Biomacromolecular carriers based hydrophobic natural products for potential cancer therapy.

Cancer is the second leading cause of death worldwide. It was estimated that 90 % of cancer-related deaths were attributable to the development of multi-drug resistance (MDR) during chemotherapy, which results in ineffective chemotherapy. Hydrophobic natural products plays a pivotal role in the field of cancer therapy, with the potential to reverse MDR in tumor cells, thereby enhancing the efficacy of tumor therapy. However, their targeted delivery is considered a major hurdle in their application. The advent of numerous approaches for encapsulating bioactive ingredients in the nanodelivery systems has improved the stability and targeted delivery of these biomolecules. The manuscript comprehensively analyses the nanodelivery systems of bioactive compounds with potential cancer therapy applications, including liposomes, emulsions, solid lipid nanoparticles (NPs), and polymeric NPs. Then, the advantages and disadvantages of various nanoagents in the treatment of various cancer types are critically discussed. Further, the application of multiple-compbine delivery methods to overcome the limitations of single-delivery have need critically analyzed, which thus could help in the designing nanodrug delivery systems for bioactive compounds in clinical settings. Therefore, the review is timely and important for development of efficient nanodelivery systems involving hydrophobic natural products to improve pharmacokinetic properties for effective cancer treatment.

Fabrication and stability of W/O/W emulsions stabilized by gum arabic and polyglycerol polyricinoleate.

BACKGROUND: In order to study the effect of adsorption of surfactant at the two interfacial layers on emulsion stability, the kinetically stable water-in-oil-in-water (W/O/W) emulsion carriers were prepared using polyglycerol polyricinoleate (PGPR) and gum arabic (GA) as emulsifiers. The relationship between the adsorption of the surfactant and the stability mechanism of the emulsions was elucidated. RESULTS: When the contents of PGPR and GA were low, the interfaces between oil and the inner and outer water phases, respectively, could not be completely covered. However, when the concentration of PGPR was higher than 60 g kg-1 , the excess PGPR was adsorbed on the interface between the oil phase and the outer water phase. When the concentration of GA reached 80 g kg-1 , more GA was adsorbed to the oil-in-water interface. Moreover, the presence of PGPR on the interface could reduce the adsorption capacity of GA. Two types of kinetically stable emulsions were obtained by optimizing the interface composition (60 g kg-1 GA/80 g kg-1 PGPR and 60 g kg-1 PGPR/80 g kg-1 GA). The kinetically stable W/O/W emulsions prepared in this study were successfully used to encapsulate a hydrophilic vitamin (vitamin B12) with an encapsulation efficiency (EE) of 80% and release efficiency (RE) of 95%. The interfacial adsorption GA can accelerate the hydrolysis of fat. CONCLUSION: Overall, this study provides a new strategy for the preparation of W/O/W emulsions, which might be beneficial for application in food, cosmetic, chemical, and pharmaceutical industries. © 2023 Society of Chemical Industry.

Interaction between potassium iodide and bovine serum albumin, ovalbumin and lysozyme under different temperature induction.

In this study, the interaction between potassium iodide and protein molecules under different temperature induction was studied, taking potassium iodide (KI) and protein molecules as a model system. The effects of KI on protein conformation, size, surface charge, binding constant, and binding site were analyzed by fluorescence spectrum, infrared spectrum, and diffusing wave spectroscopy. The results revealed that bovine serum albumin (BSA)/ovalbumin (OVA) and I-1 formed the 1: 1 complex and significantly affected the hydrodynamic radius and spatial structure. This could be attributed to the exposure of tyrosine residues inside the proteins to the polar conditions under increased temperature. The unfolding of protein structures induced the interaction between KI/KCl and proteins. As for BSA and OVA, the particle size and surface charge of the complex increased significantly in the presence of KI/KCl. KI had a strong static quenching effect on the fluorescence of BSA and OVA. Overall, these results provide insights into the physiological effects of iodine ions.

Nonclassical mechanisms to irreversibly suppress ß-hematin crystal growth.

Hematin crystallization is an essential element of heme detoxification of malaria parasites and its inhibition by antimalarial drugs is a common treatment avenue. We demonstrate at biomimetic conditions in vitro irreversible inhibition of hematin crystal growth due to distinct cooperative mechanisms that activate at high crystallization driving forces. The evolution of crystal shape after limited-time exposure to both artemisinin metabolites and quinoline-class antimalarials indicates that crystal growth remains suppressed after the artemisinin metabolites and the drugs are purged from the solution. Treating malaria parasites with the same agents reveals that three- and six-hour inhibitor pulses inhibit parasite growth with efficacy comparable to that of inhibitor exposure during the entire parasite lifetime. Time-resolved in situ atomic force microscopy (AFM), complemented by light scattering, reveals two molecular-level mechanisms of inhibitor action that prevent ß-hematin growth recovery. Hematin adducts of artemisinins incite copious nucleation of nonextendable nanocrystals, which incorporate into larger growing crystals, whereas pyronaridine, a quinoline-class drug, promotes step bunches, which evolve to engender abundant dislocations. Both incorporated crystals and dislocations are known to induce lattice strain, which persists and permanently impedes crystal growth. Nucleation, step bunching, and other cooperative behaviors can be amplified or curtailed as means to control crystal sizes, size distributions, aspect ratios, and other properties essential for numerous fields that rely on crystalline materials.

Aggregation and Growth Mechanism of Ovalbumin and Sodium Carboxymethylcellulose Colloidal Particles under Thermal Induction.

Ovalbumin (OVA)/sodium carboxymethylcellulose (CMC) colloidal particles were prepared with different compactness and morphologies by regulating the interaction between proteins and polysaccharides during heating. Electrostatic interactions between the amine groups of OVA (-NH3+) and carboxyl groups of CMC (-COO-) enhanced complex formation. The protein conformation change benefited the hydrophobic interaction between the particles. Proteins in colloidal particles were unfolded/folded under thermal induction to form aggregates having more ß-sheet structures. When the OVA/CMC ratio was 1:2, the initially loosely connected OVA/CMC aggregation changed into a uniform sphere between 25 and 90 °C. The mass ratio of OVA to CMC within the final colloidal particle (90 °C) was about 1:1.4. The OVA/CMC particle stability was maintained with hydrogen bonding, hydrophobicity, and disulfide bond. When OVA levels were predominant, OVA and CMC developed an approximately hollow sphere. Moreover, the final colloidal particle composition showed the OVA-to-CMC ratio as 3:1 (w/w). OVA bound into colloidal particle pores to increase compactness. Moreover, OVA and CMC bound to the colloidal particle while the particle shrank, thereby increasing the compactness of colloidal particles. There was a significant decrease in ABTS•+ scavenging activity of curcumin compared with that of the particles with a ratio of 1:2. Thus, the rational adjustment of the structure of colloidal particles could effectively enhance their functional characteristics, providing a new way for the controlled release of the active ingredients.

Transition Metal-Promoted Carbon-Silicon Solid Acid Catalysts for the Synthesis and Process Optimization of Benzaldehyde Glycol Acetal.

A series of transition metal (M)-promoted carbon-silicon (C-M-Si; M=Mn, Fe, Co, Ni, Cu, Zn, Zr) solid acid catalysts with designated molar ratio of M/Si=1 : 8 were fabricated and exploited for acetalization of benzaldehyde (BzH) with ethylene glycol (EG). The physical and chemical properties of these C-M-Si catalysts prepared by sol-gel method were characterized by various techniques, namely, SEM, EDS, TGA-DTG, BET, XRD, FTIR, XPS, and NH3 -TPD. Among various examined acidic C-M-Si catalysts, the C-Fe-Si catalyst exhibited the optimal catalytic activity with the benzaldehyde glycol acetal (BEGA) yield of 97.67 %, in excellent agreement with the value (97.88 %) predicted by the response surface methodology (RSM) based on a Box-Behnken design (BBD). C-Fe-Si catalyst with the high catalytic activities and excellent stability and reusability may be ascribed to the suitable acidity and uniform surface distribution of active sites requisite for the acid-catalyzed acetalization reaction.

Microwave-ultrasonic technique development coupled with natural deep eutectic solvents in anthocyanin extraction from perilla leaves (Perilla frutescens var. Acuta).

BACKGROUND: As potent antioxidants, anthocyanins can protect the body from free radicals. However, the traditional solvent extraction method has the disadvantages of requiring a high extraction temperature and long extraction time, so it is necessary to develop an efficient extraction method for anthocyanins. RESULTS: In this study, the technique of natural deep eutectic solvents (DESs) was applied to extract anthocyanins from purple perilla leaves with the aid of microwave-ultrasonic assisted extraction (MUAE). The response surface methodology (RSM), based on the Box-Behnken design (BBD), predicted the maximum extraction yield of anthocyanins to be 619.62 mg (100 g)-1 under the following conditions: x1 (ultrasonic extraction power) = 357.25 W, x2 (time) = 25.62 min, and x3 (temperature) = 57.80 °C. The biological activity of the extract obtained was evaluated by examining its radical-scavenging effect on 1,1-diphenyl-2-picrylhydrazyl, hydroxyl radical, and superoxide anion radicals. Its bacteriostatic impact was investigated on four typical bacteria: Shewanella putrefaciens (S. putrefaciens), Pseudomonas fluorescens (P. fluorescens), Escherichia coli (E. coli), and Staphylococcus aureus (S. aureus). CONCLUSION: The integrated extraction method of DESs with MUAE was efficient, energy-saving, green, and sustainable. © 2022 Society of Chemical Industry.

Improving the Intrinsic Stretchability of Fully Conjugated Polymer for Deep-Blue Polymer Light-Emitting Diodes with a Narrow Band Emission: Benefits of Self-Toughness Effect.

It is challenging to construct the intrinsically stretchable active layer of rigid conjugated polymers (CPs) toward flexible deep-blue light-emitting diodes (FLEDs). Inspired by the self-toughness effect, sacrificial hydrogen bonding (H-bonding) and a cross-linked network synergistically enabled polydiarylfluorene (PFs-NH) films to present efficient deep-blue emission and excellent intrinsic stretchability. In particular, a cross-linked network structure presenting viscoelasticity behaviors, which was successfully inherited into postprocessed films with interchain interpenetration and a crystallinity domain and behaved as energy absorption and dissipation centers, was induced by the interchain H-bonding interaction in toluene (Tol) precursor solutions where the storage moduli (G') gradually exceeded the loss moduli (G″). Subsequently, intrinsic stretchable films with a tensile rate of 30% were prepared from Tol solutions, different from the brittle films from polar solvents. Eventually, narrow band, deep-blue PLEDs showed a maximum EQE of 1.28% and a full width half-maximum (fwhm) of 28 nm. Therefore, the self-toughness effect induced by hierarchical structures will be feasible to obtain high-performance FLEDs.

Preparation, characterization and antibacterial activity of new ionized chitosan.

In order to improve the solubility and antibacterial activity of chitosan and expand its application range, ionized chitosan (ICS) was successfully synthesized from chitosan through methylation and sulfonation reactions in this study. The chemical structures of the polymers were verified by Fourier transform infrared spectroscopy (FTIR) and 1H NMR, and a series of characterizations of the polymer were carried out by analytical methods such as element analysis (EA), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC) and X-ray diffraction (XRD). The results showed that the water solubility of the modified ICS was significantly improved. The introduction of propyl sulfonic acid groups with particle size decreasing and potential increasing greatly improved the antibacterial activity of chitosan, indicating that the ICS had the potential as a water-soluble antibacterial agent.

Effect of microcrystalline cellulose under different hydrolysis durations on the stability of thyme oil emulsion.

The thyme oil emulsion was prepared using a novel type of nanocellulose obtained under different hydrolysis durations. The effect of different cellulose structures on interfacial adsorption properties of emulsion and loading efficiency of thyme oil were analyzed. The results showed that the cellulose particles became more homogeneous and hydrophilic after hydrolysis duration for 10 h. The loading efficiency of thyme oil for all emulsions reached about 80%. The retention rate of thyme oil decreased during the storage period, and rising temperatures will exacerbate the loss of thyme oil. Compared to Hd2, emulsions stabilized by Hd10 exhibited better stability and higher retention at all storage conditions. Cellulose emulsion can increase the dispersion and improve the stability of thyme oil. A smaller cellulose particle could make the emulsion become more stable. The experimental results confirmed that cellulose can be used as a stabilizer to encapsulate and transport hydrophobic active ingredient. PRACTICAL APPLICATION: The study results demonstrated that the emulsion transport system was developed using cellulose nanoparticles prepared by hydrolysis. The system can be used to load hydrophobic active substances (active peptides, curcumin, ß-carotene, essential oils, etc.). It can protect the active substance from environmental damage, enhance water solubility and stability, and improve the bioavailability of the active substance.

Ovalbumin/carboxymethylcellulose colloids: Particle compactness and interfacial stability.

A protein/polysaccharide colloidal particle was prepared via combined complex coacervation and heat-induction. When the ratio of ovalbumin (OVA) to carboxymethylcellulose (CMC) was at 1:2, loose flexible particles (low Df) with low surface hydrophobicity were obtained. Conversely, dense and compact particles (high Df) were easily formed at a higher OVA/CMC ratio. Only in the appropriate OVA/CMC ratio, pH will have a greater impact on the colloidal particles. At the pH value of 4.4, the OVA/CMC ratio had a greater impact on the colloidal particles compared to pH. The emulsion stabilized by loose particles had a mean particle size of 3888 nm and was easily flocculated and creamed. On the other hand, compact particles formed a stable emulsion, which had a higher exponent of Δr2 (0.867) and could resist flocculation during the 7 days storage. As such, the results showed that stable emulsion could be realized by utilizing compact particles as emulsifiers.

The role of glycerol on the thermal gelation of myofibrillar protein from giant squid (Dosidicus gigas) mince.

This work studies the effect of glycerol on the chemical physics of the thermal gelatin of protein from giant squid minced meat. The presence of glycerol induced changes in the nano protein particles (NPP) self-assembled structures. These nanoscale events resulted in dramatic changes on the interactions between proteins when forming gels, with the contribution of ionic interactions increasing by 17% upon gelation, that of hydrogen bonds reducing by 50%, that of hydrophobic interactions decreasing by 45%, and that of disulphide bonding increasing by 18%. Glycerol also induced cluster formation in myofibrillar solutions. As a result, incorporation of glycerol increased springiness, resilience, and adhesiveness of the formed gels by 13%, 25%, and 370% respectively. The heating gelation of myofibrillar proteins was monitored at various temperatures via recording the elastic and storage moduli. Rheology and micro-rheology studies revealed that the presence of glycerol increased G' and G″ of thermally-gelled giant squid meat.

The influence of KCl concentration on the gelation of myofibrillar protein giant squid (Dosidicus gigas) due to molecular conformation change.

Introduction: Protein gelation process is of importance in food industry. The objective of this study is to investigate the influence of salt concentration variation, which induced protein conformation change, on protein's intermolecular interactions and its gelation process. Methods: Paramyosin has been separated and purified from myofibrillar protein extracted from giant squid. Then Giant squid's paramyosin molecular mass and intermolecular interactions were quantified by means of light scattering techniques. Finally, the micro-rheology study via diffusing wave spectroscopy (DWS) technique revealed that this conformation change dramatically affected myofibrillar protein gelation process. Results: The obtained apparent molecular weight (ca 2 × 105 g/mol) suggested that protein molecules existed as dimers, while the second virial coefficient A2 significantly reduced from -3.98456 × 10-5 to -5.07575 × 10-4 ml mol/g2 when KCl concentrated from 0.15 to 1 mol/L. Light scattering data also suggest that paramyosin dimers are stiff, with a persistence length of 120 nm, almost the length of a molecule and independent of salt concentration. Mean-square displacement (MSD) of tracer particles at 5 temperatures with 4 salt concentrations displayed that this conformation change had dramatic effect. Therefore, G' and G" were remarkably altered with at least one order of magnitude difference owing to this event occurrence. Conclusions: Paramyosin conformation change due to KCl concentrated enhances attractive interactions with apparent molecular mass increase, which resulted in majority paramyosin molecules (> 99%) in dimeric form and promoted aggregates formation. DWS technique revealed that the conformation change dramatic affected this process characterized by the correlation functions, MSD, and G' and G". This study brings forward data on understanding the effect of a major salt supplement, KCl, on the chemical physics of a major muscle protein.

Formation of ß-Lactoglobulin Self-Assemblies via Liquid-Liquid Phase Separation for Applications beyond the Biological Functions.

Proteins are like miracle machines, playing important roles in living organisms. They perform vital biofunctions by further combining together and/or with other biomacromolecules to form assemblies or condensates such as membraneless organelles. Therefore, studying the self-assembly of biomacromolecules is of fundamental importance. In addition to their biological activities, protein assemblies also exhibit extra properties that enable them to achieve applications beyond their original functions. Herein, this study showed that in the presence of monosaccharides, ethylene glycols, and amino acids, ß-lactoglobulin (ß-LG) can form assemblies with specific structures, which were highly reproducible. The mechanism of the assembly process was studied through multi-scale observations and theoretical analysis, and it was found that the assembling all started from the formation of solute-rich liquid droplets via liquid-liquid phase separation (LLPS). These droplets then combined together to form condensates with elaborate structures, and the condensates finally evolved to form assemblies with various morphologies. Such a mechanism of the assembly is valuable for studying the assembly processes that frequently occur in living organisms. Detailed studies concerning the properties and applications of the obtained ß-LG assemblies showed that the assemblies exhibited significantly better performances than the protein itself in terms of autofluorescence, antioxidant activity, and metal ion absorption, which indicates broad applications of these assemblies in bioimaging, biodetection, biodiagnosis, health maintenance, and pollution treatment. This study revealed that biomacromolecules, especially proteins, can be assembled via LLPS, and some unexpected application potentials could be found beyond their original biological functions.

Preparation of ultra-long stable ovalbumin/sodium carboxymethylcellulose nanoparticle and loading properties of curcumin.

OVA (ovalbumin)/CMC (sodium carboxymethylcellulose) nanoparticles are prepared by combining complex coacervation and thermal induction. The effect of different parameters on stability of OVA/CMC nanoparticles (different ratios, pH, temperature, salt concentration and storage time) is investigated. And then the loading and stabilizing mechanism of particles on curcumin are further analyzed. After heating, OVA and CMC in particle could further cross-linking and a highly salt-tolerant and ultra-long stable nanoparticle can be formed. OVA/CMC nanoparticle with the loose structure of wool ball could effectively load curcumin with the loading content and loading efficiency of 36.40 and 95.40%, 36.30 and 92.82%, 36.0 and 94.48% for the ratios of 1:2, 1:1 and 2:1, respectively. Curcumin-loaded of OVA/CMC nanoparticles show good DPPH· scavenging activity, Ferric-reducing ability and ABTS+ scavenging activity compared with curcumin/water. The results can be useful for designing food and beverage particle with improving bioactive substances functional properties.

A predictive model for astringency based on in vitro interactions between salivary proteins and (-)-Epigallocatechin gallate.

Astringency is an important quality attribute of green tea infusion, and (-)-Epigallocatechin gallate (EGCG) is the main contributor to astringency. Turbidity was used to predict the intensity of astringency for EGCG. The interactions between the selected proteins and EGCG, and the impacts of temperature, pH, protein structure, and EGCG concentration were studied. Mucin was selected as the protein in study for the prediction of EGCG astringency intensity. A predictive model (R2 = 0.994) was developed based on the relationship between the astringency of EGCG and the turbidity of EGCG/mucin mixtures at pH 5.0 and 37 °C. The fluorescence quenching analyses showed the interactions between EGCG and the selected proteins, which induced the reversible protein molecule conformational changes. The interactions were considered as the main reason that causes the astringency of tea infusions. The results provided a biochemical approach to explore the sensory qualities of green tea.

Properties of nano protein particle in solutions of myofibrillar protein extracted from giant squid (Dosidicusgigas).

This work studied the quantitation of myofibrillar protein isolated from giant squid by three methods (Bradford, biuret, and direct ultraviolet absorbance). The results were examined in relation to compositional size exclusion chromatography, static light scattering, zeta-potential and thermal analysis; comparisons between the apparent vs. the true protein concentration revealed the existence of disk-like nano protein particles (NPP) with a height of 2-3 nm, diameters ranging from several tens nm to 140 nm, and fractal dimensions df of less than 1.3. In order to probe the heterogeneity of NPP particles, their properties were studied under consecutive dilutions: the df decreased from 1.265 to 1.087, the zeta-potential increased from -4.55 mV to -1.83 mV, the denaturation temperature reduced from 63.9 °C to 58.6 °C, and the endothermic enthalpy reduced from 0.529 J s-1 to 0.362 J s-1. In addition, ca. 90% protein molecules in solution were aggregated to form NPP.

Structural characteristics and digestibility of bovine skin protein and corn starch extruded blend complexes.

The interaction mechanism and digestibility of bovine skin protein (BSP)/corn starch (CS) blend complexes prepared by single screw extrusion were investigated. The effects of temperature and BSP/CS ratios on the physicochemical properties of BSP/CS blend complexes were analyzed. The results showed that the BSP/CS blend complexes extruded at a ratio of 3:7 had higher bulk density, texture and RVA viscosity compared with that of 7:3 and 5:5. It was mainly because the CS improved the formation of BSP/CS gel network structure through the screw extrusion. BSP and CS achieved an optimal entanglement at this ratio, potentially making pets play longer. The interaction between the -COOH of CS and the -NH3 of BSP during the process of extrusion was detected. The micrograph of blend system at ratio of 5:5 showed looser and special mosaic structure compared with other ratios, and further led to greater digestion rate. So we can design products with digestibility or longer play time by adjusting different proportions.

Chemical physics of whey protein isolate in the presence of mucin: From macromolecular interactions to functionality.

Oral processing, textural perception and functionality of colloidal foods are strongly influenced by the interactions between the salivary mucins and the food proteins. This work studies the physico-chemical aspects of mixtures of a typical food protein, whey protein isolate (WPI) and mucin. Phase separations result from aggregation between the two components at pH 7 and at pH 3. ζ-potential and fluorimetry data show that electrostatics contribute to entropically-driven interactions at pH 3, while at pH 7, two different non-electrostatic interactions, an entropically-driven and an enthalpically-driven one lead to aggregation and phase separation. Substitution of WPI with increasing mucin concentrations at pH 7 results in a marked increase of the shear viscosity in comparison with pH 3. Mucin enhances the extensional viscosity in a similar fashion, e.g. the incorporation of mucin into a WPI system at 6:4 ratio increases the extensional viscosity ≥ 3-fold (0.27-0.85 Pa s) and ≥2-fold (0.38-0.89 Pa s) at pH 3 and pH 7, respectively. These results indicate a notable increase of the extensional over shear viscosity ratio (Trouton's ratio). The above highlight the effect of the molecular-level interactions between food and salivary macromolecules on phase behavior and flow during oral processing.

Characterization of structure and stability of emulsions stabilized with cellulose macro/nano particles.

The characterization of emulsions covered with cellulose particles prepared under varying hydrolysis durations investigated. The results showed that with the increasing hydrolysis durations, the particle size distribution profiles of emulsion stabilized cellulose particles shifted to a lower particle size. This was primarily because at longer hydrolysis durations, a larger number of particles per interfacial area were expected to be adsorbed at the interface of oil droplets. At hydrolysis durations of 6 and 10 h, the mean particle diameter of emulsion had an increase of 20-30 nm after 7 days and showed good stability with storage time, which can be attributed to a relatively thick interface layer. Emulsions stabilized by cellulose particles prepared at hydrolysis durations of 6 and 10 h showed good stability against changes in pH and NaCl concentration. These results can be useful for designing food and beverage Pickering emulsions with the improved bioavailability of functional nutrients.