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In this study, the effects of different ultrasonic treatment intensities (57, 170, and 283 W/cm2) on the chemical composition, molecular chain characteristics, crystal structure, micromorphology, interfacial adsorption behavior and emulsifying properties of sugar beet pectin (SBP) were investigated. Ultrasonic treatment did not change the types of SBP monosaccharides, but it had impacts on their various monosaccharide contents. Moreover, the feruloylated, acetyl, and methoxy groups of SBP also undergo varying degrees of changes. The increase in ultrasonic treatment intensity led to transition in the molecular chain conformation of SBP from rigid semi-flexible chains to flexible chains, accompanied by modification in its crystal structure. Microstructural analysis of SBP confirmed the significant change in molecular chain conformation. Modified SBP could form an elastic interfacial film with higher deformation resistance on the oil-water interface. The SBP sample modified with 170 W/cm2 exhibited better emulsifying properties owing to its better interfacial adsorption behavior. Moreover, the emulsions prepared with modified SBP exhibited better stability capability under different environmental stresses (pH value, salt ion concentration, heating temperature and freeze-thaw treatment). The results revealed that the ultrasonic technology is useful to improve the emulsifying properties of SBP.
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Beta vulgaris , Pectinas , Beta vulgaris/química , Pectinas/química , Emulsiones/química , Ondas Ultrasónicas , Adsorción , Conformación Molecular , Concentración de Iones de HidrógenoRESUMEN
Transmembrane peptides play important roles in many biological processes by interacting with lipid membranes. This study investigates how the transmembrane domain of the influenza A virus M2 protein, M2TM, affects the structure and mechanics of model lipid bilayers. Atomic force microscopy (AFM) imaging revealed small decreases in bilayer thickness with increasing peptide concentrations. AFM-based force spectroscopy experiments complemented by theoretical model analysis demonstrated significant decreases in bilayer's Young's modulus (E) and lateral area compressibility modulus (KA). This suggests that M2TM disrupts the cohesive interactions between neighboring lipid molecules, leading to a decrease in both the bilayer's resistance to indentation (E) and its ability to resist lateral compression/expansion (KA). The large decreases in bilayer elastic parameters (i.e., E and KA) contrast with small changes in bilayer thickness, implying that bilayer mechanics are not solely dictated by bilayer thickness in the presence of transmembrane peptides. The observed significant reduction in bilayer mechanical properties suggests a softening effect on the bilayer, potentially facilitating membrane curvature generation, a crucial step for M2-mediated viral budding. In parallel, our Raman spectroscopy revealed small but statistically significant changes in hydrocarbon chain vibrational dynamics, indicative of minor disordering in lipid chain conformation. Our findings provide useful insights into the complex interplay between transmembrane peptides and lipid bilayers, highlighting the significance of peptide-lipid interactions in modulating membrane structure, mechanics, and molecular dynamics.
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In this study, an acidic polysaccharide (FVP-7 A) was isolated from Fucus vesiculosus by DEAE-Sepharose™ fast flow. The chemical composition, glycosidic bonds and in vitro fecal fermentation characteristics of FVP-7 A were studied. Results shown that FVP-7 A was a homogenous polysaccharide with average molecular weight of 30.94 kDa. Combined with FT-IR, monosaccharide composition, methylation and NMR analysis, the glycosidic bonds of FVP-7 A mainly composed of â4)-ß-D-Manp-(1â, â3)-α-L-Fucp-(1â, α-D-Manp-(1â, â3)-ß-D-Manp-(1 â and â4,6)-α-D-Manp-(1â. The zeta potential and atomic force microscopy images indicated that FVP-7 A could exist stably as a single chain-like structure in dilute solution. After gut fermentation, FVP-7 A was utilized and promoted multiple short-chain fatty acids production, especially acetic acid, butyric acid and valeric acid. For prebiotics, FVP-7 A significantly increased the relative abundance of short-chain fatty acids producing bacteria such as Bacteroides, Lachnospira, Faecalibacterium, Ruminococcus, Oscillospira and Dialister, and inhiited the growth of the harmful bacteria Shigella. These results indicated that FVP-7 A could be used as a potential dietary supplement to improve intestinal health.
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Fermentación , Fucus , Microbioma Gastrointestinal , Polisacáridos , Polisacáridos/química , Polisacáridos/farmacología , Humanos , Fucus/química , Ácidos Grasos Volátiles/metabolismo , Peso Molecular , Prebióticos , Heces/microbiología , Monosacáridos/análisis , MetilaciónRESUMEN
Curdlan is a unique (1,3)-ß-D-glucan with bioactivity and exceptional gelling properties. By chemical functionalization such as carboxymethylation, the physicochemical properties of curdlan can be significantly tailored. However, how the carboxymethylation extent of curdlan affects its rheology and gelation characteristics has yet to be fully understood. Herein, we investigated the impact of the degree of substitution (DS, ranging from 0.04 to 0.97) on the rheological and gelation behavior of carboxymethylated curdlan (CMCD). It was found that CMCD with DS below 0.20, resembling native curdlan, still retained its gelling capability. As the DS increased beyond 0.36, there was a significant increase in its water solubility instead of gelation, resulting in transparent solutions with steady/complex viscosities adhering to the Cox-Merz rule. Moreover, CMCD with high DS demonstrated the ability to undergo in-situ gelation in the presence of metal ions, attributed to the nonspecific electrostatic binding. Additionally, in vitro cytocompatibility testing showed positive compatibility across varying DS in CMCD. This research offers a holistic understanding of the viscosifying and gelling behaviors of CMCD with varying DS, thereby fostering their practical application as thickeners and gelling agents in fields ranging from food and biomedicine to cosmetics and beyond.
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beta-Glucanos , beta-Glucanos/química , Glucanos/química , Geles/química , Agua , ReologíaRESUMEN
Sodium alginate was associated to a ternary solvent composed of fructose, glycerol, and water in a 1:1:5 M ratio (FGW), classified as a natural Low Transition Temperature Mixture (LTTM), to generate various soft materials. The rheological properties of mixtures composed of sodium alginate and FGW were thoroughly analyzed and compared to their aqueous analogues. FGW-based solutions present a pronounced shear-thinning character combined to high viscosity, up to 8000 Pa.s. The overlap concentrations and intrinsic viscosities values evidence a good solvent character of FGW for alginate polymer chains. The increase of alginate concentration in FGW leads to materials with enhanced elasticity (up to 6000 Pa) and high energy of activation (55 kJ/mol). Interestingly, the addition of divalent calcium cations in FGW according to two optimized experimental protocols, allows for the generation of never described ionotropic gels in FGW under various shapes as bulk gels or beads of gels able to encapsulate extracted vegetal actives that are used in the cosmetic industry. Thus, FGW appears as a well-suited solvent of alginate to design a broad range of new biobased soft materials.
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In this study, the ginger polysaccharides extracted from hot water (HW-G) were modified with subcritical water (SW-G) to effectively regulate their immune activity, and the relationship between polysaccharide chain conformation and immune activity at different subcritical water temperatures was investigated. The results indicated that, compared with HW-G, the xylose and mannose were degraded at high temperatures. The molecular weight of ginger polysaccharide decreased from 1.083 × 106 g/mol to 3.113 × 105 g/mol after subcritical water modification (100-160 °C). The chain conformation transitioned from rigid rod chain to semi-rigid chain and eventually to random coil. The degree of relaxation of the polysaccharide chains showed a continuous increase trend. Additionally, ginger polysaccharide modified by subcritical water at 130 °C was found to promote the proliferation and phagocytosis of 264.7 cells more obviously and signally increase the secretion levels of NO, IL-6, TNF-α and IL-1ß. When the subcritical water temperature exceeds 130 °C, the activity of ginger polysaccharide begins to decline rapidly. These findings demonstrate a close correlation between polysaccharide chain conformation and immunomodulatory activity, confirming the feasibility of the subcritical water temperature effect as a means of immune activity regulation, which opens up a new approach to obtaining highly active polysaccharides.
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Agua , Zingiber officinale , Temperatura , Polisacáridos/farmacología , AntioxidantesRESUMEN
In this study, three acidic polysaccharides (OFPP-1, OFPP-2 and OFPP-3) were isolated from the pulps of Opuntia dillenii Haw. fruits, and their chain conformations, physicochemical and rheological properties were investigated. The molecular weight and conformational parameters (Mw, Mn, Mz, Rg and Rh) of OFPPs in 0.1 M NaNO3 solution were detected by HPSEC-MALLS-RI. In addition, based on the parameters ρ and v, it was concluded that these three polysaccharide chains exhibited sphere-like conformation in 0.1 M NaNO3 solution, which was consistent with AFM and TEM observations. Furthermore, the Congo Red experiment showed that OFPP-2 had a triple-helix structure, which may be conducive to its biological activity. This study also found that OFPPs were semi-crystalline structures with high thermal and pH stability. The rheological analyses indicated that the apparent viscosity of OFPPs solutions exhibited concentration-, temperature-, and pH-dependence, and the viscoelasticity of them was affected by molecular characteristics and concentration. The results of this study are helpful to elucidate the structure-activity relationship of OFPPs. Moreover, this study can provide theoretical reference for the application of OFPPs as bioactive ingredients or functional materials in the food, pharmaceutical and cosmetic industries and the development and utilization of the O. dillenii Haw. fruits resource.
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Opuntia , Opuntia/química , Frutas/química , Polisacáridos/química , ViscosidadRESUMEN
Tuning the optoelectronic properties of donor-acceptor conjugated polymers (D-A CPs) is of great importance in designing various organic optoelectronic devices. However, there remains a critical challenge in precise control of bandgap through synthetic approach, since the chain conformation also affects molecular orbital energy levels. Here, D-A CPs with different acceptor units are explored that show an opposite trend in energy band gaps with the increasing length of oligothiophene donor units. By investigating their chain conformation and molecular orbital energy, it is found that the molecular orbital energy alignment between donor and acceptor units plays a crucial role in dictating the final optical bandgap of D-A CPs. For polymers with staggered orbital energy alignment, the higher HOMO with increasing oligothiophene length leads to a narrowing of the optical bandgap despite decreased chain rigidity. On the other hand, for polymers with sandwiched orbital energy alignment, the increased band gap with increasing oligothiophene length originates from the reduction of bandwidth due to more localized charge density distribution. Thus, this work provides a molecular understanding of the role of backbone building blocks on the chain conformation and bandgaps of D-A CPs for organic optoelectronic devices through the conformation design and segment orbital energy alignment.
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Dietary carbohydrates are unexploited in the by-products of economically valuable Phyllostachys pracecox bamboo shoots. A residue-derived polysaccharide (PBSR1) was aqueously extracted from the processing waste of this bamboo shoot species. Its primary structure and advanced conformation were elucidated by a combined analysis of spectroscopy, chromatography, 2D nuclear magnetic resonance, laser light scattering and atomic microscopy. The results indicated PBSR1 was a triple-helix galactan consisting of â6)-ß-D-Galp and â3)-ß-D-Galp in linear with an 863 KD molecular weight (Mw). The relationship between the radius of gyration (Rg) and intrinsic viscosity ([η]) on Mw were established as Rg = 1.95 × 10-2Mw0.52±0.03 (nm) and [η] = 9.04 × 10-1Mw0.56±0.02 (mL/g) for PBSR1 in saline solution at 25 °C, which indicated it adopted a triple-helix chain shape with a height of 1.60 ± 0.12 nm supported by a red shift of λmax in Congo red analysis. The thermodynamic test (TG) displayed that it had excellent thermal stability for the food industry. Further, those unique structure features furnish PBSR1 on antioxidation with EC50 of 0.65 mg/mL on DPPH· and an ORAC value of 329.46 ± 12.1 µmol TE/g. It also possessed pronounced immunostimulation by up-regulating pro-inflammatory signals including NO, IL-6, TNF-α and IL-1ß in murine cells. Our studies provided substantial data for the high-valued application of residues and a better understanding of the structure-function relationship of polysaccharide.
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The traditional κ-carrageenan (κCG)-based hydrogel obtained from hot water can rupture easily under mechanical loading. To address this vulnerability, here we presented a robust all-κCG hydrogel without employing the second synthetic network. By simply regulating the polymer chains from random coil to stiff chain conformation in NaOH/urea solvent system via the freeze-thawing process, the as-prepared hydrogel with homogeneous structure can display an enhanced stretchability from 42.1 to 156 %, while maintaining the similar fracture stress. Moreover, upon the stepwise mechanical training and subsequent incubation in KCl aqueous solution, more helical segments of κCG were aligned and involved into the association domains, thus leading to the increment in both the crystallinity and anisotropy. Consequently, a fast self-strengthening behavior occurred, and a more stretchable (fracture strain up to 396 %), strong (stress â¼ 0.55 MPa) and tough (â¼1.52 MJ m-3) κCG hydrogel was obtained. In comparison to the traditional one, the fracture strain and toughness are increased by 8.5 and 11.5 times, respectively. In addition, this κCG hydrogel can demonstrate good recovery and shape-memory behaviors under medium deformation. Hence, this tough all-κCG hydrogel is expected to be tailored into the biomaterials as the wearable device, artificial tendon, and cartilage in the future.
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Duloxetine hydro-chloride (trade name Cymbalta) is marketed as a single enanti-omer (S)-N-methyl-3-(naphthalen-1-yl-oxy)-3-(thio-phen-2-yl)propyl-am-in-ium chloride, C18H20NOS+·Cl-, which is twice as effective as the (R)-enanti-omer in serotonin uptake. Here, we report the crystal structure of duloxetine hydro-chloride in its racemic form (space group Pna21), where it shows significant differences in the mol-ecular conformation and packing in its extended structure compared to the previously reported (S)-enanti-omer crystal structure. Mol-ecules of this type, comprising aromatic groups with a single side chain terminated in a protonated secondary amine, are commonly found in active anti-depressants. A Cambridge Structural Database survey of mol-ecules with these features reveals a strong correlation between side-chain conformation and the crystal packing: an extended side chain leads to mol-ecules packed into separated layers of hydro-phobic and ionic hydro-philic phases. By comparison, mol-ecules with bent side chains, such as racemic duloxetine hydro-chloride, lead to crystal-packing motifs where an ionic hydro-philic phase is encapsulated within a hydro-phobic shell.
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Fucoidans are valuable marine polysaccharides with various bioactivities and physicochemical properties. However, its digestive properties, mucoadhesive properties, and bioactivity in the gastrointestinal tract are still unclear. In this study, simulated digestion, fecal fermentation in vitro, and rheology models were utilized to investigate the chain conformation, influence on gut microbiota, and mucin adhesive properties of fucoidan from the sea cucumber Thelenota ananas (Ta-FUC). The results showed that Ta-FUC was nondigestible with a temporary decrease in molecular weight in gastric conditions, accompanied by the chain conformation becoming more flexible. Moreover, Ta-FUC exhibited strong mucin adhesive function in the simulated intestinal environment, with supramolecular disulfide, hydrogen, and hydrophobic interactions in order of intensity. During fermentation, Ta-FUC was degraded by the intestinal flora to produce various short-chain fatty acids and promoted the relative abundance of Bacteroidota and Firmicutes, reducing the proportion of Proteobacteria. Therefore, these results indicate that Ta-FUC could be a potential prebiotic and ingredient for developing targeted delivery systems in the functional food and pharmaceutical industries.
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Microbioma Gastrointestinal , Pepinos de Mar , Animales , Intestinos , Pepinos de Mar/química , Polisacáridos/química , FermentaciónRESUMEN
Substrate side chain conformation impacts reactivity during glycosylation and glycoside hydrolysis and is restricted by many glycosidases and glycosyltransferases during catalysis. We show that the side chains of gluco and manno iminosugars can be restricted to predominant conformations by strategic installation of a methyl group. Glycosidase inhibition studies reveal that iminosugars with the gauche,gauche side chain conformations are 6- to 10-fold more potent than isosteric compounds with the gauche,trans conformation; a manno-configured iminosugar with the gauche,gauche conformation is a 27-fold better inhibitor than 1-deoxymannojirimycin. The results are discussed in terms of the energetic benefits of preorganization, particularly when in synergy with favorable hydrophobic interactions. The demonstration that inhibitor side chain preorganization can favorably impact glycosidase inhibition paves the way for improved inhibitor design through conformational preorganization.
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1-Desoxinojirimicina , Glicósido Hidrolasas , Conformación Molecular , Glicósido Hidrolasas/metabolismo , Glicósidos , Inhibidores Enzimáticos/químicaRESUMEN
Ophiopogonis Radix polysaccharides with various bioactivities have caught people's attention in the pharmaceutical and functional food industries. It is necessary to reveal their structures, chain conformations, and solvent behaviors. A neutral polysaccharide named ORP-1 with molecular weight of 3667 Da was obtained from Ophiopogonis Radix. It was composed of d-fructofuranose and d-glucopyranose in the ratio of 0.85:0.15. Methylation, FT-IR and NMR analysis indicated ORP-1 consisted of 2,6-linked-Fruf units as the main chain and 1-linked-Glcp residue at the end. Congo red assay showed ORP-1 had no triple-helix structure. The observation of TEM and AFM found ORP-1 could self-assemble to form colloidal aggregate in water. This phenomenon was verified using CMC determination and MD simulation. Furthermore, intermolecular hydrogen bonds and hydrophobic interactions would be the main forces driving the aggregate. These results provided reference for the study of the chain conformation and behavior of polysaccharides in aqueous solution.
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Rojo Congo , Polisacáridos , Humanos , Espectroscopía Infrarroja por Transformada de Fourier , Polisacáridos/química , Agua , Extractos Vegetales/química , Solventes , Peso MolecularRESUMEN
In this study, ultrasonic effects on structure, chain conformation and morphology of pectin extracted from Premna microphylla Turcz (PEP) and its probable mechanism were investigated. In the process of ultrasonic treatments, the chains of PEP were fractured rapidly within the initial 10 min and then the degradation rate gradually slowed down. The primary structure of PEP nearly remained unchanged after ultrasonic degradation. The rigid semi-flexible chains of PEP were converted into flexible chains, flexible coils, even compact coils. Sonication at low intensity for short time made PEP molecular chains curly collapse and tighten up. Long duration sonication at high intensity generated excessive small rigidness segments that mutually aggregated because of hydrogen bonds and inhibited the self-coiling of PEP chains. Atomic force microscopy (AFM) analysis supported the conformation transition of PEP chains. The results provided a fundamental basis for orientation design and process control of PEP structure.
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Lamiaceae , Pectinas , Enlace de Hidrógeno , Lamiaceae/química , Conformación Molecular , Pectinas/química , UltrasonidoRESUMEN
The present study aimed to evaluate the influence of ultrasound assisted H2O2/ascorbic acid reaction on the structural characteristic and immunostimulatory activity of a ß-D-glucan isolated from D. indusiata, so as to reveal its potential structure-immunostimulatory activity relationship. A purified ß-D-glucan, named as DP, was quickly isolated from D. indusiata, and further identified as a 1,3-ß-D-glucan with 1,6-ß-D-Glcp as branched chains, which exhibited a rigid rod chain conformation in 0.9 % (w/v) of NaCl solution. Furthermore, results showed that the primary structure of DP was overall stable after the degradation by ultrasound assisted H2O2/ascorbic acid reaction. However, the molar mass and chain conformation of DP obviously changed. In addition, DP and its degraded products exerted remarkable immunostimulatory activity in vitro and in vivo, which could activate the nuclear factor-κB (NF-κB) signaling pathway through toll-like receptor 4 (TLR4). Indeed, the immunostimulatory activity of DP was closely-correlated to its molar mass and chain conformation. An appropriate degradation of molar mass could promote its immunostimulatory activity. While the transformation of chain conformation from rigid rod to random coil could cause the significant decrease of its immunostimulatory activity. These findings are beneficial to better understanding the structure-immunostimulatory activity relationship of ß-D-glucans from edible mushrooms.
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Glucanos , beta-Glucanos , Ácido Ascórbico , Basidiomycota , Glucanos/química , Glucanos/farmacología , Peróxido de Hidrógeno , FN-kappa B , Cloruro de Sodio , Receptor Toll-Like 4 , beta-Glucanos/química , beta-Glucanos/farmacologíaRESUMEN
The aim of this study was to investigate the effects of ultrasound with different frequency modes on the chemical structure, chain conformation, and immune activity of lentinan from Lentinus edodes; the structure-activity relationship of lentinan was also discussed. The results showed that, compared with original lentinan (extracted using hot water), although ultrasonic treatment did not change the monosaccharide composition and main functional groups of lentinan, it significantly changed its chain conformation. Especially at 60, 40/60, and 20/40/60 kHz, according to atomic force microscopy and solution chain conformation parameters, lentinan transformed from a rigid triple-helix chain to a flexible single-helix chain, and the side-chain was severely broken. Under this condition, lentinan had the worst immune activity. However, at 20/40 and 20/60 kHz, the rigid triple-helix chain transformed into a loose and flexible triple-helix chain, showing the strongest immune activity. These results indicated that dual-frequency ultrasound had significant effects on the conformation of lentinan, and the conformation characteristics of polysaccharide chain such as spiral number, stiffness and flexibility, and side-chain played an important role in immune activity. This study shows the great potential of ultrasound with different frequency modes in carbohydrate food processing, which may have important reference value and practical significance.
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A novel water-soluble mannogalactan (SSPS1) with an average molecular weight of 2.04 × 104 Da was obtained from the fruiting bodies of the Sanghuangporus sanghuang. It revealed that SSPS1 was composed of d-galactose, d-mannose, l-fucose, 3-O-methylgalactose and d-glucose in a ratio of 6.2:3.9:3.1:2.1:1.0. The structural elucidation of SSPS1 consisted of 1, 6-linked α-D-Galp, 1, 6-linked α-D-Manp and 1, 6-linked 3-O-methyl-α-D-Galp backbone with branching at O-2 of 1, 6-α-D-mannosyl residues by α-L-Fucp and α-D-Glcp units. The conformational parameters suggested that a flexible chain conformation of SSPS1 in solution based on light scattering and atomic force microscopy imaging. Intriguingly, it presented potent anticancer activity on HepG2 cell with Rq and Ra values increased dramatically up to 73.93 nm and 53.92 nm compared with the control. The analysis of flow cytometry indicated SSPS1 could induce the apoptosis of HepG2 cells and arrest them via S phase. Western blot assay further uncovered that apoptosis process was triggered by SSPS1 via a mitochondria-mediated signaling pathway, which was evidenced by an increased ratio of Bax/Bcl-2, the release of cytochrome c and the strong activation of caspase-3 and 9. Taken together, these results suggested that SSPS1 might be applied in functional food as an anticancer agent.
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Ascomicetos , Basidiomycota , Cuerpos Fructíferos de los Hongos , Células Hep G2 , HumanosRESUMEN
Fluorescence resonance energy transfer (FRET) is a non-invasive characterization method for studying molecular structures and dynamics, providing high spatial resolution at nanometer scale. Over the past decades, FRET-based measurements are developed and widely implemented in synthetic polymer systems for understanding and detecting a variety of nanoscale phenomena, enabling significant advances in polymer science. In this review, the basic principles of fluorescence and FRET are briefly discussed. Several representative research areas are highlighted, where FRET spectroscopy and imaging can be employed to reveal polymer morphology and kinetics. These examples include understanding polymer micelle formation and stability, detecting guest molecule release from polymer host, characterizing supramolecular assembly, imaging composite interfaces, and determining polymer chain conformations and their diffusion kinetics. Finally, a perspective on the opportunities of FRET-based measurements is provided for further allowing their greater contributions in this exciting area.
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Transferencia Resonante de Energía de Fluorescencia , Polímeros , Transferencia Resonante de Energía de Fluorescencia/métodos , Polímeros/química , Micelas , Estructura Molecular , DifusiónRESUMEN
Intestinal dysbiosis is one of the major causes of the occurrence of metabolic syndromes, such as obesity, diabetes, nonalcoholic fatty liver disease, and cardiovascular diseases. Polysaccharide-based microbial therapeutic strategies have excellent potential in the treatment of metabolic syndromes, but the underlying regulatory mechanisms remain elusive. Identification of the internal regulatory mechanism of the gut microbiome and the interaction mechanisms involving bacteria and the host are essential to achieve precise control of the gut microbiome and obtain valuable clinical data. Polysaccharides cannot be directly digested; the behavior in the intestinal tract is considered a "bridge" between microbiota and host communication. To provide a relatively comprehensive reference for researchers in the field, we will discuss the polysaccharide extraction and purification processes and chemical and structural characteristics, focusing on the polysaccharides in gut microbiota through the immune system, gut-liver axis, gut-brain axis, energy axis interactions, and potential applications.