Hydrophobic Ag Research Articles

Rücktitelbild: Photoluminescence Quenching of Hydrophobic Ag29 Nanoclusters Caused by Molecular Decoupling during Aqueous Phase Transfer and EmissionRecovery through Supramolecular Recoupling (Angew. Chem. 12/2024)

Rücktitelbild: Photoluminescence Quenching of Hydrophobic Ag₂₉ Nanoclusters Caused by Molecular Decoupling during Aqueous Phase Transfer and EmissionRecovery through Supramolecular Recoupling (Angew. Chem. 12/2024)

Back Cover: Photoluminescence Quenching of Hydrophobic Ag29 Nanoclusters Caused by Molecular Decoupling during Aqueous Phase Transfer and EmissionRecovery through Supramolecular Recoupling (Angew. Chem. Int. Ed. 12/2024)

Back Cover: Photoluminescence Quenching of Hydrophobic Ag₂₉ Nanoclusters Caused by Molecular Decoupling during Aqueous Phase Transfer and EmissionRecovery through Supramolecular Recoupling (Angew. Chem. Int. Ed. 12/2024)

Photoluminescence Quenching of Hydrophobic Ag29 Nanoclusters Caused by Molecular Decoupling during Aqueous Phase Transfer and EmissionRecovery through Supramolecular Recoupling

AbstractExploiting emissive hydrophobic nanoclusters for hydrophilic applications remains a challenge because of photoluminescence (PL) quenching during phase transfer. In addition, the mechanism underlying PL quenching remains unclear. In this study, the PL‐quenching mechanism was examined by analyzing the atomically precise structures and optical properties of a surface‐engineered Ag29 nanocluster with an all‐around‐carboxyl‐functionalized surface. Specifically, phase‐transfer‐triggered PL quenching was justified as molecular decoupling, which directed an unfixed cluster surface and weakened the radiative transition. Furthermore, emission recovery of the quenched nanoclusters was accomplished by using a supramolecular recoupling approach through the glutathione‐addition‐induced aggregation of cluster molecules, wherein the restriction of intracluster motion and intercluster rotation strengthened the radiative transition of the clusters. The results of this work offer a new perspective on structure‐emission correlations for atomically precise nanoclusters and hopefully provide insight into the fabrication of highly emissive cluster‐based nanomaterials for downstream hydrophilic applications.

Removal of Oily Contaminants from Water by Using the Hydrophobic Ag Nanoparticles Incorporated Dopamine Modified Cellulose Foam.

The presence of oil-related contaminants in water has emerged as a severe threat to the environment. The separation of these contaminants from water has become a great challenge, and extensive efforts are being made to develop suitable, environmentally friendly materials. Highly hydrophobic materials are effective in the selective separation of oil from water. In this work, silver (Ag)-incorporated, highly hydrophobic dopamine-modified cellulose sponge was prepared by functionalizing with the range of alkyl silanes. The Ag nanoparticle-incorporated dopamine provided the appropriate roughness, whereas the alkyl component provided the low surface energy that made it selective towards oil. It was found that the alkyl groups with a longer chain length were more effective in enhancing the hydrophobicity of the Ag nanoparticle-incorporated, dopamine-modified cellulose. The developed materials were characterized by Fourier transform infrared spectroscopy (FTIR), field emission-scanning electron microscopy (FE-SEM), energy-dispersive X-ray spectroscopy (EDX), elemental mapping, and contact angle goniometry. The maximum water contact angle on the functionalized surfaces was observed at 148.4°. The surface of the C18s-Ag-DA-Cell-F showed excellent selectivity towards the oily component that rapidly permeated, and water was rejected wholly. The developed material showed a separation efficiency of 96.2% for the oil/water mixture. The C18s-Ag-DA-Cell-F material showed excellent reusability. Due to their environmentally friendly nature, excellent selectivity, and good separation efficiency, the functionalized cellulose materials can be used to separate oil and water effectively.

Imprinted Polymer Beads Loaded with Silver Nanoparticles for Antibacterial Applications.

After the emergence of multidrug-resistant strains, antibiotic resistance in bacteria has become an important problem. Thus, materials for combating multidrug-resistant bacteria are of vital importance. In this work, we developed an antibacterial material that can selectively capture and destruct bacteria on the basis of their physical characteristics. To achieve bacterial capture and deactivation with a single material, we used bacterial cells as templates to synthesize surface-imprinted polymer beads in bacteria-stabilized Pickering emulsions. Acrylate-functionalized polyethylenimine was used to coat the bacterial surface so that the coated bacteria can act as a particle stabilizer to establish an oil-in-water Pickering emulsion. Hydrophobic Ag nanoparticles were introduced into the oil phase composed of cross-linking monomers. Bacteria-imprinted beads (BIB) were obtained after the oil phase was polymerized. Bacterial binding experiments confirmed the importance of the imprinted sites for specific recognition with the target bacteria. The Ag nanoparticles embedded inside the polymer beads enhanced bacterial inactivation and reduced the leakage of heavy metal in aquatic environment. The combination of bacteria-imprinting with delivery of general-purpose antibacterial reagents offers a useful approach toward selective capture and destruction of bacteria.

Formation of Copolymer-Ag Nanoparticles Composite Micelles in Three-dimensional Co-flow Focusing Microfluidic Device

A novel method was presented to create composite micelles of amphiphilic copolymers and Ag nanoparticles (NPs) in a three-dimensional co-flow focusing microfluidic device (3D CFMD). Self-assembly of the copolymers was initiated by the fast mixing of water and a blend dispersion of hydrophobic Ag NPs and amphiphilic copolymers. At the same time, the hydrophobic Ag NPs enter the core of copolymer micelles, based on the hydrophobic interaction. The copolymer-Ag NPs composite micelles have a core-shell structure with copolymer shell and Ag NPs core. COMSOL Multiphysics is used to simulate the concentration distribution of copolymers and Ag NPs under different flow rates. Co-assembly microfluidic conditions are determined based on simulation results. Under suitable microfluidic conditions, both block copolymers and gradient copolymers can co-assemble with hydrophobic Ag NPs to form composite micelles, respectively. This microfluidic coassembly method will have a good prospect in the preparation of composite micelles of amphiphilic copolymers and metal nanoparticles.

Triggerable H2O2-Cleavable Switch of Paper-Based Biochips Endows Precision of Chemometer/Ratiometric Electrochemical Quantification of Analyte in High-Efficiency Point-of-Care Testing.

In this work, a triggerable H2O2-cleavable fluid switch mediated paper-based biochip, being amenable to multiplexing and quantitative analysis with the dual-response output of visual screening and ratiometric electrochemistry, was developed for sensitive detection of target on-site. By properly implanting hydrophobic Ag-H2O2 responsive material in specific zone to form a programmable fluid switch, the biochip could achieve different modes of blocking/connecting switching automatically. In order to improve the test performance, a ratiometric electrochemical signal readout was designed, which was enhanced by a secondary in situ growth method fabricating trepang-shaped Au modified paper working electrode. In virtue of hybridization chain reaction, classic competitive recognition interactions of aptamer and target, and ratiometric internally calibrated mechanisms, ultrasensitive detection of the target was realized. To acquire a more quantitative and straightforward naked eye visual screening, the hydrophobic Ag switch was triggered by stimulating instructions from H2O2, thus reconnecting the electrochemical and ratiometric units automatically and resulting in a "signal on" visual fluidic flow on the chemometer characterized by the accurate distance of color development as a detection motif. With MCF-7 and K562 cells as models, wider linear detection ranges from 150 to 1.0 × 107 and 220 to 7.0 × 106 cells mL-1 for MCF-7 and K562 cells, respectively, were achieved. Meanwhile, thanks to the paper fluid chemometer, an acceptable screening detection limit of 103 cells mL-1 was obtained in the quantitative colorimetric assays. The proposed paper-based biochips opened up new horizons for designing of integratable, easy-to-use, and precise point-of-care testing devices.

Hand-Held Femtogram Detection of Hazardous Picric Acid with Hydrophobic Ag Nanopillar SERS Substrates and Mechanism of Elasto-Capillarity

Picric acid (PA) is a severe environmental and security risk due to its unstable, toxic, and explosive properties. It is also challenging to detect in trace amounts and in situ because of its highly acidic and anionic character. Here, we assess sensing of PA under nonlaboratory conditions using surface-enhanced Raman scattering (SERS) silver nanopillar substrates and hand-held Raman spectroscopy equipment. The advancing elasto-capillarity effects are explained by molecular dynamics simulations. We obtain a SERS PA detection limit on the order of 20 ppt, corresponding attomole amounts, which together with the simple analysis methodology demonstrates that the presented approach is highly competitive for ultrasensitive analysis in the field.

Chiroptically Active Plasmonic Nanoparticles Having Hidden Helicity and Reversible Aqueous Solvent Effect on Chiroptical Activity.

The geometrical prerequisite for forming a helix is P (helical pitch) > d (wire diameter). Limited by the current development of nanofabrication techniques, it is difficult to minimize d and consequently P to the sub-10 nm molecule-comparable scale, preventing the study of chiral plasmonics at dimensions approaching the physical limit. Herein, glancing angle deposition is operated at substrate temperature of 0 °C and high speed of substrate rotation to generate silver nanoparticles (AgNPs) with nominal P < d. The AgNPs have intrinsic chiroptical activity characterized by circular dichroism (CD), originating from the hidden helicity. With increasing P from 3 to 66 nm, the plasmonic mode barely shifts but shows a logarithmic increase in CD amplitude. Immersing AgNPs in water causes the plasmonic mode to redshift and rise in CD amplitude, i.e., a water effect on chiroptical activity. Hydrophilic AgNP arrays with low array porosity show a reversible water effect, but hydrophobic Ag nanospiral arrays with P > d and high array porosity have an irreversible water effect. This work introduces a cost-effective, facile approach to minimize P to sub-10 nm at a regular substrate temperature, paving the way to study chiral plasmonics approaching the physical limit and exploit chirality-related bioapplications typically operated in aqueous solutions to tackle significant health and environmental problems.

Polarity‐reversal‐producing phase transfer of hydrophilic silver nanoclusters capped by a hyperbranched polymer from water to nonpolar organic solvents

ABSTRACTHyperbranched poly(ethylene imine) (PEI)‐capped Ag nanoclusters, synthesized starting from an aqueous environment, dispersed well in water and most polar organic solvents. However, with the addition of 1,4‐dioxane, the PEI‐capped Ag nanoclusters could be separated completely to obtain hydrophilic and hydrophobic Ag nanoclusters. Through this facile method, the successful phase transfer of PEI‐capped Ag nanoclusters from the aqueous phase to the nonpolar organic phase, such as from water to carbon tetrachloride, chloroform, and methylene bichloride, was easily realized. The polarity reversal of Ag nanoclusters were considered to be associated with the conformational change of PEI on the basis of the hydrophobic methylene groups of polymer backbone facing the external side or internal side, and this polarity reversal was irreversible. Moreover, PEIs with higher molecular weights showed a higher efficiency of phase transfer of the Ag nanoclusters. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016, 133, 43206.

Facile synthesis of SERS active Ag nanoparticles in the presence of tri-n-octylphosphine sulfide

A facile and novel way was reported here for the synthesis of hydrophobic Ag nanoparticles (NPs), using AgNO 3, tri-n-octylphosphine (TOP) and sulfur (S) powder in process. TOP was used as solvent, reducing agent and stabilizer. S could chelate with excessive TOP to form trioctylphosphine sulfide (TOPS), which served as second capping agent. The hydrophobic Ag NPs could be transformed into hydrophilic state through ligand exchange. Furthermore, surface-enhanced Raman scattering (SERS) spectra of 4-aminothiophenol (4-ATP) were obtained on the hydrophobic and hydrophilic Ag NPs modified substrates, indicating that the as-synthesized Ag NPs had great potential for high sensitive optical detection applications.

Shear and elongational flow behavior of acrylic thickener solutions

We investigate the effect of hydrophobic ag- gregation in alkali-swellable acrylic thickener solutions on shear and extensional flow properties at technically relevant polymer concentrations using the commer- cial thickener Sterocoll FD as model system. Appar- ent molecular weight of aggregates in water is Mw ≈ 10 8 g/mol and decreases by more than an order of magnitude in ethanol. Zero shear viscosity η0 is low and shear thinning is weak compared to the high molecular weight of the aggregates. Linear viscoelastic relaxation is described by the Zimm theory up to frequencies of 10 4 rad/s, demonstrating that no entanglements are present in these solutions. This is further supported by the concentration dependence of η0 and is attributed to strong association within the aggregates. Extensional flow behavior is characterized using the capillary break- up extensional rheometry technique including high- speed imaging. Solutions with φ ≥ 1% undergo uniform deformation and show pronounced strain hardening up to large Hencky strains. Elongational relaxation

Using silver nanoparticle to enhance current response of biosensor

In this paper, we present a simple procedure to increase the sensitivity of a glucose biosensor. The feasibility of an amperometric glucose biosensor based on immobilization of glucose oxidase (GOx) in silver (Ag) sol was investigated for the first time. GOx was simply mixed with Ag nanoparticles and cross-linked with a polyvinyl butyral (PVB) medium by glutaraldehyde. Then a platinum electrode was coated with the mixed solution. The effects of the amount of the Ag particles used, with respect to the current response for enzyme electrodes, were studied. A set of experimental results indicate that the current response for the enzyme electrode containing hydrophobic Ag sol increased from 0.531 to 31.17 microA in the solution of 10 mmol/L beta-D glucose. The time reaching the steady-state current response reduced from 60 to 20s, three times less than those without Ag particles involved.

Counting efficiency and detection limit of condensation nuclei counters for submicrometer aerosols: II. Measurements with monodisperse hydrophobic Ag and hygroscopic NaCl aerosols with particle diameters between 2 and 100 nm

Submicrometer hydrophobic Ag and hygroscopic NaCl aerosols with particle diameters between 2 and 100 nm are generated by means of a condensation aerosol generator and a differential mobility analyzer. Particle size, size distribution, and shape are examined by means of the transmission electron microscopy and diffusion batteries. The aerosol concentration is absolutely determined by means of an aerosol filter electrometer. The counting efficiency of three condensation nuclei counters (GE-CNC1, GE-CNC2, and photographic CNC) are measured down to particle sizes of 2 nm and the influence of particle charge and concentration is tested. The results of counting efficiency and detection limit for hydrophobic Ag and hygroscopic NaCl aerosols of the photographic CNC are compared to theoretical considerations of Part I (H. G. Scheibel and J. Porstendörfer, J. Colloid Interface Sci. 109, 261–274, 1986). The counting efficiency depends on wall losses and on the particle material. The results for hydrophobic Ag aerosols show satisfactory agreement with Fletcher's theory, whereas the soluble NaCl particles show deviations from the theoretical evaluations. The Kelvin curve describes in no case the counting efficiency results.