypoxic solid tumors in clinics, which is an urgent problem to be solved. Herein, we develop an oxygen-independent supramolecular photodynamic agent that produces hydroxyl radical (•OH) by oxidizing water in the presence of intracellularly abundant pyruvic acid under oxygen-free conditions. A fluorene-substituted BODIPY was designed as the electron donor and coassembled with perylene diimide as the electron acceptor to form the quadruple hydrogen-bonded supramolecular photodynamic agent. Detailed mechanism studies reveal that intermolecular electron transfer and charge separation upon light irradiation result in an efficient generation of radical ion pairs. Under oxygen-free conditions, the cationic radicals directly oxidize water to generate highly cytotoxic •OH, and the anionic radicals transfer electrons to pyruvic acid, realizing the catalytic cycle. Thus, this photodynamic agent exhibited superb photocytotoxicity even under severe hypoxic environments and excellent in vivo antitumor efficacy on HeLa-bearing mouse models. This work provides a strategy for constructing oxygen-independent photodynamic agents, which opens up an avenue for effective PDT against hypoxic tumors.

Rotors tailoring molecular stacking for constructing multi-stimuli-responsive luminescent materials.

We report a multi-stimuli-responsive luminescent material containing rotor moieties. It forms two types of crystals, G and O. The emission of G can be modulated by multiple external stimuli, whereas O does not show such responsiveness. The X-ray structure analysis reveals that the rotors are critical for the polymorphic emission and stimuli response properties.

Collagen hydrolysates improve the efficiency of sodium alginate-encapsulated tea polyphenols in beads and the storage stability after commercial sterilization.

This study showed that sodium alginates (SA)-based beads reinforced with collagen hydrolysates (CHs) significantly increased an encapsulation rate of tea polyphenols (TP) from 34.54 % to 85.06 % when the mass ratio of SA: CHs increased from1.5:0 to 1.5:0.5. And after the 30-day storage at 37 °C, the retention rate of TP in beads with CHs at the solutions with pH = 4.0 or pH = 7.0 increased from 61.10 % to 80.21 %, or from 67.72 % to 80.47 % after sterilization at 98 °C or 121 °C for 30 min, respectively. Also, the addition of CHs at 0.5 % resulted in a greater retention of the polyphenolic compositions values of TP determined by UPLC-Orbitrap-MS system. Additionally, the DPPH and ABTS+ free-radical scavenging capacities and ferric-reducing antioxidant power of beads with CHs after sterilization at 98 °C or 121 °C for 30 min were significantly higher than which without CHs. Physical phenomena based on ζ-potential, particle size, fluorescence, UV spectroscopy and confocal laser scanning microscope showed that tightly non-covalent complexes of CHs in combination to TP could be uniformly and stably distributed in the network of SA solution for encapsulating TP in SA-based beads. These findings provided suggestions for the co-encapsulation design and development of hydrophilic nutritive compounds based on CHs in SA-based beads.

Circularly Polarized Laser Emission from Homochiral Superstructures based on Achiral Molecules with Conformal Flexibility.

Without external chiral intervention, it is a challenge to form homochirality from achiral molecules with conformational flexibility. We here report on a rational strategy that uses multivalent noncovalent interactions to clamp the molecular conformations of achiral D-A molecules. These interactions overcome the otherwise dominant dipole-dipole interactions and thus disfavor their symmetric antiparallel stacking. It in turn facilitates parallel packing, leading to spontaneous symmetry breaking during crystallization and thus the formation of homochiral conglomerates. When this emergent homochirality is coupled with optical gain characteristics of the molecules, the homochiral crystals are explored as excellent circularly polarized micro-lasers with low lasing threshold (16.4 µJ cm-2 ) and high dissymmetry factor glum (0.9). This study therefore provides a facile design strategy for supramolecular chiral materials and active laser ones without the necessity of intrinsic chiral element.

Effect of Medium Chain Triglycerides on the Digestion and Quality Characteristics of Tea Polyphenols-Fortified Cooked Rice.

Nowadays, medium chain triglycerides (MCT) with special health benefits have been increasingly applied for fortifying food products. Therefore, the present work aimed to investigate the effects of MCT on traditional tea polyphenols-fortified cooked rice (TP-FCR). It was visualized by DSC, CLSM, XRD, FT-IR, and Raman spectroscopy. The higher content of starch-MCT complexes with an increase in the relative crystallinity and the generation of short-range ordered structures contributed to a more ordered and compact molecular arrangement, which can hinder the action of digestive enzymes on starch. SEM demonstrated that MCT transformed the microstructure of TP-FCR into a denser and firmer character, making it an essential component hindering the accessibility of digestive enzymes to starch granules and slowing the release of tea polyphenols in TP-FCR to attenuate starch digestion. Consequently, the addition of MCT reduced the polyphenol-regulated starch digestibility from 74.28% in cooked white rice to 64.43% in TP-FCR, and further down to 50.82%. Besides, MCT also reduced the adhesiveness and improved the whiteness of TP-FCR. The findings suggested that MCT incorporation could be a potential strategy in cooked rice production to achieve high sensory quality and low glycemic cooked rice.

Evaluation of Salt Tolerance Mechanism and Study on Salt Tolerance Relationship of Different Salt-Tolerant Wheat Varieties.

The physiological and biochemical indexes of different salt-tolerant wheat cultivars under salt stress are affected to different degrees. The changes in physiological and biochemical indexes in salt-tolerant wheat varieties are moderate, while salt-sensitive wheat varieties have bigger changes. In this article, through comprehensive utilization of germination and seedling indoor test morphological indexes, physiological and biochemical index, and output index, combined with the evaluation mechanism of wheat's salt resistance, different salt tolerance types in the middle and lower reaches of the Yangtze River in Shandong province were studied; a collection of 100 wheat varieties and 11 wheat varieties planted over a large area were classified into three groups: strong salt resistance, medium salt resistance, and weak salt resistance. Comparative analysis of different wheat varieties' salt resistance evaluation mechanism was performed, as well as the analysis of the germination rate of wheat varieties, coleoptile growth situation, emergence rate, protect wheat seeding rate, tillering rate, seedling height, root length, seedling dry weight, wet weight, number of leaves, plant growth situation, agronomic characters of the Na+/K+ ratio, and other physiological and biochemical indexes such as salt resistance index. The evaluation mechanism of salt tolerance and the relationship of salt tolerance of different wheat varieties were obtained. The results showed that there were significant differences in salt tolerance among the 100 wheat varieties at the germination stage. Among them, three varieties, YM (Yangmai) 25, YM (Yangmai) 24, and EM (Emai) 25, had the strongest salt tolerance at the germination stage, reaching the level of the salt tolerance variety DK 961, and the salt tolerance was in the first level, while NM 17, NM 23, and other 21 varieties reached the level of the salt tolerance. These 24 varieties with strong salt tolerance at the germination stage can be used to screen the salt tolerance of wheat planted in the saline soil of Jiangsu coastal beach.

Supramolecular photodynamic agents for simultaneous oxidation of NADH and generation of superoxide radical.

Given that Type-I photosensitizers (PSs) have hypoxia tolerance, developing general approaches to prepare Type-I PSs is of great importance, but remains a challenge. Here, we report a supramolecular strategy for the preparation of Type-I photodynamic agents, which simultaneously generate strong oxidizing cationic radicals and superoxide radicals, by introducing electron acceptors to the existing Type-II PSs. As a proof-of-concept, three electron acceptors were designed and co-assembled with a classical PS to produce quadruple hydrogen-bonded supramolecular photodynamic agents. The photo-induced electron transfer from the PS to the adjacent electron acceptor occurs efficiently, leading to the generation of a strong oxidizing PS+• and an anionic radical of the acceptor, which further transfers an electron to oxygen to form O2-•. In addition, these photodynamic agents induce direct photocatalytic oxidation of NADH with a turnover frequency as high as 53.7 min-1, which offers an oxygen-independent mechanism to damage tumors.