Dual-Function Wearable Hydrogel Optical Fiber for Monitoring Posture and Sweat pH.

In recent years, wearable devices have been widely used for human health monitoring. Such monitoring predominantly relies on the principles of optics and electronics. However, electronic detection is susceptible to electromagnetic interference, and traditional optical fiber detection is limited in functionality and unable to simultaneously detect both physical and chemical signals. Hence, a wearable, embedded asymmetric color-blocked optical fiber sensor based on a hydrogel has been developed. Its sensing principle is grounded in the total internal reflection within the optical fiber. The method for posture sensing involves changes in the light path due to fiber bending with color blocks providing wavelength-selective modulation by absorption changes. Sweat pH sensing is facilitated by variations in fluorescence intensity triggered by sweat-induced conformational changes in Rhodamine B. With just one fiber, it achieves both physical and chemical signal detection. Fabricated using a molding technique, this fiber boasts excellent biocompatibility and can accurately discern single and multiple bending points, with a recognition range of 0-90° for a single segment, a detection limit of 0.02 mm-1 and a sweat pH sensing linear regression R2 of 0.993, alongside great light propagation properties (-0.6 dB·cm-1). With its extensive capabilities, it holds promise for applications in medical monitoring.

Hydrophilicity and Pore Structure Enhancement in Polyurethane/Silk Protein-Bismuth Halide Oxide Composite Films for Photocatalytic Degradation of Dye.

Polyurethane/silk protein-bismuth halide oxide composite films were fabricated using a blending-wet phase transformationin situsynthesis method. The crystal structure, micromorphology, and optical properties were conducted using XRD, SEM, and UV-Vis DRS characterize techniques. The results indicated that loaded silk protein enhanced the hydrophilicity and pore structure of the polyurethane composite films. The active species BiOX were observed to grow as nanosheets with high dispersion on the internal skeleton and silk protein surface of the polyurethane-silk protein film. The photocatalytic efficiency of BiOX/PU-SF composite films was assessed through the degradation of Rhodamine B under visible light irradiation. Among the tested films, the BiOBr/PU-SF composite exhibited the highest removal rate of RhB at 98.9%, surpassing the removal rates of 93.7% for the BiOCl/PU-SF composite and 85.6% for the BiOI/PU-SF composite. Furthermore, an active species capture test indicated that superoxide radical (•O2-) and hole (h+) species played a predominant role in the photodegradation process.

"Core/Shell" Nanocomposites as Photocatalysts for the Degradation of the Water Pollutants Malachite Green and Rhodamine B.

"Core/shell" composites are based on a ferrite core coated by two layers with different properties, one of them is an isolator, SiO2, and the other is a semiconductor, TiO2. These composites are attracting interest because of their structure, photocatalytic activity, and magnetic properties. Nanocomposites of the "core/shell" МFe2O4/SiO2/TiO2 (М = Zn(II), Co(II)) type are synthesized with a core of MFe2O4 produced by two different methods, namely the sol-gel method (SG) using propylene oxide as a gelling agent and the hydrothermal method (HT). SiO2 and TiO2 layer coating is performed by means of tetraethylorthosilicate, TEOS, Ti(IV) tetrabutoxide, and Ti(OBu)4, respectively. A combination of different experimental techniques is required to prove the structure and phase composition, such as XRD, UV-Vis, TEM with EDS, photoluminescence, and XPS. By Rietveld analysis of the XRD data unit cell parameters, the crystallite size and weight fraction of the polymorphs anatase and rutile of the shell TiO2 and of the ferrite core are determined. The magnetic properties of the samples, and their activity for the photodegradation of the synthetic industrial dyes Malachite Green and Rhodamine B are measured in model water solutions under UV light irradiation and simulated solar irradiation. The influence of the water matrix on the photocatalytic activity is determined using artificial seawater in addition to ultrapure water. The rate constants of the photocatalytic process are obtained along with the reaction mechanism, established using radical scavengers where the role of the radicals is elucidated.

Benzorhodol derived far-red/near-infrared fluorescent probes for selective and sensitive detection of butyrylcholinesterase activity in living cells and the non-alcoholic fatty liver of zebrafish.

Liver diseases are a growing public health concern and the development of non-alcoholic fatty liver disease (NAFLD) has a significant impact on human metabolism. Butyrylcholinesterase (BChE) is a vital biomarker for NAFLD, making it crucial to monitor BChE activity with high sensitivity and selectivity. In this study, we designed and synthesized a range of benzorhodol-derived far-red/near-infrared fluorescent probes, FRBN-B, NF-SB, and NF-B, for the quantitative detection and imaging of BChE. These probes differed in the size of their conjugated systems and in the number of incorporated cyclopropanecarboxylates, acting as the recognition site for BChE. Comprehensive characterization showed that FRBN-B and NF-SB fluorescence was triggered by BChE-mediated hydrolysis, while an additional cyclopropanecarboxylate in NF-B impeded the fluorescence release. High selectivity towards BChE was observed for FRBN-B and NF-SB, with a detection limit of 7.2 × 10-3 U mL-1 for FRBN-B and 1.9 × 10-3 U mL-1 for NF-SB. The probes were further employed in the evaluation of BChE inhibitor efficacy and imaging of intracellular BChE activity. Additionally, FRBN-B was utilized for imaging the BChE activity level in liver tissues in zebrafish, demonstrating its potential as a diagnostic tool for NAFLD.

Biothiols-activated near-infrared frequency up-conversion luminescence probe for early evaluation of drug-induced hepatotoxicity.

A novel biothiols-sensitive near-infrared (NIR) fluorescent probe RhDN based on a rhodamine skeleton was developed for early detection of drug-induced hepatotoxicity in living mice. RhDN can be used not only as a conventional large stokes shift fluorescent (FL) probe, but also as a kind of anti-Stokes frequency upconversion luminescence (FUCL) molecular probe, which represents a long wavelength excitation (808 nm) to short wavelength emission (760 nm), and response to Cys/Hcy/GSH with high sensitivity. Compared with traditional FL methods, the FUCL method exhibited a lower detection limit of Cys, Hcy, and GSH in 75.1 nM, 101.8 nM, and 84.9 nM, respectively. We exemplify RhDN for tracking endogenously biothiols distribution in living cells and further realize real-time in vivo bioimaging of biothiols activity in mice with dual-mode luminescence system. Moreover, RhDN has been successfully applied to visualize the detection of drug-induced hepatotoxicity in living mice. Overall, this report presents a unique approach to the development of large stokes shift NIR FUCL molecular probes for in vitro and in vivo biothiols biosensing.

High-Resolution Fluorespirometry to Assess Dynamic Changes in Mitochondrial Membrane Potential in Human Immune Cells.

Peripheral mononuclear cells (PBMCs) exhibit robust changes in mitochondrial respiratory capacity in response to health and disease. While these changes do not always reflect what occurs in other tissues, such as skeletal muscle, these cells are an accessible and valuable source of viable mitochondria from human subjects. PBMCs are exposed to systemic signals that impact their bioenergetic state. Thus, expanding our tools to interrogate mitochondrial metabolism in this population will elucidate mechanisms related to disease progression. Functional assays of mitochondria are often limited to using respiratory outputs following maximal substrate, inhibitor, and uncoupler concentrations to determine the full range of respiratory capacity, which may not be achievable in vivo. The conversion of adenosine diphosphate (ADP) to adenosine triphosphate (ATP) by ATP-synthase results in a decrease in mitochondrial membrane potential (mMP) and an increase in oxygen consumption. To provide a more integrated analysis of mitochondrial dynamics, this article describes the use of high-resolution fluorespirometry to measure the simultaneous response of oxygen consumption and mitochondrial membrane potential (mMP) to physiologically relevant concentrations of ADP. This technique uses tetramethylrhodamine methylester (TMRM) to measure mMP polarization in response to ADP titrations following maximal hyperpolarization with complex I and II substrates. This technique can be used to quantify how changes in health status, such as aging and metabolic disease, affect the sensitivity of mitochondrial response to energy demand in PBMCs, T-cells, and monocytes from human subjects.

Rhodamine 19 Alkyl Esters as Effective Antibacterial Agents.

Mitochondria-targeted antioxidants (MTAs) have been studied quite intensively in recent years as potential therapeutic agents and vectors for the delivery of other active substances to mitochondria and bacteria. Their most studied representatives are MitoQ and SkQ1, with its fluorescent rhodamine analog SkQR1, a decyl ester of rhodamine 19 carrying plastoquinone. In the present work, we observed a pronounced antibacterial action of SkQR1 against Gram-positive bacteria, but virtually no effect on Gram-negative bacteria. The MDR pump AcrAB-TolC, known to expel SkQ1, did not recognize and did not pump out SkQR1 and dodecyl ester of rhodamine 19 (C12R1). Rhodamine 19 butyl (C4R1) and ethyl (C2R1) esters more effectively suppressed the growth of ΔtolC Escherichia coli, but lost their potency with the wild-type E. coli pumping them out. The mechanism of the antibacterial action of SkQR1 may differ from that of SkQ1. The rhodamine derivatives also proved to be effective antibacterial agents against various Gram-positive species, including Staphylococcus aureus and Mycobacterium smegmatis. By using fluorescence correlation spectroscopy and fluorescence microscopy, SkQR1 was shown to accumulate in the bacterial membrane. Thus, the presentation of SkQR1 as a fluorescent analogue of SkQ1 and its use for visualization should be performed with caution.

A firm-push-to-open and light-push-to-lock strategy for a general chemical platform to develop activatable dual-modality NIR-II probes.

Activatable near-infrared (NIR) imaging in the NIR-II range is crucial for deep tissue bioanalyte tracking. However, designing such probes remains challenging due to the limited availability of general chemical strategies. Here, we introduced a foundational platform for activatable probes, using analyte-triggered smart modulation of the π-conjugation system of a NIR-II-emitting rhodamine hybrid. By tuning the nucleophilicity of the ortho-carboxy moiety, we achieved an electronic effect termed "firm-push-to-open and light-push-to-lock," which enables complete spirocyclization of the probe before sensing and allows for efficient zwitterion formation when the light-pushing aniline carbamate trigger is transformed into a firm-pushing aniline. This platform produces dual-modality NIR-II imaging probes with ~50-fold fluorogenic and activatable photoacoustic signals in live mice, surpassing reported probes with generally below 10-fold activatable signals. Demonstrating generality, we successfully designed probes for hydrogen peroxide (H2O2) and hydrogen sulfide (H2S). We envision a widespread adoption of the chemical platform for designing activatable NIR-II probes across diverse applications.

Removal of pollutants through photocatalysis, adsorption, and electrochemical sensing by a unique plasmonic structure of palladium and strontium oxide nanoparticles sandwiched between 2D nanolayers.

The redesigned engineering building of nanocomposite (NCP) depends on metal oxides of palladium oxide (PdO) nanoparticles (NPs) conjugate with the n-type semiconductor of strontium oxide (SrO) NPs on the electron carrier surface of graphene oxide (GO) and reduce graphene oxide (rGO) nanosheet is the main target of the current work. The low efficiency of PdO (n-type) and SrO (p-type) gave an overview of the increasing generation electron efficiency via building the ohmic area on the GO and rGO surface using the Z-scheme mechanism. The efficiency of the NCP surface for destroying organic pollutants such as mixed dyes of Rhodamine B and methylene blue (RhB/MB), as against insecticides like imidacloprid, and the removal of heavy metals such as chromium ions was studied. The production of clean water against pollutants materials was investigated through adsorption and photocatalytic processes, electrochemical, and spectroscopy methods to detect the activity of NCP. The rate constant of the adsorption pollutants is 0.1776 min-1 (MB), 0.3489 min-1 (RhB), 0.3627 min-1 (imidacloprid), and 0.5729 min-1 (Cr3+). The photocatalytic rate recorded at 0.01218 min-1 (MB), 0.0096 min-1 (RhB), appeared degradation rate at 0.0086 min-1 (imidacloprid), 0.0019 min-1 (Cr6+), and 0.0471 min-1 (Cr3+). The adsorption and photocatalytic efficiency of nanocatalyst (NCP) was calculated at 91% (RhB), 93% (MB), 73% (imidacloprid), 63% (Cr3+), while the photocatalytic efficiency is 63% (RhB), 94% (MB), 86% (imidacloprid), 33% (Cr3+). The recyclability of NCP was tested for five cycles, and the efficiency was discovered at 55% after the fifth cycle. The cytotoxicity of NCP was studied to detect the safety of the fabricated materials. The study validates that the fabricated nanocomposite exhibits great potential as an innovative material for producing clean water.

Oxygen-deficient AgIO3 for efficiently photodegrading organic contaminants under natural sunlight.

Defect engineering is regarded as an effective strategy to boost the photo-activity of photocatalysts for organic contaminants removal. In this work, abundant surface oxygen vacancies (Ov) are created on AgIO3 microsheets (AgIO3-OV) by a facile and controllable hydrogen chemical reduction approach. The introduction of surface Ov on AgIO3 broadens the photo-absorption region from ultraviolet to visible light, accelerates the photoinduced charges separation and migration, and also activates the formation of superoxide radicals (•O2-). The AgIO3-OV possesses an outstanding degradation rate constant of 0.035 min-1, for photocatalytic degrading methyl orange (MO) under illumination of natural sunlight with a light intensity is 50 mW/cm2, which is 7 and 3.5 times that of the pristine AgIO3 and C-AgIO3 (AgIO3 is calcined in air without generating Ov). In addition, the AgIO3-OV also exhibit considerable photoactivity for degrading other diverse organic contaminants, including azo dye (rhodamine B (RhB)), antibiotics (sulflsoxazole (SOX), norfloxacin (NOR), chlortetracycline hydrochloride (CTC), tetracycline hydrochloride (TC) and ofloxacin (OFX)), and even the mixture of organic contaminants (MO-RhB and CTC-OFX). After natural sunlight illumination for 50 min, 41.4% of total organic carbon (TOC) for MO-RhB mixed solution can be decreased over AgIO3-OV. In a broad range of solution pH from 3 to 11 or diverse water bodies of MO solution, AgIO3-OV exhibits attractive activity for decomposing MO. The MO photo-degradation process and mechanism over AgIO3-OV under natural sunlight irradiation has been systemically investigated and proposed. The toxicities of MO and its degradation intermediates over AgIO3-OV are compared using Toxicity Estimation Software (T.E.S.T.). Moreover, the non-toxicity of both AgIO3-OV catalyst and treated antibiotic solution (CTC-OFX mixture) are confirmed by E. coli DH5a cultivation test, supporting the feasibility of AgIO3-OV catalyst to treat organic contaminants in real water under natural sunlight illumination.

Unlocking enhanced photocatalytic power: Donor-acceptor synergy in non-metallic g-C3N4 hollow nanospheres.

Selecting safe, non-toxic, and non-metallic semiconductor materials that facilitate the degradation of pollutants in water stands out as an optimal approach to combat environmental pollution. Herein, graphitic carbon nitride (g-C3N4)-based hollow nanospheres nonmetallic photocatalyst modified with covalent organic framework materials named TpMA, based on 1, 3, 5-trimethylchloroglucuronide (Tp) and melamine (MA), was successfully synthesized (abbreviated as CNTP). The ordered electron donor-acceptor structure inherent in TpMA contributed to enhancing the transport efficiency of photogenerated carriers in CNTP. The CNTP photocatalysts exhibited excellent performance in degrading rhodamine B and tetracycline in visible light, with optimal degradation rates reached more than 90% in 60 and 80 min, respectively, which were 5.3 and 3.0 times higher than those of pure CNNS. The increased photocatalytic efficiency observed in CNTP composites could be traced back to the covalently connection between the two molecules, forming a π-conjugated system that facilitated the separative efficiency of photogenerated electron-hole pairs and intensified the utilization of visible light. This study provided a new means to design and fabricate highly efficient and environmentally friendly non-metallic photocatalytic materials.

Engineering a far-red fluorescent probe for rapid detection of Hg(II) ions in both cells and zebrafish.

Abnormal accumulation of mercury ions (Hg2+) in organisms can lead to severe central nervous system and other diseases. Therefore, the monitoring and detection of Hg2+ are of great significance for human health and environmental safety. Herein, we designed and synthesized a novel far-red to NIR emission fluorescent probe (Rho-Hg) based on rhodamine derivative as the fluorophore and thiospirolactone as the recognition site for turn-on detecting of Hg2+ in living cells and zebrafish. The probe Rho-Hg displayed superior sensitivity (detection limit = 17.5 nM), rapid response (<1 min), colorimetric change, high selectivity, and moderate pH stability. Leveraging this probe, we realized the real-time monitoring of Hg2+ in real samples, living cells and zebrafish. By fostering zebrafish embryos and larvae in Hg2+-containing nutrient solution, we noticed that Hg2+ was ingested into the zebrafish liver when zebrafish were grown up to 3 days old, and thus we successfully monitored the accumulation and changes of Hg2+ during zebrafish growth and development. Thus, the probe Rho-Hg could be a powerful tool for sensitive and real-time monitoring of Hg2+ in living systems.

Ratiometric fluorescence method comprising carbon dots and rhodamine 6G encapsulated in metal-organic framework microcubes for curcumin detection.

A ratiometric fluorescence method comprising carbon dots (CDs) and rhodamine 6G (Rh-6G) encapsulated in the microcubes of metal-organic framework (MOF-5) is introduced for the sensitive detection of curcumin (Cur) in condiments. CDs@MOF-5@Rh-6G, synthesized by the adsorption of Rh-6G on MOF-5 embedded with CDs, showed two distinct emission peaks at 435 and 560 nm under excitation at 335 nm, and could be used for Cur detection by ratiometric fluorescence. In the presence of Cur, the fluorescence of the CDs at 435 nm (F435) was quenched by Cur owing to internal filtering and dynamic quenching effects, whereas the emission of Rh-6G at 560 nm (F560) remained unchanged (335 nm is the excitation wavelength, 435 and 560 nm are the emission wavelengths, in which F435/F560 values are used as the output results). Under optimal conditions, a linear relationship was observed between the Cur concentration (in the range 0.1-5 µmol/L) and F435/F560 value for CDs@MOF-5@Rh-6G, with a detection limit of 15 nmol/L. Notably, the proposed method could accurately detect Cur in mustard, curry, and red pepper powders. Therefore, this study could improve the quality control of food and facilitate the development of sensitive ratiometric fluorescence probes.

Multi-ion detection chemosensor based on rhodamine for turn-on fluorescence sensing and bioimaging of Fe3+, Al3+, Cr3+, and Hg2+ under different channels.

A novel rhodamine-based multi-ion fluorescent sensor, RGN, was designed and synthesized for the highly selective detection of mercury ions (Hg2+) in ethanol and water systems, as well as trivalent cations (Fe3+, Al3+, and Cr3+) in acetonitrile and water systems using a two-step Schiff base reaction method. Nuclear magnetic titration experiments and theoretical calculations demonstrated that the sensor achieved the detection of the aforementioned metal ions through the fluorescence turn-on phenomenon induced by lactam ring-opening. Density functional theory (DFT) calculation results showed decreased HOMO-LUMO energy gaps and increased dipole moments, indicating the effective coordination of the sensor with the corresponding metal ions to form more stable complexes, thereby achieving detection objectives. Furthermore, the fluorescence turn-on sensor RGN exhibited relatively low detection limits, with limits of detection (LOD) for Fe3+, Al3+, Cr3+, and Hg2+ being 10.20 nM, 14.66 nM, 58.78 nM, and 73.33 nM, respectively. Finally, practical applications of sensor RGN in environmental water samples, L929 cells, and zebrafish were demonstrated, indicating its potential for detecting and tracking Fe3+, Al3+, Cr3+, and Hg2+ in environmental samples and biological systems, with prospects for biomedical applications in the diagnosis and treatment of heavy metal ion-induced diseases.

When covalent organic frameworks meet zeolites: Enhancing rhodamine B removal through the synergy in the emerging organic-inorganic nanoadsorbents.

The development of new porous materials has attracted intense attention as adsorbents for removing pollutants from wastewater. However, pure inorganic and organic porous materials confront various problems in purifying the wastewater. In this work, we integrated a covalent organic framework (TpPa-1) with an inorganic zeolite (TS-1) for the first time via a solvothermal method to fabricate new-type nanoadsorbents. The covalent organic framework/zeolite (TpPa-1/TS-1) nanoadsorbents combined the merits of the zeolite and COF components and possessed efficient adsorptive removal of organic contaminants from solution. Structural morphology and chemical composition characterization by powder X-ray diffraction, scanning electron microscopy, Fourier-transform infrared spectroscopy, X-ray photoelectron spectroscopy, transmission electron microscopy and thermogravimetric analysis demonstrated the successful preparation of TpPa-1/TS-1 composite nanoadsorbents. The resultant composite adsorbent TpPa-1/TS-1 removed rhodamine B at 1.7 and 2.6 times the efficiency of TpPa-1 and TS-1, respectively. Additional investigation revealed that the Freundlich adsorption isotherm and the pseudo-second-order kinetic model could be employed to represent the adsorption process more appropriately. Thermodynamic calculation analysis showed that the adsorption process proceeded spontaneously and exothermically. Besides, the effects of pH, absorbent mass and ionic strength on the adsorption performance were systematically investigated. The prepared composite adsorbent showed a slight decrease in removal efficiency after eight cycles of repeated use, and real water environment experiments also showed the high stability of the adsorbent. The enhanced performance can be attributed to electrostatic interaction, acid-base interaction, hydrogen bonding and π-π interactions.

Time-Separated Pulse Release-Activation of an Enzyme from Alginate-Polyethylenimine Hydrogels Using Electrochemically Generated Local pH Changes.

ß-Glucosidase (EC 3.2.1.21) from sweet almond was encapsulated into pH-responsive alginate-polyethylenimine (alginate-PEI) hydrogel. Then, electrochemically controlled cyclic local pH changes resulting from ascorbate oxidation (acidification) and oxygen reduction (basification) were used for the pulsatile release of the enzyme from the composite hydrogel. Activation of the enzyme was controlled by the very same pH changes used for ß-glucosidase release, separating these two processes in time. Importantly, the activity of the enzyme, which had not been released yet, was inhibited due to the buffering effect of PEI present in the gel. Thus, only a portion of the released enzyme was activated. Both enzymatic activity and release were monitored by confocal fluorescence microscopy and regular fluorescent spectroscopy. Namely, commercially available very little or nonfluorescent substrate 4-methylumbelliferyl-ß-d-glucopyranoside was hydrolyzed by ß-glucosidase to produce a highly fluorescent product 4-methylumbelliferone during the activation phase. At the same time, labeling of the enzyme with rhodamine B isothiocyanate was used for release observation. The proposed work represents an interesting smart release-activation system with potential applications in biomedical field.

A Wettability Contrast SERS Droplet Assay for Multiplexed Analyte Detection.

Droplet assay platforms have emerged as a significant methodology, providing distinct advantages such as sample compartmentalization, high throughput, and minimal analyte consumption. However, inherent complexities, especially in multiplexed detection, remain a challenge. We demonstrate a novel strategy to fabricate a plasmonic droplet assay platform (PDAP) for multiplexed analyte detection, enabling surface-enhanced Raman spectroscopy (SERS). PDAP efficiently splits a microliter droplet into submicroliter to nanoliter droplets under gravity-driven flow by wettability contrast between two distinct regions. The desired hydrophobicity and adhesive contrast between the silicone oil-grafted nonadhesive hydrophilic zone with gold nanoparticles is attained through (3-aminopropyl) triethoxysilane (APTES) functionalization of gold nanoparticles (AuNPs) using a scotch-tape mask. The wettability contrast surface facilitates the splitting of aqueous droplets with various surface tensions (ranging from 39.08 to 72 mN/m) into ultralow volumes of nanoliters. The developed PDAP was used for the multiplexed detection of Rhodamine 6G (Rh6G) and Crystal Violet (CV) dyes. The limit of detection for 120 nL droplet using PDAP was found to be 134 pM and 10.1 nM for Rh6G and CV, respectively. These results align with those from previously reported platforms, highlighting the comparable sensitivity of the developed PDAP. We have also demonstrated the competence of PDAP by testing adulterant spiked milk and obtained very good sensitivity. Thus, PDAP has the potential to be used for the multiplexed screening of food adulterants.

A rhodamine-based fluorescent probe used to determine nitroxyl (HNO) in lysosomes.

The reactive nitrogen species (RNS) in lysosomes play a major role during the regulation of lysosomal microenvironment. Nitroxyl (HNO) belongs to active nitrogen species (RNS) and is becoming a potential diagnostic and therapeutic biomarker. However, the complex synthesis routes of HNO in biosystem always hinder the exact determination of HNO in living cells. Here, a rhodamine-based fluorescent probe used to determine nitroxyl (HNO) in lysosomes was constructed and synthesized. 2-(Diphenylphosphino)benzoate was utilized as the sensing unit for HNO and morpholine was chose as the targeting group for lysosome. Before the addition of HNO, the probe displayed a spirolactone structure and almost no fluorescence was found. After the addition of HNO, the probe existed as a conjugated xanthene form and an intense green fluorescence was observed. The fluorescent probe possessed fast response (3 min) and high selectivity for HNO. Furthermore, fluorescence intensity of the probe linearly related with the HNO concentration in the range of 6.0 × 10-8 to 6.0 × 10-5 mol L-1. The detection limit was found to be 1.87 × 10-8 mol L-1 for HNO. Moreover, the probe could selectively targeted lysosome with excellent biocompatibility and had been effectually utilized to recognize exogenous HNO in A549 cells.

Green construction of self-floating polysaccharide-based hydrogels with catalytic activity for efficient organic pollutants reduction.

This study employed an anionic heteropolysaccharide extracted from overgrown Enteromorpha and homopolysaccharide pullulan to fabricate a self-floating hydrogel by introducing bubble templates. Subsequently, green in-situ reduction and immobilization of silver nanoparticles (Ag NPs) in the hydrogel were successfully achieved without additional reducing agents. The heteropolysaccharide from Enteromorpha provides carboxyl and sulfate groups for Ag+ ions complexation, which is beneficial for the in-situ reduction of Ag NPs and inhibits their aggregation. The incorporation of bubble templates facilitates the creation of a hierarchical pore structure in the hydrogel, giving it self-floating properties for easy recycling, while the hierarchical network with rich anchor sites ensuring adequate traction for Ag NPs dispersion and stabilization. By adjusting polysaccharide content and using bubble templates, Ag NPs smaller than 10 nm can be obtained. The composite hydrogel exhibits tunable catalytic activity and excellent degradation towards Rhodamine B, Methyl Orange, and 4-Nitrophenol, with the normalized rate constant (knor) of 78.89, 59.08, and 30.42 min-1 g-1, respectively. Notably, the reduction efficiency remained above 98 % after 6 recycles with little leaching of Ag NPs, benefiting from its self-floating ability for easy recovery in practical applications.

Evaluation of polymersome permeability as a fundamental aspect towards the development of artificial cells and nanofactories.

Polymersomes are synthetic vesicles with potential use in healthcare, chemical transformations in confined environment (nanofactories), and in the construction of artificial cells and organelles. In this framework, one of the most important features of such supramolecular structures is the permeability behavior allowing for selective control of mass exchange between the inner and outer compartments. The use of biological and synthetic nanopores in this regard is the most common strategy to impart permeability nevertheless, this typically requires fairly complex strategies to enable porosity. Yet, investigations concerning the permeability of polymer vesicles to different analytes still requires further exploration and, taking these considerations into account, we have detailed investigated the permeability behavior of a variety of polymersomes with regard to different analytes (water, protons, and rhodamine B) which were selected as models for solvents, ions, and small molecules. Polymersomes based on hydrophilic blocks of poly[N-(2-hydroxypropyl)methacrylamide] (PHPMA) or PEO (poly(ethylene oxide)) linked to the non-responsive blocks poly[N-(4-isopropylphenylacetamide)ethyl methacrylate] (PPPhA) or poly(methyl methacrylate) (PMMA), or to the stimuli pH-responsive block poly[2-(diisopropylamino)ethyl methacrylate] (PDPA) have been investigated. Interestingly, the produced PEO-based vesicles are notably larger than the ones produced using PHPMA-containing block copolymers. The experimental results reveal that all the vesicles are inherently permeable to some extent with permeability behavior following exponential profiles. Nevertheless, polymersomes based on PMMA as the hydrophobic component were demonstrated to be the least permeable to the small molecule rhodamine B as well as to water. The synthetic vesicles based on the pH-responsive PDPA block exhibited restrictive and notably slow proton permeability as attributed to partial chain protonation upon acidification of the medium. The dye permeability was evidenced to be much slower than ion or solvent diffusion, and in the case of pH-responsive assemblies, it was demonstrated to also depend on the ionic strength of the environment. These findings are understood to be highly relevant towards polymer selection for the production of synthetic vesicles with selective and time-dependent permeability, and it may thus contribute in advancing biomimicry and nanomedicine.