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1.
J Phys Condens Matter ; 36(21)2024 Feb 27.
Artigo em Inglês | MEDLINE | ID: mdl-38354419

RESUMO

We present a comprehensive investigation of the crystal and magnetic structures of the van der Waals antiferromagnetα-RuCl3using single crystal x-ray and neutron diffraction. The crystal structure at room temperature is a monoclinic (C2/m). However, with decreasing temperature, a remarkable first-order structural phase transition is observed, leading to the emergence of a rhombohedral (R3-) structure characterized by three-fold rotational symmetry forming an isotropic honeycomb lattice. On further cooling, a zigzag-type antiferromagnetic order develops belowTN=6∼6.6K. The critical exponent of the magnetic order parameter was determined to beß=0.11(1), which is close to the two-dimensional Ising model. Additionally, the angular dependence of the magnetic critical field of the zigzag antiferromagnetic order for the polarized ferromagnetic phase reveals a six-fold rotational symmetry within theab-plane. These findingsreflect the symmetry associated with the Ising-like bond-dependent Kitaev spin interactions and underscore the universality of the Kitaev interaction-dominated antiferromagnetic system.

2.
ACS Appl Mater Interfaces ; 16(1): 1370-1379, 2024 Jan 10.
Artigo em Inglês | MEDLINE | ID: mdl-38117479

RESUMO

The extracellular matrix (ECM) is the fundamental acellular element of human tissues, providing their mechanical structure while delivering biomechanical and biochemical signals to cells. Three-dimensional (3D) tissue models commonly use hydrogels to recreate the ECM in vitro and support the growth of cells as organoids and spheroids. Collagen-nanocellulose (COL-NC) hydrogels rely on the blending of both polymers to design matrices with tailorable physical properties. Despite the promising application of these biomaterials in 3D tissue models, the architecture and network organization of COL-NC remain unclear. Here, we investigate the structural effects of incorporating NC fibers into COL hydrogels by small-angle neutron scattering (SANS) and ultra-SANS (USANS). The critical hierarchical structure parameters of fiber dimensions, interfiber distance, and coassembled open structures of NC and COL in the absence and presence of cells were determined. We found that NC expanded and increased the homogeneity in the COL network without affecting the inherent fiber properties of both polymers. Cells cultured as spheroids in COL-NC remodeled the hydrogel network without a significant impact on its architecture. Our study reveals the polymer organization of COL-NC hydrogels and demonstrates SANS and USANS as exceptional techniques to reveal nano- and micron-scale details on polymer organization, which leads to a better understanding of the structural properties of hydrogels to engineer novel ECMs.


Assuntos
Matriz Extracelular , Hidrogéis , Humanos , Hidrogéis/química , Matriz Extracelular/química , Colágeno/química , Organoides
3.
J Colloid Interface Sci ; 652(Pt B): 1609-1619, 2023 Dec 15.
Artigo em Inglês | MEDLINE | ID: mdl-37666193

RESUMO

HYPOTHESIS: Poly(N-isopropylacrylamide) [PNIPAM]-grafted cellulose nanofibers (CNFs) are new thermo-responsive hydrogels which can be used for a wide range of applications. Currently, there is no clear understanding of the precise mechanism by which CNFs and PNIPAM interact together. Here, we hypothesize that the physical crosslinking of grafted PNIPAM on CNF inhibits the free movement of individual CNF, which increases the gel strength while sustaining its thermo-responsive properties. EXPERIMENTS: The thermo-responsive behaviour of PNIPAM-grafted CNFs (PNIPAM-g-CNFs), synthesized via silver-catalyzed decarboxylative radical polymerization, and PNIPAM-blended CNFs (PNIPAM-b-CNFs) was studied. Small angle neutron scattering (SANS) combined with Ultra-SANS (USANS) revealed the nano to microscale conformation changes of these polymer hybrids as a function of temperature. The effect of temperature on the optical and viscoelastic properties of hydrogels was also investigated. FINDINGS: Grafting PNIPAM from CNFs shifted the lower critical solution temperature (LCST) from 32 °C to 36 °C. Below LCST, the PNIPAM chains in PNIPAM-g-CNF sustain an open conformation and poor interaction with CNF, and exhibit water-like behaviour. At and above LCST, the PNIPAM chains change conformation to entangle and aggregate nearby CNFs. Large voids are formed in solution between the aggregated PNIPAM-CNF walls. In comparison, PNIPAM-b-CNF sustains liquid-like behaviour below LCST. At and above LCST, the blended PNIPAM phase separates from CNF to form large aggregates which do not affect CNF network and thus PNIPAM-b-CNF demonstrates low viscosity. Understanding of temperature-dependent conformation of PNIPAM-g-CNFs engineer thermo-responsive hydrogels for biomedical and functional applications.

4.
Nanomaterials (Basel) ; 13(7)2023 Apr 02.
Artigo em Inglês | MEDLINE | ID: mdl-37049350

RESUMO

Supercapacitors are candidates with the greatest potential for use in sustainable energy resources. Extensive research is being carried out to improve the performances of state-of-art supercapacitors to meet our increased energy demands because of huge technological innovations in various fields. The development of high-performing materials for supercapacitor components such as electrodes, electrolytes, current collectors, and separators is inevitable. To boost research in materials design and production toward supercapacitors, the up-to-date collection of recent advancements is necessary for the benefit of active researchers. This review summarizes the most recent developments of water-in-salt (WIS) and deep eutectic solvents (DES), which are considered significant electrolyte systems to advance the energy density of supercapacitors, with a focus on two-dimensional layered nanomaterials. It provides a comprehensive survey of 2D materials (graphene, MXenes, and transition-metal oxides/dichalcogenides/sulfides) employed in supercapacitors using WIS/DES electrolytes. The synthesis and characterization of various 2D materials along with their electrochemical performances in WIS and DES electrolyte systems are described. In addition, the challenges and opportunities for the next-generation supercapacitor devices are summarily discussed.

5.
Pharmaceutics ; 15(3)2023 Feb 23.
Artigo em Inglês | MEDLINE | ID: mdl-36986601

RESUMO

Nanomedicine has garnered significant interest owing to advances in drug delivery, effectively demonstrated in the treatment of certain diseases. Here, smart supermagnetic nanocomposites based on iron oxide nanoparticles (MNPs) coated with Pluronic F127 (F127) were developed for the delivery of doxorubicin (DOX) to tumor tissues. The XRD patterns for all samples revealed peaks consistent with Fe3O4, as shown by their indices (220), (311), (400), (422), (511), and (440), demonstrating that the structure of Fe3O4 did not change after the coating process. After loading with DOX, the as-prepared smart nanocomposites demonstrated drug-loading efficiency and drug-loading capacity percentages of 45 ± 0.10 and 17 ± 0.58% for MNP-F127-2-DOX and 65 ± 0.12 and 13 ± 0.79% for MNP-F127-3-DOX, respectively. Moreover, a better DOX release rate was observed under acidic conditions, which may be credited to the pH sensitivity of the polymer. In vitro analysis demonstrated the survival rate of approximately 90% in HepG2 cells treated with PBS and MNP-F127-3 nanocomposites. Furthermore, after treatment with MNP-F127-3-DOX, the survival rate decreased, confirming cellular inhibition. Hence, the synthesized smart nanocomposites showed great promise for drug delivery in liver cancer treatment, overcoming the limitations of traditional therapies.

6.
Commun Biol ; 6(1): 124, 2023 01 31.
Artigo em Inglês | MEDLINE | ID: mdl-36721030

RESUMO

Group A Streptococcus (GAS) is a strict human pathogen possessing a unique pathogenic trait that utilizes the cooperative activity of NAD+-glycohydrolase (NADase) and Streptolysin O (SLO) to enhance its virulence. How NADase interacts with SLO to synergistically promote GAS cytotoxicity and intracellular survival is a long-standing question. Here, the structure and dynamic nature of the NADase/SLO complex are elucidated by X-ray crystallography and small-angle scattering, illustrating atomic details of the complex interface and functionally relevant conformations. Structure-guided studies reveal a salt-bridge interaction between NADase and SLO is important to cytotoxicity and resistance to phagocytic killing during GAS infection. Furthermore, the biological significance of the NADase/SLO complex in GAS virulence is demonstrated in a murine infection model. Overall, this work delivers the structure-functional relationship of the NADase/SLO complex and pinpoints the key interacting residues that are central to the coordinated actions of NADase and SLO in the pathogenesis of GAS infection.


Assuntos
Streptococcus , Estreptolisinas , Humanos , Animais , Camundongos , Proteínas de Bactérias , NAD+ Nucleosidase
7.
Nat Commun ; 13(1): 343, 2022 01 17.
Artigo em Inglês | MEDLINE | ID: mdl-35039508

RESUMO

A depleted antimicrobial drug pipeline combined with an increasing prevalence of Gram-negative 'superbugs' has increased interest in nano therapies to treat antibiotic resistance. As cubosomes and polymyxins disrupt the outer membrane of Gram-negative bacteria via different mechanisms, we herein examine the antimicrobial activity of polymyxin-loaded cubosomes and explore an alternative strategy via the polytherapy treatment of pathogens with cubosomes in combination with polymyxin. The polytherapy treatment substantially increases antimicrobial activity compared to polymyxin B-loaded cubosomes or polymyxin and cubosomes alone. Confocal microscopy and neutron reflectometry suggest the superior polytherapy activity is achieved via a two-step process. Firstly, electrostatic interactions between polymyxin and lipid A initially destabilize the outer membrane. Subsequently, an influx of cubosomes results in further membrane disruption via a lipid exchange process. These findings demonstrate that nanoparticle-based polytherapy treatments may potentially serve as improved alternatives to the conventional use of drug-loaded lipid nanoparticles for the treatment of "superbugs".


Assuntos
Farmacorresistência Bacteriana Múltipla , Nanopartículas/química , Antibacterianos/farmacologia , Bactérias/efeitos dos fármacos , Membrana Celular/química , Membrana Celular/efeitos dos fármacos , Farmacorresistência Bacteriana Múltipla/efeitos dos fármacos , Quimioterapia Combinada , Células HEK293 , Humanos , Bicamadas Lipídicas/química , Testes de Sensibilidade Microbiana , Microscopia Confocal , Polimixina B/farmacologia
8.
Sci Rep ; 12(1): 775, 2022 Jan 14.
Artigo em Inglês | MEDLINE | ID: mdl-35031677

RESUMO

We report on experimental evidence of non-conversional pairing in In and Sn nanoparticle assemblies. Spontaneous magnetizations are observed, through extremely weak-field magnetization and neutron-diffraction measurements, to develop when the nanoparticles enter the superconducting state. The superconducting transition temperature TC shifts to a noticeably higher temperature when an external magnetic field or magnetic Ni nanoparticles are introduced into the vicinity of the superconducting In or Sn nanoparticles. There is a critical magnetic field and a critical Ni composition that must be reached before the magnetic environment will suppress the superconductivity. The observations may be understood when assuming development of spin-parallel superconducting pairs on the surfaces and spin-antiparallel superconducting pairs in the core of the nanoparticles.

9.
Langmuir ; 37(44): 13046-13058, 2021 Nov 09.
Artigo em Inglês | MEDLINE | ID: mdl-34696591

RESUMO

We have examined the spatial distributions of polymer chains in blend films of weakly segregated polystyrene-block-poly(methyl methacrylate) [P(S-b-MMA)] and deuterated polystyrene (dPS). By fine-tuning the composition (ϕPS+dPS = 63.8 vol %) of the total PS/dPS component and annealing temperature (230 and 270 °C), P(S-b-MMA)/dPS blend films mainly form perforated layers with a parallel orientation (hereafter PLs//). The distributions of dPS in PLs// were probed by grazing-incidence small-angle neutron scattering (GISANS) and time-of-flight neutron reflectivity (ToF-NR). GISANS and ToF-NR results offer evidence that dPS chains preferentially locate at the free surface and within the PS layers for blend films that were annealed at 230 °C. Upon annealing at 270 °C, dPS chains distribute within PS layers and perforated PMMA layers. Nevertheless, dPS chains still retain a surface preference for thin films. In contrast, such surface segregation of dPS chains is prohibited for thick films when annealed at 270 °C.

10.
Acta Biomater ; 126: 433-444, 2021 05.
Artigo em Inglês | MEDLINE | ID: mdl-33774200

RESUMO

Glaucoma, a major cause of irreversible blindness worldwide, is associated with elevated intraocular pressure (IOP) and progressive loss of retinal ganglion cells (RGCs) that undergo apoptosis. A mechanism for RGCs injury involves impairment of neurotrophic support and exogenous supply of neurotrophic factors has been shown to be beneficial. However, neurotrophic factors can have widespread effects on neuronal tissues, thus targeting neurotrophic support to injured neurons may be a better neuroprotective strategy. In this study, we have encapsulated LM22A-4, a small neurotrophic factor mimetic, into Annexin V-conjugated cubosomes (L4-ACs) for targeted delivery to injured RGCs in a model of acute IOP elevation, which is induced by acute IOP elevation. We have tested cubosomes formulations that encapsulate from 9% to 33% LM22A-4. Our data indicated that cubosomes encapsulating 9% and 17% LM22A-4 exhibited a mixture of Pn3m/Im3m cubic phase, whereas 23% and 33% showed a pure Im3m cubic phase. We found that 17% L4-ACs with Pn3m/Im3m symmetries showed better in-situ and in-vitro lipid membrane interactions than the 23% and 33% L4-ACs with Im3m symmetry. In vivo experiments showed that 17% L4-ACs targeted the posterior retina and the optic nerve head, which prevented RGCs loss and improved functional outcomes in a mouse model of acute IOP elevation. These results provide evidence that Annexin V-conjugated cubosomes-based LM22A-4 delivery may be a useful targeted approach to prevent the progression of RGCs loss in glaucoma. STATEMENT OF SIGNIFICANCE: Recent studies suggest that the therapy of effectively delivering neurotrophic factors to the injured retinal ganglion cells (RGCs) could promote the survival of RGCs in glaucoma. Our present work has for the first time used cubosomes as an active targeted delivery system and have successfully delivered a neuroprotective drug to the damaged RGCs in vivo. Our new cubosomal formulation can protect apoptotic cell death in vitro and in vivo, showing that cubosomes are a promising drug carrier system for ocular drug delivery and glaucoma treatment. We have further found that by controlling cubosomes in Pn3m phase we can facilitate delivery of neuroprotective drug through apoptotic membranes. This data, we believe, has important implications for future design and formulation of cubosomes for therapeutic applications.


Assuntos
Glaucoma , Disco Óptico , Animais , Benzamidas , Modelos Animais de Doenças , Glaucoma/tratamento farmacológico , Pressão Intraocular , Camundongos , Células Ganglionares da Retina
11.
Biochim Biophys Acta Biomembr ; 1863(9): 183587, 2021 09 01.
Artigo em Inglês | MEDLINE | ID: mdl-33639106

RESUMO

In Gram-negative bacteria, the ß-barrel assembly machinery (BAM) complex catalyses the assembly of ß-barrel proteins into the outer membrane, and is composed of five subunits: BamA, BamB, BamC, BamD and BamE. Once assembled, - ß-barrel proteins can be involved in various functions including uptake of nutrients, export of toxins and mediating host-pathogen interactions, but the precise mechanism by which these ubiquitous and often essential ß-barrel proteins are assembled is yet to be established. In order to determine the relative positions of BAM subunits in the membrane environment we reconstituted each subunit into a biomimetic membrane, characterizing their interaction and structural changes by Quartz Crystal Microbalance with Dissipation monitoring (QCM-D) and neutron reflectometry. Our results suggested that the binding of BamE, or a BamDE dimer, to BamA induced conformational changes in the polypeptide transported-associated (POTRA) domains of BamA, but that BamB or BamD alone did not promote any such changes. As monitored by neutron reflectometry, addition of an unfolded substrate protein extended the length of POTRA domains further away from the membrane interface as part of the mechanism whereby the substrate protein was folded into the membrane.


Assuntos
Lipoproteínas/química , Fosfatidilcolinas/química , Difração de Nêutrons , Técnicas de Microbalança de Cristal de Quartzo
12.
ACS Appl Mater Interfaces ; 12(40): 44485-44498, 2020 Oct 07.
Artigo em Inglês | MEDLINE | ID: mdl-32942850

RESUMO

Treatment of multidrug-resistant (MDR) bacterial infections increasingly relies on last-line antibiotics, such as polymyxins, with the urgent need for discovery of new antimicrobials. Nanotechnology-based antimicrobials have gained significant importance to prevent the catastrophic emergence of MDR over the past decade. In this study, phytantriol-based nanoparticles, named cubosomes, were prepared and examined in vitro by minimum inhibitory concentration (MIC) and time-kill assays against Gram-negative bacteria: Acinetobacter baumannii, Klebsiella pneumoniae, and Pseudomonas aeruginosa. Phytantriol-based cubosomes were highly bactericidal against polymyxin-resistant, lipopolysaccharide (LPS)-deficient A. baumannii strains. Small-angle neutron scattering (SANS) was employed to understand the structural changes in biomimetic membranes that replicate the composition of these LPS-deficient strains upon treatment with cubosomes. Additionally, to further understand the membrane-cubosome interface, neutron reflectivity (NR) was used to investigate the interaction of cubosomes with model bacterial membranes on a solid support. These results reveal that cubosomes might be a new strategy for combating LPS-deficient Gram-negative pathogens.


Assuntos
Acinetobacter baumannii/efeitos dos fármacos , Antibacterianos/farmacologia , Álcoois Graxos/farmacologia , Klebsiella pneumoniae/efeitos dos fármacos , Lipopolissacarídeos/antagonistas & inibidores , Pseudomonas aeruginosa/efeitos dos fármacos , Antibacterianos/química , Composição de Medicamentos , Farmacorresistência Bacteriana Múltipla/efeitos dos fármacos , Álcoois Graxos/química , Lipopolissacarídeos/farmacologia , Testes de Sensibilidade Microbiana , Microscopia Eletrônica de Transmissão , Tamanho da Partícula , Espalhamento a Baixo Ângulo , Propriedades de Superfície , Difração de Raios X
13.
Nanomaterials (Basel) ; 10(7)2020 Jul 04.
Artigo em Inglês | MEDLINE | ID: mdl-32635511

RESUMO

The Fe-doped NiO nanoparticles that were synthesized using a co-precipitation method are characterized by enhanced room-temperature ferromagnetic property evident from magnetic measurements. Neutron powder diffraction experiments suggested an increment of the magnetic moment of 3d ions in the nanoparticles as a function of Fe-concentration. The temperature, time, and field-dependent magnetization measurements show that the effect of Fe-doping in NiO has enhanced the intraparticle interactions due to formed defect clusters. The intraparticle interactions are proposed to bring additional magnetic anisotropy energy barriers that affect the overall magnetic moment relaxation process and emerging as room temperature magnetic memory. The outcome of this study is attractive for the future development of the room temperature ferromagnetic oxide system to facilitate the integration of spintronic devices and understanding of their fundamental physics.

14.
ACS Omega ; 5(8): 3849-3856, 2020 Mar 03.
Artigo em Inglês | MEDLINE | ID: mdl-32149211

RESUMO

Magnetic properties of fully oxygenated bare CuO nanoparticles have been investigated using magnetization, X-ray diffraction, neutron diffraction, and Raman scattering measurements. The Langevin field profile is clearly revealed in the isothermal magnetization of 8.8 nm CuO nanoparticle assembly even at 300 K, revealing a 172 times enhancement of the ferromagnetic responses over that of bulk CuO. Surface magnetization of 8.8 nm CuO reaches 18% of the core magnetization. The Cu spins in 8.8 nm CuO order below 400 K, which is 1.7 times higher than the 231 K observed in bulk CuO. A relatively simple magnetic structure that may be indexed using a modulation vector of (0.2, 0, 0.2) was found for the 8.8 nm CuO, but no magnetic incommensurability was observed in bulk CuO. The Cu spins in 8.8 nm CuO form spin density waves with length scales of 5 chemical unit cells long along the crystallographic a- and c-axis directions. Considerable amounts of electronic charge shift from around the Cu lattice sites toward the interconnecting regions of two neighboring Cu-Cu ions, resulting in a stronger ferromagnetic direct exchange interaction for the neighboring Cu spins in 8.8 nm CuO.

15.
J Colloid Interface Sci ; 568: 234-244, 2020 May 15.
Artigo em Inglês | MEDLINE | ID: mdl-32092552

RESUMO

HYPOTHESIS: The water absorption capacity of nanocellulose (NC) foam is tailored by crosslinking with polyethyleneimine (PEI) and hexamethylenediamine (HMDA). The interaction of amine groups in PEI and HMDA with the carboxylic groups (COO-) of NC affects the foam structure which reduces its swelling capacity. EXPERIMENTS: Functionalised NC foams were prepared by TEMPO (2,2,6,6,-tetramethylpiperidine-1-oxyl) oxidation of bleached pulp, followed by fibrillation into a hydrogel, adding a crosslinker and freeze drying the hydrogel into a foam. The structure of the NC foam characterised by rheology, SANS (Small Angle Neutron Scattering), SAXS (Small Angle X-ray Scattering) and cryo-SEM (cryo-Scanning Electron Microscopy) was related to absorption and swelling properties. FINDINGS: The NC foam has the highest water absorption capacity at 132 g water/g foam. PEI-NC foam has a water absorption capacity of 71 g water/g foam, which further decreases to 47 g water/g foam for the HMDA-NC foam. Small angle scattering reveals the elementary fibril of NC is 3-5 nm thick and forms fiber bundles. In water, these bundles swell differently for the different types of foam which affects the water absorption capacity of the network. The structural analysis of the foam was related to the swelling capacity. The structure of NC foam can be engineered for specific applications for biomedical, agriculture or food industries.


Assuntos
Celulose/química , Reagentes de Ligações Cruzadas/química , Nanopartículas/química , Celulose/síntese química , Reagentes de Ligações Cruzadas/síntese química , Estrutura Molecular , Tamanho da Partícula , Propriedades de Superfície
16.
Langmuir ; 35(43): 14017-14030, 2019 Oct 29.
Artigo em Inglês | MEDLINE | ID: mdl-31577149

RESUMO

Ultraviolet irradiation (UVI) of varied duration caused cross-linking and neutralization of polystyrene (PS) homopolymers of molar mass (Mn) from 6 to 290 kg mol-1 on a silicon-oxide surface. An optimal neutral skin layer on the surface of the PS was obtained via brief UVI in air (UVIA), by which the PS had no preferential interaction with either block in the copolymer. UVI in an inert environment (gaseous dinitrogen) (UVIN) stabilized the PS layers via cross-linking and enabled the PS networks to have an effective adhesive contact with the underlying substrate. Thorough examination of domain orientations and spatial orders of a series of block copolymer, polystyrene-block-poly(methyl methacrylate) (PS-b-PMMA), thin films deposited on these UVI-treated PS support layers yielded clear evidence that a dense layer of neutralized PS chains was required for the perpendicular orientation of PS-b-PMMA nanodomains. In particular, in addition to neutralization, two factors-the densities of physical entanglements and of chemical crosslinks-both in UVI-treated PS should be considered for the perpendicular orientation of nanolamellae and nanocylinders in symmetric and asymmetric PS-b-PMMA thin films. The density of physical entanglement in PS depends intrinsically on Mn of the PS, whereas the density of chemical cross-links was controlled with a varied duration of UVIN. Sufficiently large densities of physical entanglements and chemical cross-links can prevent PS-b-PMMA chains from penetrating through the neutral skin layer. The total density of physical entanglements and chemical cross-links required for the perpendicular orientation is correlated with the dimensions of the PS-b-PMMA chains.

17.
Proc Natl Acad Sci U S A ; 116(9): 3722-3727, 2019 02 26.
Artigo em Inglês | MEDLINE | ID: mdl-30808758

RESUMO

Staphylococcus aureus is a notorious human bacterial pathogen with considerable capacity to develop antibiotic resistance. We have observed that human infections caused by highly drug-resistant S. aureus are more prolonged, complicated, and difficult to eradicate. Here we describe a metabolic adaptation strategy used by clinical S. aureus strains that leads to resistance to the last-line antibiotic, daptomycin, and simultaneously affects host innate immunity. This response was characterized by a change in anionic membrane phospholipid composition induced by point mutations in the phospholipid biosynthesis gene, cls2, encoding cardiolipin synthase. Single cls2 point mutations were sufficient for daptomycin resistance, antibiotic treatment failure, and persistent infection. These phenotypes were mediated by enhanced cardiolipin biosynthesis, leading to increased bacterial membrane cardiolipin and reduced phosphatidylglycerol. The changes in membrane phospholipid profile led to modifications in membrane structure that impaired daptomycin penetration and membrane disruption. The cls2 point mutations also allowed S. aureus to evade neutrophil chemotaxis, mediated by the reduction in bacterial membrane phosphatidylglycerol, a previously undescribed bacterial-driven chemoattractant. Together, these data illustrate a metabolic strategy used by S. aureus to circumvent antibiotic and immune attack and provide crucial insights into membrane-based therapeutic targeting of this troublesome pathogen.


Assuntos
Farmacorresistência Bacteriana/genética , Proteínas de Membrana/genética , Staphylococcus aureus Resistente à Meticilina/genética , Infecções Estafilocócicas/genética , Transferases (Outros Grupos de Fosfato Substituídos)/genética , Antibacterianos/farmacologia , Daptomicina/farmacologia , Farmacorresistência Bacteriana/imunologia , Regulação Bacteriana da Expressão Gênica/efeitos dos fármacos , Interações Hospedeiro-Patógeno/imunologia , Humanos , Evasão da Resposta Imune/genética , Evasão da Resposta Imune/imunologia , Proteínas de Membrana/metabolismo , Staphylococcus aureus Resistente à Meticilina/imunologia , Staphylococcus aureus Resistente à Meticilina/metabolismo , Staphylococcus aureus Resistente à Meticilina/patogenicidade , Testes de Sensibilidade Microbiana , Infecções Estafilocócicas/imunologia , Infecções Estafilocócicas/microbiologia , Transferases (Outros Grupos de Fosfato Substituídos)/metabolismo
18.
Langmuir ; 34(25): 7416-7427, 2018 06 26.
Artigo em Inglês | MEDLINE | ID: mdl-29863876

RESUMO

We investigated the relationship between the self-assembled morphology of poly( tert-butyl acrylate)- block-poly(6-[4-(4'-methoxyphenylazo)phenoxy]hexyl methacrylate) (P tBA- b-PAzoMA) block copolymers and their photoresponsive and fluorescence behaviors. The morphology of P tBA- b-PAzoMA copolymers was manipulated by dissolving them in mixed dimethylformamide (DMF)/hexanol solvents. When P tBA- b-PAzoMA was dissolved in DMF-rich (neutral) solvents, a favorable interaction between the DMF molecules and both blocks resulted in a random-coiled conformation. The unconfined morphology facilitated the formation of both nonassociated and head-to-head organized azobenzene mesogens, which promoted fluorescence emission. When hexanol, a P tBA-selective solvent, was added to DMF, the solvency of P tBA- b-PAzoMA worsened, leading to its assembly into micelles, with PAzoMA in the micelle core. The confinement of azobenzene moieties in the micelle core hindered their trans-to- cis photoisomerization, thereby considerably decreasing the kinetics of photoisomerization and the population of cis isomers. Additionally, a nanoconfined geometry resulted in compactly packed chromophores, causing fluorescence loss. When P tBA- b-PAzoMA was exposed to UV light, the increased number of cis isomers hampered the closely packed mesogens, resulting in a substantial enhancement of fluorescence emission. When the mole fraction of the PAzoMA block was increased, P tBA- b-PAzoMA formed clusters, causing the slow kinetics of photoisomerization and fluorescence quenching.

19.
ACS Omega ; 2(8): 4227-4236, 2017 Aug 31.
Artigo em Inglês | MEDLINE | ID: mdl-31457717

RESUMO

A large enhancement of the Ni and Cr ferromagnetic moments under UV-light irradiation has been detected in 55 nm thick K0.98Ni[Cr(CN)6]0.70[(H2O)6]0.30·0.11H2O Prussian blue analogues coated on 240 nm Rb0.76Co[Fe(CN)6]0.74[(H2O)6]0.26·0.56H2O nanocubes. Two separate magnetic transitions were found. The one at 72 K marks the magnetic ordering of the Ni and Cr ions on the shell. A higher degree of electronic connection along the Ni-N-C-Cr-C-N-Ni chains was achieved by the incorporation of a larger amount of K+ ions into the voids enclosed by the NiN6 and CrC6 octahedra, which was used to understand the appearance of photoenhanced ferromagnetism in the K-Ni-Cr network. A weak moment developed in the core below 10 K, corresponding to separate ordering of the Co and Fe ions in the Rb-Co-Fe network. Photoinduced ferromagnetism of the Co and Fe ions in the Rb-Co-Fe was also detected.

20.
Langmuir ; 32(46): 12166-12174, 2016 11 22.
Artigo em Inglês | MEDLINE | ID: mdl-27802053

RESUMO

The interactions between ions and phospholipids are closely associated with the structures and functions of cell membrane. Instead of conventional aqueous systems, we systematically investigated the effects of inorganic ions on the self-assembly of lecithin, a zwitterionic phosphatidylcholine, in cyclohexane. Previous studies have shown that addition of inorganic salts with specific divalent and trivalent cations can transform lecithin organosols into organogels. In this study, we focused on the effect of monovalent alkali halides. Fourier transform infrared spectroscopy was used to demonstrate that the binding strength of the alkali cations with the phosphate of lecithin is in the order Li+ > Na+ > K+. More importantly, the cation-phosphate interaction is affected by the paired halide anions, and the effect follows the series I- > Br- > Cl-. The salts of stronger interactions with lecithin, including LiCl, LiBr, LiI, and NaI, were found to induce cylindrical micelles sufficiently long to form organogels, while others remain organosols. A mechanism based on the charge density of ions and the enthalpy change of the ion exchange between alkali halides and lecithin headgroup is provided to explain the contrasting interactions and the effectiveness of the salts to induce organogelation.

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