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Journal of the American Chemical Society Jul 2024Construction of mesoporous frameworks by noncovalent bonding still remains a great challenge. Here, we report a micelle-directed nanocluster modular self-assembly...
Construction of mesoporous frameworks by noncovalent bonding still remains a great challenge. Here, we report a micelle-directed nanocluster modular self-assembly approach to synthesize a novel type of two-dimensional (2-D) hydrogen-bonded mesoporous frameworks (HMFs) for the first time based on nanoscale cluster units (1.0-3.0 nm in size). In this 2-D structure, a mesoporous cluster plate with ∼100 nm in thickness and several micrometers in size can be stably formed into uniform hexagonal arrays. Meanwhile, such a porous plate consists of several (3-4) dozens of layers of ultrathin mesoporous cluster nanosheets. The size of the mesopores can be precisely controlled from 11.6 to 18.5 nm by utilizing the amphiphilic diblock copolymer micelles with tunable block lengths. Additionally, the pore configuration of the HMFs can be changed from spherical to cylindrical by manipulating the concentration of the micelles. As a general approach, various new HMFs have been achieved successfully via a modular self-assembly of nanoclusters with switchable configurations (nanoring, Keggin-type, and cubane-like) and components (titanium-oxo, polyoxometalate, and organometallic clusters). As a demonstration, the titanium-oxo cluster-based HMFs show efficient photocatalytic activity for hydrogen evolution (3.6 mmol gh), with a conversion rate about 2 times higher than that of the unassembled titanium-oxo clusters (1.5 mmol gh). This demonstrates that HMFs exhibited enhanced photocatalytic activity compared with unassembled titanium-oxo clusters units.
PubMed: 38916547
DOI: 10.1021/jacs.4c03538 -
Nano Letters Jun 2024Targeting telomere maintenance has emerged as a promising strategy for hepatocellular carcinoma (HCC) treatment. However, given the duality of the telomere-telomerase...
Targeting telomere maintenance has emerged as a promising strategy for hepatocellular carcinoma (HCC) treatment. However, given the duality of the telomere-telomerase axis in telomere maintenance, a comprehensive strategy is urgently needed. Herein, we develop a poly(amino acid) (D-PAAs)-based strategy for spatiotemporal codelivery of telomerase inhibitor, BIBR1523, and AKT inhibitor, isobavachalcone. By leveraging D-PAAs' modifiability, we synthesize polymer-inhibitor conjugates (PB and PI) and a folic acid-decorated tumor-targeting vector (PF). These building blocks undergo micellization to fabricate a codelivery nanomedicine (P-BI@P-FA) by exploiting D-PAAs' noncovalent assembly. P-BI@P-FA improves the pharmacokinetics, tumor selectivity, and bioavailability of small molecule inhibitors and initiates a dual telomere-specific inhibition by combining telomerase deactivation with telomere disruption. Furthermore, a hybrid tumor-targeting magnetic nanosystem is designed using D-PAAs and manganese dioxide to showcase magnetic resonance imaging capacities. Our D-PAAs-based strategy addresses the pressing need for telomere-specific HCC treatment while allowing for diagnostic application, presenting a promising avenue for nanomedicine design.
PubMed: 38916238
DOI: 10.1021/acs.nanolett.4c01767 -
BioRxiv : the Preprint Server For... Jun 2024Vaccines are an indispensable public health measure that have enabled the eradication, near elimination, and prevention of a variety of pathogens. As research continues...
Vaccines are an indispensable public health measure that have enabled the eradication, near elimination, and prevention of a variety of pathogens. As research continues and our understanding of immunization strategies develops, subunit vaccines have emerged as exciting alternatives to existing whole vaccine approaches. Unfortunately, subunit vaccines often possess weak antigenicity, requiring delivery devices and adjuvant supplementation to improve their utility. Peptide amphiphile micelles have recently been shown to function as both delivery devices and self-adjuvanting systems that can be readily associated with molecular adjuvants to further improve vaccine-mediated host immunity. While promising, many "design rules" associated with the plethora of underlying adjustable parameters in the generation of a peptide amphiphile micelle vaccine have yet to be uncovered. This work explores the impact micellar adjuvant complexation method and incorporated antigen type have on their ability to activate dendritic cells and induce antigen specific responses. Interestingly, electrostatic complexation of CpG to micelles resulted in improved dendritic cell activation over hydrophobic association and antigen|adjuvant co-localization influenced cell-mediated, but not antibody-mediated immune responses. These exciting results complement those previously published to build the framework of a micelle vaccine toolbox that can be leveraged for future disease-specific formulations.
PubMed: 38915689
DOI: 10.1101/2024.06.10.598369 -
World Journal of Microbiology &... Jun 2024Liamocins, a group of high-density glycolipids, are only produced by certain strains of the yeast-like fungi in the genus Aureobasidium. Until now, few studies have...
Liamocins, a group of high-density glycolipids, are only produced by certain strains of the yeast-like fungi in the genus Aureobasidium. Until now, few studies have focused on the surfactant properties of liamocins produced from the highly diverse tropical strains of Aureobasidium. Therefore, the aims of this research were to screen the liamocin production from tropical strains of Aureobasidium spp. and to characterize their surfactant properties. A total of 41 strains of Thai Aureobasidium spp. were screened for their ability to produce liamocins, and the products were detected using matrix-assisted laser desorption/ionization time-of-flight mass spectrometry and thin-layer chromatography. Of those strains, 30 strains of Aureobasidium spp. tested were found to produce liamocins with yields ranging from 0.53 to 10.60 g/l. The nature of all crude liamocins was heterogeneous, with different compositions and ratios depending on the yeast strain. These liamocins exhibited relatively high emulsifying activity against vegetable oils tested, with an emulsification index of around 40-50%; the emulsion stability of some liamocins was up to 30 days. The obtained critical micelle concentration values were varied, with those of liamocins produced from A. pullulans, A. melanogenum and A. thailandense falling in ranges from 7.70 to 119.78, 10.73 to > 1,000, and 68.56 to > 1,000 mg/l, respectively. The emulsification activity of liamocins was higher than that of the analytical grade rhamnolipids. These compounds showed strong surface tension reduction in a sodium chloride concentration range of 2-12% (w/v), pH values between 3 and 7, and temperatures between 4 and 121 °C. This is the first report of liamocins produced by A. thailandense.
Topics: Glycolipids; Aureobasidium; Surface-Active Agents; Thailand; Chromatography, Thin Layer; Plant Oils; Spectrometry, Mass, Matrix-Assisted Laser Desorption-Ionization; Emulsifying Agents; Emulsions
PubMed: 38914906
DOI: 10.1007/s11274-024-04058-z -
Langmuir : the ACS Journal of Surfaces... Jun 2024The nonradiative pathway leading to the photoisomerization of a cyanine dye is well-established information. However, the modulations induced in the photoisomerization...
The nonradiative pathway leading to the photoisomerization of a cyanine dye is well-established information. However, the modulations induced in the photoisomerization pathway by a Keggin-type polyoxometalate in a confined media is new. Our study reveals that, in the presence of pluronic block copolymers F-108 and P-123, phosphomolybdic acid hydrate (PMA) promotes the aggregation of 3,3'-diethylthiadicarbocyanine iodide (DTDCI). The absorption spectra show a clear indication of a red-shifted trimer band in F-108 and P-123, whereas it is absent in F-127 and P-84. Fluorescence emission studies suggest that, in the presence of PMA, the rate of photoisomerization is accelerated in F-108, P-123, and P-84 micelles, whereas it is retarded in F-127 micelles. Time-resolved studies in the presence of PMA indicate the preference of F-108, P-84, and P-123 toward the trapped conformer of DTDCI, whereas F-127 favors the formation of photoisomer of DTDCI. Our findings imply the importance of the interplay between the hydrophobic and electrostatic interactions between the DTDCI cations and the PMA anions in nonionic micelles of varying hydrophilic-lipophilic balance (HLB). Dynamic light scattering (DLS) data suggest a modulation by PMA in the intermicellar electrostatic repulsions of a hydrophilic copolymer micelle, whereas its unaffected in a hydrophobic copolymeric micelle.
PubMed: 38913761
DOI: 10.1021/acs.langmuir.4c01086 -
Nanomedicine (London, England) Jun 2024To assess the chemo-immunomodulatory effects of doxorubicin-loaded cerium oxide nanoparticles coated with oleyl amine-linked cyclic RGDfK peptide (CeNP+Dox+RGD) to...
To assess the chemo-immunomodulatory effects of doxorubicin-loaded cerium oxide nanoparticles coated with oleyl amine-linked cyclic RGDfK peptide (CeNP+Dox+RGD) to target both gliomas and its tumor microenvironment (TME) via integrin receptors. CeNP+Dox+RGD nanoparticles are synthesized by the sequential addition of cerium III chloride heptahydrate, beta-cyclodextrin, oleic acid, and F127 micelle (CeNP). Doxorubicin was then loaded into CeNPs and coated with oleyl amine-linked cyclic RGDfK peptide to form stable CeNP+Dox+RGD nanoparticles. CeNP+Dox+RGD nanoparticles crossed blood-brain barrier (BBB) effectively and demonstrated threefold enhanced survivability in glioma-bearing mice. The IHC profiling of glial tumor cross-sections showed increased CD80 expression (M1 TAMs) and decreased arginase-1 expression (M2 TAMs). CeNP+Dox+RGD can be an immunotherapeutic treatment option to combat glioblastoma.
PubMed: 38912661
DOI: 10.1080/17435889.2024.2350357 -
Frontiers in Immunology 2024Vitamin E, which is also known as tocopherol, is a compound with a polyphenol structure. Its esterified derivative, Vitamin E succinate (VES), exhibits unique anticancer...
BACKGROUND
Vitamin E, which is also known as tocopherol, is a compound with a polyphenol structure. Its esterified derivative, Vitamin E succinate (VES), exhibits unique anticancer and healthcare functions as well as immunomodulatory effects. Natural polysaccharides are proved to be a promising material for nano-drug delivery systems, which show excellent biodegradability and biocompatibility. In this study, we employed a novel polysaccharide-vitamin E succinate polymer (BSP-VES) micelles to enhance the tumor targeting and anti-colon cancer effect of andrographolide (AG).
METHODS
BSP-VES polymer was synthesized through esterification and its structure was confirmed using 1H NMR. AG@BSP-VES was prepared via the dialysis method and the drug loading, entrapment efficiency, stability, and safety were assessed. Furthermore, the tumor targeting ability of AG@BSP-VES was evaluated through targeted cell uptake and imaging. The antitumor activity of AG@BSP-VES was measured using MTT assay, Live&Dead cell staining, and cell scratch test.
RESULTS
In this study, we successfully loaded AG into BSP-VES micelles (AG@BSP-VES), which exhibited good stability, biosafety and sustained release effect. In addition, AG@BSP-VES also showed excellent internalization capability into CT26 cells compared with NCM460 cells . Meanwhile, the specific delivery of AG@BSP-VES micelles into subcutaneous and colon tumors was observed compared with normal colon tissues during the whole experiment process (1-24 h). What's more, AG@BSP-VES micelles exhibited significant antitumor activities than BSP-VES micelles and free AG.
CONCLUSION
The study provides a meaningful new idea and method for application in drug delivery system and targeted treatment of colon cancer based on natural polysaccharides.
Topics: Micelles; Animals; Colonic Neoplasms; Diterpenes; Humans; Mice; Cell Line, Tumor; Polysaccharides; Antineoplastic Agents; Drug Delivery Systems; Xenograft Model Antitumor Assays; Drug Carriers; Nanoparticles; Nanoparticle Drug Delivery System; Mice, Nude; Mice, Inbred BALB C
PubMed: 38911867
DOI: 10.3389/fimmu.2024.1380229 -
Industrial & Engineering Chemistry... Jun 2024A novel investigation of the effects of the hydrophilic and hydrophobic segments of hydrophobically modified ethoxylated urethanes (HEURs) on the rheological properties...
A novel investigation of the effects of the hydrophilic and hydrophobic segments of hydrophobically modified ethoxylated urethanes (HEURs) on the rheological properties of their aqueous solutions, latex-based emulsions, and waterborne paints is demonstrated. Different HEUR thickeners were produced by varying the poly(ethylene glycol) (PEG) molecular weight and terminal hydrophobic size. Results reveal that the strength of hydrophobic associations and, consequently, the rheological properties of HEUR formulations can be effectively controlled by modifying the structure of the hydrophobic segment, specifically, the combination of diisocyanate and monoalcohol. This allows for the on-demand attainment of diverse rheological behaviors ranging from predominantly Newtonian profiles exhibiting lower viscosities to markedly pseudoplastic behaviors with significantly higher viscosities. The length of the hydrophilic group appears to affect viscosity only marginally up to a molecular weight of 23,000 g/mol, with more notable effects at 33,000 g/mol. Additionally, it was indicated that the rheological responses observed in water solutions provide a reliable forecast of their behavior in latex-based emulsions and waterborne paints. Coarse-grained molecular dynamics (CG-MD) simulations were also applied to gain insight into HEUR micelle dynamics in aqueous solutions. Guided by the DBSCAN algorithm, the simulations successfully captured the concentration-dependent behavior and the impact of hydrophilic chain length, aligning with the experimental viscosity trends. Various metrics were employed to provide a comprehensive analysis of the micellization process, including the hydrophobic cluster volume, the total micellar volume, the aggregation number, and the number of chains interconnecting with other micelles.
PubMed: 38911482
DOI: 10.1021/acs.iecr.4c00253 -
Macromolecules Feb 2024The design of functional polymeric materials with tunable response requires a synergetic use of macromolecular architecture and interactions. Here, we combine...
The design of functional polymeric materials with tunable response requires a synergetic use of macromolecular architecture and interactions. Here, we combine experiments with computer simulations to demonstrate how physical properties of gels can be tailored at the molecular level, using star block copolymers with alternating block sequences as a paradigm. Telechelic star polymers containing attractive outer blocks self-assemble into soft patchy nanoparticles, whereas their mirror-image inverted architecture with inner attractive blocks yields micelles. In concentrated solutions, bridged and interpenetrated hexagonally packed nanocylinders are formed, respectively, with distinct structural and rheological properties. The phase diagrams exhibit a peculiar re-entrance where the hexagonal phase melts upon both heating and cooling because of solvent-block and block-block interactions. The bridged nanostructure is characterized by similar deformability, extended structural coherence, enhanced elasticity, and yield stress compared to micelles or typical colloidal gels, which make them promising and versatile materials for diverse applications.
PubMed: 38911231
DOI: 10.1021/acs.macromol.3c02088 -
Talanta Jun 2024The certification of cosmetic products has always been a prominent concern. Here, we have developed a pH sensor and applied it in the field of cosmetic safety....
The certification of cosmetic products has always been a prominent concern. Here, we have developed a pH sensor and applied it in the field of cosmetic safety. Initially, we designed two probes, CH with aggregation-induced emission (AIE) effect and the near-infrared fluorophore derivative CYTYR. By encapsulating them with DSPE-PEG2000-NH, we obtained the CHCY-lipo nano-micelles with fluorescence resonance energy transfer (FRET) response. By combining them into a sensor array called pC, we achieved sensitive detection of a wide pH range, ranging from 4.69 to 9.25. To validate the performance of the pC sensor array, we employed a multi-channel mode and applied it to differentiate commercial anti-aging creams. Through linear discriminant analysis and 3D fingerprint analysis, the pC sensor array successfully distinguished anti-aging creams from different countries, providing a rapid and accurate method for cosmetic safety identification. The results of this study demonstrate the potential of the pC sensor array for quick authentication of cosmetic products, offering significant support and application prospects in safeguarding consumer health.
PubMed: 38909596
DOI: 10.1016/j.talanta.2024.126447