Peptide-Directed Synthesis of Aggregation-Induced Emission Enhancement-Active Gold Nanoclusters for Single- and Two-Photon Imaging of Lysosome and Expressed αvß3 Integrin Receptors.

This study explores the synthesis and characterization of aggregation-induced emission enhancement (AIEE)-active gold nanoclusters (AuNCs), focusing on their near-infrared luminescence properties and potential applications in biological imaging. These AIEE-active AuNCs were synthesized via the NaBH4-mediated reduction of HAuCl4 in the presence of peptides. We systematically investigated the influence of the peptide sequence on the optical features of the AuNCs, highlighting the role of glutamic acid in enhancing their quantum yield (QY). Among the synthesized peptide-stabilized AuNCs, EECEE-stabilized AuNCs exhibited the maximum QY and a pronounced AIEE effect at pH 5.0, making them suitable for the luminescence imaging of intracellular lysosomes. The AIEE characteristic of the EECEE-stabilized AuNCs was demonstrated through examinations using transmission electron microscopy, dynamic light scattering, zeta potential analysis, and single-particle imaging. The formation of the EECEE-stabilized AuNCs was confirmed by size-exclusion chromatography and mass spectrometry. Spectroscopic and electrochemical examinations uncover the formation process of EECEE-stabilized AuNCs, comprising EECEE-mediated reduction, NaBH4-induced nucleation, complex aggregation, and subsequent cluster growth. Furthermore, we demonstrated the utility of these AuNCs as luminescent probes for intracellular lysosomal imaging, leveraging their pH-responsive AIEE behavior. Additionally, cyclic arginylglycylaspartic acid (RGD)-modified AIEE dots, derived from cyclic RGD-linked peptide-induced aggregation of EECEE-stabilized AuNCs, were developed for single- and two-photon luminescence imaging of αvß3 integrin receptor-positive cancer cells.

Aptamer-based flares hybridized with single-stranded DNA-conjugated MoS2 nanosheets for ratiometric fluorescence sensing and imaging of potassium ions and adenosine triphosphate in human fluids and living cells.

Addressing the limitations observed in previous studies, where the quantitative range of nanoprobes for detecting K+ and adenosine triphosphate (ATP) did not cover concentrations found within living cells, the present study aimed to develop ratiometric nanoprobes that can accurately sense changes in K+ and ATP levels in living cells and quantify them in human fluids. The proposed nanoprobes consisted of recognition flares modified with 6-carboxyfluorescein (FAM) and 5-carboxytetramethylrhodamine (TAMRA), along with thiolate single-stranded DNA (ssDNA) and molybdenum disulfide nanosheets (MoS2 NSs). The thiolate ssDNA acts as a linker between the flares and the MoS2 NSs, directly forming a functional nanostructure at room temperature. The direct conjugation of labeled flares to the MoS2 NSs simplifies the fabrication process. In the absence of K+ and ATP, the hybridization of flares and thiolate ssDNA caused FAM to move away from TAMRA, suppressing the fluorescence resonance energy transfer (FRET) process. However, upon the introduction of K+ and ATP, the flares undergo a structural transformation via the formation of G-quadruplex formation and the generation of hairpin-shaped structures, respectively. This structural change leads to the release of the flares from the ssDNA-conjugated nanosheet surface. The release of the flares brings FAM and TAMRA into close proximity, allowing FRET to occur, leading to FRET and static quenching. By monitoring the ratio between the fluorescence intensities of FAM and TAMRA, the concentration of K+ (5-100 mM) and ATP (0.3-5 mM) can be accurately determined by the proposed nanoprobes. The advantages of these nanoprobes lie in their ability to provide ratiometric measurements, which enhance the accuracy and reliability of the quantification process. The proposed nanoprobes offer potential applications as ratiometric imaging probes for monitoring K+ and ATP-related reactions in living cells, providing valuable insights into cellular processes. Additionally, they can be employed for determining the levels of K+ and ATP in human fluids, offering potential diagnostic applications in various clinical settings.

Peptide-modified carbon dot aggregates for ultrasensitive detection of lipopolysaccharide through aggregation-induced emission enhancement.

This study fabricated yellow-emitting CDs (Y-CDs) by hydrothermal treatment of citric acid and urea and applied them as a fluorescence turn-on platform for sensitive and selective detection of lipopolysaccharide (LPS) based on the non-shifted AIEE of peptide-stabilized CD aggregates. The designed peptide (named K3) consisting of aggregation-active and LPS-recognition units triggered the aggregation of Y-CDs, switching on their fluorescence through the blue-shifted AIEE process. The formed K3-stabilized Y-CD aggregates (K3-YCDAs) specifically interacted with LPS at neutral pH, demonstrating that the sequence of the decorated peptide was highly connected with their selectivity and sensitivity. The K3-YCDAs provided a fast response time (within 5 min) to detect LPS with a quantification range of 0.5-100.0 nM and a limit of detection (LOD, signal-to-noise ratio of 3) of 300.0 pM. By integrating ultrafiltration membranes as a concentration device with K3-YCDAs as a sensing probe, the LOD for LPS was further reduced to 3.0 pM. The determination of picomolar levels of plasma LPS by the K3-YCDAs coupled to the centrifugation ultrafiltration was demonstrated to fall within the specificity range of clinical interest for sepsis patients. Also, the K3-YCDAs served as a fluorescent probe to selectively image and quantify E. coli cells. The distinct advantages of the K3-YCDAs for LPS include fast response time, wide linear range, low detection limit, and excellent selectivity compared to previously reported sensors.

Tapping the potential of a glucosamine polysaccharide-diatomaceous earth hybrid adsorbent in the solid phase extraction of a persistent organic pollutant and toxic pesticide 4,4'-DDT from water.

A chitosan (a glucosamine polysaccharide)-diatomaceous earth hybrid was studied for the adsorption of 4,4'-dichloro-diphenyl-trichloroethane (4,4'-DDT), a persistent organic pollutant and organochlorine pesticide compound from water. The diverse adsorption process parameters were studied and the modified adsorbent was characterized through XRD, SEM-EDX, FT-IR, XRF, BET and TGA analysis. The concentration of 4,4'-DDT was measured using gas chromatography-tandem mass spectrometry (GC-MS/MS) by adopting a validated analytical procedure. The Langmuir and Freundlich isotherms ascertained the adsorption capacity. The optimum pH and temperature for 4,4'-DDT adsorption were found to be between 5.0 and 7.0 and 20 and 30 °C respectively. Thermodynamic parameters confirmed that the adsorption of DDT on chitosan modified with diatomaceous earth was an exothermic process. The data obtained from kinetics and intra-particle diffusion showed that the composite material is able to sequester 4,4'-DDT and this is reflected in the Langmuir adsorption capacity of 0.968 mg g-1. The adsorbed 4,4'-DDT was successfully eluted with ethyl acetate and recycling studies showed that the modified chitosan can be used for three cycles with significant adsorption performance and this adsorbent proved its efficacy in removing 4,4'-DDT from farm water.

Self-Assembly of Poly(ethyleneimine)-Modified g-C3N4 Nanosheets with Lysozyme Fibrils for Chromium Detoxification.

We disclose a straightforward approach to fabricate nanocomposites for efficient capture of Cr(VI) from an aqueous solution through the self-assembly of poly(ethyleneimine)-modified graphitic carbon nitride nanosheets (PEI-g-C3N4 NSs) and lysozyme fibrils (LFs). The as-made PEI-g-C3N4 NSs@LFs exhibited mesoporous structures with a high specific surface area of 39.6 m2 g-1, a large pore volume of 0.25 cm3 g-1, several functional groups (e.g., -N, -NH, -NH2, and -COOH), and a zero-point charge at pH 9.1. These merits allow the PEI-g-C3N4 NSs@LFs to further enhance their physical adsorption and electrostatic attraction with the negatively charged Cr(VI) species of HCrO4- and CrO42-, which is beneficial for the uptake of Cr(VI), >80%, from an aqueous solution in a wide pH range. Interestingly, X-ray photoelectron spectra indicate that the PEI-g-C3N4 NSs@LFs converted Cr(VI) to Cr(III) through visible-light-induced photoreduction. The adsorption of Cr(VI) on the surface of PEI-g-C3N4 NSs@LFs was found to obey the Freundlich isotherm model, signifying that they have a heterogeneous surface for the multilayer uptake of Cr(VI). In contrast, the PEI-g-C3N4 NSs and LFs as Cr(VI) adsorbents followed the Langmuir isotherm model. Adsorption kinetic studies showed that the uptake of Cr(VI) through the PEI-g-C3N4 NSs@LFs was highly correlated with a pseudo-first-order model, suggesting that physisorption dominates the interaction of Cr(VI) and the PEI-g-C3N4 NSs@LFs. In real-life applications, the PEI-g-C3N4 NSs@LFs were used for the detoxification of the total chromium in the industrial effluent and sludge samples.

Prospective application of diethylaminoethyl cellulose (DEAE-cellulose) with a high adsorption capacity toward the detoxification of 2,4-dichlorophenoxyacetic acid (2,4-D) from water.

Detoxification of pesticide residues requires effective methods. In this regard, the adsorption efficiency of diethylaminoethyl cellulose (DEAE-cellulose) as an adsorbent material for the removal of 2,4-dichlorophenoxyacetic acid (2,4-D) from water at different concentrations, times, pH and temperature was evaluated comprehensively. The obtained results showed that DEAE-cellulose has greater efficacy to eliminate 2,4-D from water with a high Langmuir maximum adsorption capacity of 429.18 mg g-1 at pH 7.0. Kinetic models and thermodynamics were investigated at length. The adsorption mechanism was understood by way of electrostatic, hydrogen bonding, and Lewis acid-base type interactions. Extensive analytical characterization of the DEAE-cellulose adsorbent before and after 2,4-D adsorption was performed and liquid chromatography with a tandem mass spectrometer (LC-MS/MS) was used for the quantification of 2,4-D. The regeneration of DEAE-cellulose was achievable using dilute formic acid and the DEAE-cellulose adsorbent showed high ability in the removal of 2,4-D from the agriculture run-off water.

L-cystine-linked BODIPY-adsorbed monolayer MoS2 quantum dots for ratiometric fluorescent sensing of biothiols based on the inner filter effect.

This study fabricated a dual-emission probe consisting of monolayer MoS2 quantum dots (M - MoS2 QDs) and L-cystine-linked boron-dipyrromethene (L-Cys-BODIPY) molecules for ratiometric sensing of biothiols, thiol product-related enzyme reactions, and ratiometric imaging of glutathione (GSH)-related reactions in HeLa cells. The formation of L-Cys-BODIPY-adsorbed M - MoS2 QDs (named as BODIPY-M-MoS2 QDs) was demonstrated by comparing them with M - MoS2 QDs using transmission electron microscopy, atomic force microscopy, and X-ray photoelectron spectroscopy. The BODIPY-M-MoS2 QDs exhibited dual-emission bands, excellent biocompatibility, and good resistance to photobleaching. It was found that the adsorbed L-Cys-BODIPY molecules rarely quenched the fluorescence of M - MoS2 QDs, and meanwhile, they were self-quenched by π-π stacking between each BODIPY backbones. The presence of biothiols induced the reduction of weakly fluorescent L-Cys-BODIPY to strongly fluorescent of L-cysteine-conjugated BODIPY. Since having a much higher molar absorption coefficient than L-Cys-BODIPY, the liberated L-cysteine-conjugated BODIPY behaved as an effective inner filter to absorb the excitation light and subsequently quenched the fluorescence of M - MoS2 QDs. The appearance of L-cysteine-conjugated BODIPY could barely affected to the fluorescence lifetime of M - MoS2 QDs, confirming the inner filter effect of L-cysteine-conjugated BODIPY onto the fluorescence of M - MoS2 QDs. The present probe not only provided a linear ratiometric response to 1-10 mM GSH, 1-10 µM cysteine, and 1-10 µM of homocysteine but also remarkably showed the ratiometric detection of thiol products from the reactions of 1-900 units L-1 S-adenosylhomocysteine (SAH) hydrolase and SAH as well as 1-850 units L-1 GSH reductase and disulfide GSH. Additionally, the present probe was well-suited for ratiometric imaging of intracellular GSH levels in non-treated and drug-treated HeLa cells.

Cerium(iii)-directed assembly of glutathione-capped gold nanoclusters for sensing and imaging of alkaline phosphatase-mediated hydrolysis of adenosine triphosphate.

Aggregation-induced emission enhancement (AIEE) of thiolated gold nanoclusters (AuNCs) has emerged as an attractive and alternative strategy to improve their brightness. This study demonstrates Ce(iii)-triggered AIEE of glutathione-capped AuNCs (GSH-AuNCs) through the coordination between two carboxylic groups of GSH and Ce(iii). The cluster size and valence state of GSH-AuNCs are almost identical to those of a Ce(iii)-induced assembly of GSH-AuNCs (named Ce(iii)-GSH-AuNCs). More importantly, the as-prepared Ce(iii)-GSH-AuNCs exhibit a higher quantum yield (up to 13%), longer luminescence lifetime, and shorter maximum luminescence peak than GSH-AuNCs. Additionally, Ce(iii)-GSH-AuNCs possess redox-switchable luminescence, high salt stability, and long-term storage stability. These findings provide clear evidence that the Ce(iii)-triggered aggregation of GSH-AuNCs is a crucial factor to improve the luminescence property of GSH-AuNCs. Intriguingly, the presence of adenosine triphosphate (ATP) switches off the luminescence of Ce(iii)-GSH AuNCs through the significant formation of Ce(iii)-ATP complexes. Furthermore, the ATP-induced luminescence quenching of Ce(iii)-GSH-AuNCs can be paired with the alkaline phosphatase (ALP)-ATP system to design a turn-on luminescent probe for ALP; the limit of detection for ALP is estimated to be 0.03 U L-1. Also, the biocompatibility of Ce(iii)-GSH-AuNCs enables the proposed system to detect ALP in human serum and HeLa cells.

Synthesis and Characterization of Two-Dimensional Transition Metal Dichalcogenide Magnetic MoS2@Fe3O4 Nanoparticles for Adsorption of Cr(VI)/Cr(III).

Recently, two-dimensional transition metal dichalcogenides (TMDs) have received tremendous attention in many fields including environmental remediation. Magnetic nanoparticles (Fe3O4NPs) decorated with MoS2 (MoS2@Fe3O4NPs) have been synthesized via a new one-step synthesis route and utilized as an efficient adsorbent for removal of Cr(VI)/Cr(III) from aqueous solutions. The obtained MoS2@Fe3O4NPs with numerous surface hydroxyl groups show uniform size and shape, excellent water-dispersibility, and superior magnetic property to enhance the adsorption. The physicochemical properties of the adsorbent prior to and after adsorption of Cr(VI)/Cr(III) were extensively characterized using several advanced instrumental techniques.The adsorption of Cr(VI)/Cr(III) on MoS2@Fe3O4NPs was performed under batch conditions aiming at identification of optimal contact time, pH value of chromium solution, and influence of the presence of competitive ions. This study was supported by modeling of adsorption equilibrium and kinetics by using empirical equations.

Effective adsorption of hexavalent chromium through a three center (3c) co-operative interaction with an ionic liquid and biopolymer.

Biopolymers as well as ionic liquids are known for their potential applications. In this work, we report the utility of chitosan as an excellent platform for impregnating the ionic liquid, tetraoctylammonium bromide by ultrasonication and its subsequent adsorption for chromium(VI). The effective mass transfer due to sonication coupled with the hydrogen bonding interaction between chitosan-ionic liquid and the electrostatic interaction involving the amino groups in chitosan and hexavalent chromium governs this three center (3c) co-operative mechanism. The adsorption followed a pseudo second order kinetics with a Langmuir adsorption capacity of 63.69 mg g(-1). Various isotherm models were used to correlate the experimental data and the adsorption process is exothermic with a decreased randomness at the solid-solution interface. The thermodynamics of the spontaneous adsorption process could be explained through a positive co-operative effect between the host (chitosan) and the guest (ionic liquid). The adsorbed chromium(VI) could be converted to ammonium chromate using ammonium hydroxide, thereby regenerating the adsorbent. The method could be translated into action in the form of practical application to a real sample containing chromium.