Aqueous Nanoparticle Dispersions Research Articles

Comparison of Microfluidic Synthesis of Silver Nanoparticles in Flow and Drop Reactors at Low Dean Numbers.

This study evaluates the performance of continuous flow and drop-based microfluidic devices for the synthesis of silver nanoparticles (AgNPs) under identical hydrodynamic and chemical conditions. Flows at low values of Dean number (De < 1) were investigated, where the contribution of the vortices forming inside the drop to the additional mixing inside the reactor should be most noticeable. In the drop-based microfluidic device, discrete aqueous drops serving as reactors were generated by flow focusing using silicone oil as the continuous phase. Aqueous solutions of reagents were supplied through two different channels merging just before the drops were formed. In the continuous flow device, the reagents merged at a Tee junction, and the reaction was carried out in the outlet tube. Although continuous flow systems may face challenges such as particle concentration reduction due to deposition on the channel wall or fouling, they are often more practical for research due to their operational simplicity, primarily through the elimination of the need to separate the aqueous nanoparticle dispersion from the oil phase. The results demonstrate that both microfluidic approaches produced AgNPs of similar sizes when the hydrodynamic conditions defined by the values of De and the residence time within the reactor were similar.

Application of nano-TiO2 and micro-ZnO on cementitious surfaces for self-cleaning façades by spray coating and dip coating: A comparative study

Building façades are constantly exposed to atmospheric pollution and various external agents that can degrade their aesthetic qualities and introduce degradation patterns that affect the durability and performance of the materials. Façades with self-cleaning properties are important in the modern construction industry and the conservation of historic buildings, as they reduce costs and allow the preservation of original surfaces without the need for invasive interventions that could compromise cultural heritage. This study does a comparative analysis of the application of photocatalytic coatings composed of aqueous dispersions of titanium dioxide nanoparticles (TiO₂) and zinc oxide microparticles (ZnO) on cementitious substrates for use on façades by two functionalisation methods: spray coating and dip coating. A comprehensive characterisation was carried out using techniques such as scanning electron microscopy (SEM), X-ray diffraction (XRD), and diffuse reflectance spectroscopy (DRS) to assess the morphology, crystal structure and light absorption properties of the photocatalyst particles while Energy Dispersive Spectroscopy (EDS) and scanning electron microscopy (SEM) were employed to evaluate the substrate. The self-cleaning performance was evaluated by monitoring the degradation of Rhodamine B (RhB) dye under simulated sunlight. Spectrophotometric analysis was used to assess the colour coordinates using a standard colour system (CIELAB colour space). The results showed that the photocatalytic coatings improved the surfaces' self-cleaning properties while maintaining the substrate's original aesthetics. Spray-applied micro-ZnO-based coatings showed the most significant effectiveness in terms of self-cleaning.

Uptake of Magnetite Nanoparticles on Polydopamine Films Deposited on Gold Surfaces: A Study by AFM and XPS.

Polydopamine has the capacity to adhere to a large variety of materials and this property offers the possibility to bind nanoparticles to solid surfaces. In this work, magnetite nanoparticles were deposited on gold substrates coated with polydopamine films. The aim of this work was to investigate the effects of the composition and morphology of the PDA layers on the sticking of magnetite nanoparticles. The polydopamine coating of gold surfaces was achieved by the oxidation of alkaline solutions of dopamine with various reaction times. The length of the reaction time to form PDA was expected to influence the composition and surface roughness of the PDA films. Magnetite nanoparticles were deposited on these polydopamine films by immersing the samples in aqueous dispersions of nanoparticles. The morphology at the nanometric scale and the composition of the surfaces before and after the deposition of magnetite nanoparticles were investigated by means of AFM and XPS. We found that the amount of magnetite nanoparticles on the surface did not vary monotonically with the reaction time of PDA formation, but it was at the minimum after 20 min of reaction. This behavior may be attributed to changes in the chemical composition of the coating layer with reaction time.

A strategy of consistent X-ray and neutron double-difference pair distribution function analysis of nanoparticle dispersions

AbstractIt has been demonstrated that the X-ray pair distribution function (PDF) formalism allows for the identification of very small signal contributions in multi-component systems by the difference and double-difference PDF (dd-PDF) approach. Due to their stronger interaction with light elements compared to X-rays, neutrons are often beneficial or complementary for the characterization of modern materials. Here, it is demonstrated that the dd-PDF strategy previously developed for X-ray PDF data can successfully be applied to neutron PDF data despite much lower count rates compared to X-rays. The dd-PDF strategy was employed for the investigation of aqueous iron oxide nanoparticle (IONP) dispersions. At the Near and InterMediate Range Order Diffractometer (NIMROD) at ISIS, the IONPs could even be investigated in pure water, whereas at the Nanoscale Ordered Materials Diffractometer (NOMAD) at SNS, heavy water had to be used, but additional information could be retrieved from modelling the data of IONP powder in the dry state and with adsorbed (heavy) water. The simple and robust approach can easily be adapted for the use in other multicomponent systems, like heterogenous catalysts or battery systems. Graphical Abstract

Development of hard X-ray photoelectron spectroscopy in liquid cells using optimized microfabricated silicon nitride membranes.

We present first hard X-ray photoelectron spectroscopy (HAXPES) results of aqueous salt solutions and dispersions of gold nanoparticles in liquid cells equipped with specially designed microfabricated thin silicon nitride membranes, with thickness in the 15-25 nm range, mounted in a high-vacuum-compatible environment. The experiments have been performed at the HAXPES endstation of the GALAXIES beamline at the SOLEIL synchrotron radiation facility. The low-stress membranes are fabricated from 100 mm silicon wafers using standard lithography techniques. Platinum alignment marks are added to the chips hosting the membranes to facilitate the positioning of the X-ray beam on the membrane by detecting the corresponding photoemission lines. Two types of liquid cells have been used, a static one built on an Omicron-type sample holder with the liquid confined in the cell container, and a circulating liquid cell, in which the liquid can flow in order to mitigate the effects due to beam damage. We demonstrate that the membranes are mechanically robust and able to withstand 1 bar pressure difference between the liquid inside the cell and vacuum, and the intense synchrotron radiation beam during data acquisition. This opens up new opportunities for spectroscopic studies of liquids.

Photocatalytic Hydrogen Generation in Surfactant-Free, Aqueous Organic Nanoparticle Dispersions.

Hydrogen generation in electrostatically stabilized, aqueous organic nanoparticle dispersions is investigated. For this purpose, organic nanoparticle dispersions are synthesized in water by nanoprecipitation from tetrahydrofuran and stabilized by charging through strong molecular electron acceptors. The dispersions are stable for more than 10 weeks on the shelf and during the photocatalytic process, despite the continuous transfer of charges between the reactants. The hydrogen generation in the electrostatically stabilized dispersions outperforms the hydrogen generation in organic nanoparticle dispersions which contain the common stabilizer sodium dodecyl sulfate.

Effect of Temperature, Oil Type, and Copolymer Concentration on the Long-Term Stability of Oil-in-Water Pickering Nanoemulsions Prepared Using Diblock Copolymer Nanoparticles.

A poly(glycerol monomethacrylate) (PGMA) precursor was chain-extended with 2,2,2-trifluoroethyl methacrylate (TFEMA) via reversible addition-fragmentation chain transfer (RAFT) aqueous emulsion polymerization. Transmission electron microscopy (TEM) studies confirmed the formation of well-defined PGMA52-PTFEMA50 spherical nanoparticles, while dynamic light scattering (DLS) studies indicated a z-average diameter of 26 ± 6 nm. These sterically stabilized diblock copolymer nanoparticles were used as emulsifiers to prepare oil-in-water Pickering nanoemulsions: either n-dodecane or squalane was added to an aqueous dispersion of nanoparticles, followed by high-shear homogenization and high-pressure microfluidization. The Pickering nature of such nanoemulsion droplets was confirmed via cryo-transmission electron microscopy (cryo-TEM). The long-term stability of such Pickering nanoemulsions was evaluated by analytical centrifugation over a four-week period. The n-dodecane droplets grew in size significantly faster than squalane droplets: this is attributed to the higher aqueous solubility of the former oil, which promotes Ostwald ripening. The effect of adding various amounts of squalane to the n-dodecane droplet phase prior to emulsification was also explored. The addition of up to 40% (v/v) squalane led to more stable nanoemulsions, as judged by analytical centrifugation. The nanoparticle adsorption efficiency at the n-dodecane-water interface was assessed by gel permeation chromatography when using nanoparticle concentrations of 4.0, 7.0, or 10% w/w. Increasing the nanoparticle concentration not only produced smaller droplets but also reduced the adsorption efficiency, as confirmed by TEM studies. Furthermore, the effect of varying the nanoparticle concentration (2.5, 5.0, or 10% w/w) on the long-term stability of n-dodecane-in-water Pickering nanoemulsions was explored over a four-week period. Nanoemulsions prepared at higher nanoparticle concentrations were more unstable and exhibited a faster rate of Ostwald ripening. The nanoparticle adsorption efficiency was monitored for an aging nanoemulsion prepared at a copolymer concentration of 2.5% w/w. As the droplets ripened over time, the adsorption efficiency remained constant (∼97%). This suggests that nanoparticles desorbed from the shrinking smaller droplets and then readsorbed onto larger droplets over time. Finally, the effect of temperature on the stability of Pickering nanoemulsions was examined. Storing these Pickering nanoemulsions at elevated temperatures led to faster rates of Ostwald ripening, as expected.

Nanoparticles of Push-Pull Triphenylamine-Based Molecules for Light-Controlled Stimulation of Neuronal Activity.

Organic semiconductor materials with a unique set of properties are very attractive for interfacing biological objects and can be used for noninvasive therapy or detection of biological signals. Here, we describe the synthesis and investigation of a novel series of organic push-pull conjugated molecules with the star-shaped architecture, consisting of triphenylamine as a branching electron donor core linked through the thiophene π-spacer to electron-withdrawing alkyl-dicyanovinyl groups. The molecules could form stable aqueous dispersions of nanoparticles (NPs) without the addition of any surfactants or amphiphilic polymer matrixes with the average size distribution varying from 40 to 120 nm and absorption spectra very similar to those of human eye retina pigments such as rods and green cones. Variation of the terminal alkyl chain length of the molecules forming NPs from 1 to 12 carbon atoms was found to be an efficient tool to modulate their lipophilic and biological properties. Possibilities of using the NPs as light nanoactuators in biological systems or as artificial pigments for therapy of degenerative retinal diseases were studied both on the model planar bilayer lipid membranes and on the rat cortical neurons. In the planar bilayer system, the photodynamic activity of these NPs led to photoinactivation of ion channels formed by pentadecapeptide gramicidin A. Treatment of rat cortical neurons with the NPs caused depolarization of cell membranes upon light irradiation, which could also be due to the photodynamic activity of the NPs. The results of the work gave more insight into the mechanisms of light-controlled stimulation of neuronal activity and for the first time showed that fine-tuning of the lipophilic affinity of NPs based on organic conjugated molecules is of high importance for creating a bioelectronic interface for biomedical applications.

Waterborne Polymer Coatings with Bright Noniridescent Structural Colors.

Structural color pigments offer an efficient, sustainable, and environmentally friendly approach to obtain waterborne polymer coatings. We developed polymer-based spherical photonic pigments to incorporate in aqueous dispersions of polymer nanoparticles used to obtain waterborne polymer films. Our spherical photonic pigments are assembled from polymer nanoparticles and are highly stable in water dispersion, maintaining their optical properties in the final polymer films. Unlike conventional dyes and pigments, which are prone to photobleaching because they are based on the absorption of light, photonic pigments rely on the selective reflection of light by their nanostructure and therefore are not photodegraded. Furthermore, different colors can be obtained from the same materials, changing only their nanostructure, in this case, the size of the polymer nanoparticles. Our novel spherical photonic pigments are noniridescent and can be incorporated in aqueous polymer nanoparticle dispersions without deteriorating their structure to produce waterborne polymer coatings with structural color. This approach for structural colored waterborne polymer coatings is efficient, simple, and environmentally friendly, offering excellent prospects for application in paints and coatings.

Ground-state electron transfer in all-polymer donor:acceptor blends enables aqueous processing of water-insoluble conjugated polymers

Water-based conductive inks are vital for the sustainable manufacturing and widespread adoption of organic electronic devices. Traditional methods to produce waterborne conductive polymers involve modifying their backbone with hydrophilic side chains or using surfactants to form and stabilize aqueous nanoparticle dispersions. However, these chemical approaches are not always feasible and can lead to poor material/device performance. Here, we demonstrate that ground-state electron transfer (GSET) between donor and acceptor polymers allows the processing of water-insoluble polymers from water. This approach enables macromolecular charge-transfer salts with 10,000× higher electrical conductivities than pristine polymers, low work function, and excellent thermal/solvent stability. These waterborne conductive films have technological implications for realizing high-performance organic solar cells, with efficiency and stability superior to conventional metal oxide electron transport layers, and organic electrochemical neurons with biorealistic firing frequency. Our findings demonstrate that GSET offers a promising avenue to develop water-based conductive inks for various applications in organic electronics.

Synthesis of Poly(propylene oxide)-Poly(N,N'-dimethylacrylamide) Diblock Copolymer Nanoparticles via Reverse Sequence Polymerization-Induced Self-Assembly in Aqueous Solution.

Sterically-stabilized diblock copolymer nanoparticles comprising poly(propylene oxide) (PPO) cores are prepared via reverse sequence polymerization-induced self-assembly (PISA) in aqueous solution. N,N'-Dimethylacrylamide (DMAC) acts as a cosolvent for the weakly hydrophobic trithiocarbonate-capped PPO precursor. Reversible addition-fragmentation chain transfer (RAFT) polymerization of DMAC is initially conducted at 80% w/w solids with deoxygenated water. At 30-60% DMAC conversion, the reaction mixture is diluted to 5-25% w/w solids. The PPO chains become less solvated as the DMAC monomer is consumed, which drives in situ self-assembly to form aqueous dispersions of PPO-core nanoparticles of 120-190 nm diameter at 20 °C. Such RAFT polymerizations are well-controlled (Mw/Mn ≤ 1.31), and more than 99% DMAC conversion is achieved. The resulting nanoparticles exhibit thermoresponsive character: dynamic light scattering and transmission electron microscopy studies indicate the formation of more compact spherical nanoparticles of approximately 33 nm diameter on heating to 70 °C. Furthermore, 15-25% w/w aqueous dispersions of such nanoparticles formed micellar gels that undergo thermoreversible (de)gelation on cooling to 5 °C.

Tailored nanoparticles for magnetic hyperthermia: Highly stable aqueous dispersion of Mn-substituted magnetite superparamagnetic nanoparticles by double surfactant coating for improved heating efficiency

This study presents a significant advancement in cancer therapy through the application of Mn-substituted magnetite superparamagnetic (SPM) nanoparticles, highlighting the potential of magnetic fluid hyperthermia (MFH) as an effective modality. However, its clinical applications have been limited by challenges such as low heating performance, agglomeration of magnetic nanoparticles (MNPs) in blood veins, and cytotoxicity. To address these crucial issues, surface engineered MNPs were synthesised by adopting a reverse micelles-based co-precipitation approach that effectively overcomes MNP agglomeration, ensuring uniform dispersion of the nanoparticles. Through careful optimization of Mn ion substitution within magnetite, we have achieved a significant enhancement in the heating performance of the magnetite SPM nanoparticles. The substitution of Mn2+ ions in magnetite has notably increased the specific absorption rate (SAR) value, as evidenced by a remarkable 181% increase (SAR: 510 kW/kg) obtained using the Box Lucas Method. This enhancement can be attributed to the elevated saturation magnetization resulting from the appropriate cation distribution within the MNPs. Furthermore, the increase in spin relaxation time with higher Mn concentration also contributes to the improvement in SAR values as MNPs retain their magnetic moments for an extended period before relaxing, leading to enhanced energy dissipation and higher SAR values. The hemolysis assays demonstrated minimal hemolysis rates (<5%) when exposed to red blood cells (RBCs), confirming the high biocompatibility of the MNPs. Additionally, MTT assays revealed excellent cytocompatibility (>90% cell viability) for Human Embryonic Kidney (HEK-293) cells across all compositions, further affirming the potential of these MNPs for clinical treatments. Overall, this study unveils a sustainable approach for cancer therapy using Mn-substituted magnetite SPM nanoparticles. Their remarkable heating performance and excellent biocompatibility make them promising for clinical applications in MFH.

Stability of binary colloidal mixtures of Au noble metal and ZnS semiconductor nanoparticles

Controlling the stability of colloidal nanoparticles in multicomponent systems, i.e., mixtures of colloids, is of vital importance for product formulations and separation processes of nanoparticles. However, very few studies are currently found in literature regarding the generation of binary colloids by mixing of colloidal nanoparticles, particularly small nanoparticles (< 20 nm). In this study, we report on the development of a stable binary colloid made of nanoparticles of different sizes and compositions. As a model system for this study, we mixed aqueous dispersions of gold nanoparticles (Au NPs) and ZnS quantum dots (QDs). We investigated the stability of Au NPs with three different surface ligands after mixing them with ZnS QDs, both before and after functionalization of the Au NPs with bis(p-sulfonatophenyl) phenylphosphine (BSPP). We used UV–visible spectroscopy as the primary method to monitor stability of nanoparticles in the binary mixture over time. We found out that the released thioglycerol and acetate from the surface of ZnS QDs to the binary mixture induces agglomeration in Au NPs. The surface chemistry and the purification process of Au NPs after their synthesis and surface treatment were identified as key parameters to regulate the stability in the mixture. Thus, we successfully achieved a stable mixture of BSPP-functionalized Au NPs with ZnS QDs as a model of a stable binary mixture. We believe that this study is important to stimulate research directed towards real-world multicomponent formulations including their characterization and the understanding of surface interactions.

Aqueous Dispersion of Manganese-Zinc Ferrite Nanoparticles Protected by PEG as a T2 MRI Temperature Contrast Agent.

Mixed manganese-zinc ferrite nanoparticles coated with PEG were studied for their potential usefulness in MRI thermometry as temperature-sensitive contrast agents. Particles in the form of an 8.5 nm core coated with a 3.5 nm layer of PEG were fabricated using a newly developed, one-step method. The composition of Mn0.48Zn0.46Fe2.06O4 was found to have a strong thermal dependence of magnetization in the temperature range between 5 and 50 °C. Nanoparticles suspended in an agar gel mimicking animal tissue and showing non-significant impact on cell viability in the biological test were studied with NMR and MRI over the same temperature range. For the concentration of 0.017 mg/mL of Fe, the spin-spin relaxation time T2 increased from 3.1 to 8.3 ms, while longitudinal relaxation time T1 shows a moderate decrease from 149.0 to 125.1 ms. A temperature map of the phantom exposed to the radial temperature gradient obtained by heating it with an 808 nm laser was calculated from T2 weighted spin-echo differential MR images. Analysis of temperature maps yields thermal/spatial resolution of 3.2 °C at the distance of 2.9 mm. The experimental relaxation rate R2 data of water protons were compared with those obtained from calculations using a theoretical model incorporating the motion averaging regime.

Evaluation of Magnetic Hyperthermia Efficiency of PEG-Coated Fe3O4 Nanoparticles

Magnetic nanoparticle hyperthermia has drawn considerable interest in cancer therapy. In this study, we report the synthesis of PEG-coated Fe3O4 nanoparticles and evaluate their suitability for magnetic hyperthermia applications. Fe3O4 nanoparticles were synthesized by the chemical coprecipitation method, which are coated with polyethylene glycol (PEG). PEG-coated Fe3O4 nanoparticles were characterized by X-ray powder diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), vibrating sample magnetometer (VSM), dynamic light scattering (DLS) and transmission electron microscopy (TEM). Synthesized nanoparticles possess inverse-spinel structural with a crystallite size of 9.1[Formula: see text]nm. From the M-H hysteresis loops, it was confirmed that the synthesized Fe3O4 nanoparticles were superparamagnetic. The physical size of bare Fe3O4 nanoparticles, as determined from the HR-TEM, is [Formula: see text][Formula: see text]nm, and the corresponding hydrodynamic size of PEG-coated Fe3O4 nanoparticles is [Formula: see text][Formula: see text]nm. Magnetic hyperthermia efficiency of PEG-coated Fe3O4 nanoparticles was determined as a function of magnetic field frequency (162–935.6[Formula: see text]kHz), field strength (5–12[Formula: see text]mT) and nanoparticle concentration (1–100[Formula: see text]mg/mL). Temperature rise in an aqueous dispersion of PEG-coated Fe3O4 nanoparticles was measured for 20[Formula: see text]min. The specific loss power (SLP) was calculated by the corrected slope method. SLP values of PEG-coated Fe3O4 nanoparticles increase with magnetic field frequency and field strength and decrease with nanoparticle concentration. The optimum hyperthermia performance of PEG-coated Fe3O4 nanoparticles was observed for 935.6[Formula: see text]kHz frequency, 10[Formula: see text]mT field strength and 25[Formula: see text]mg/mL concentration. Under these conditions, the measured SLP of PEG-coated Fe3O4 nanoparticles was 4.43[Formula: see text]W/g. These results show that the synthesized PEG-coated Fe3O4 nanoparticles could be a potential candidate for magnetic hyperthermia treatment of cancer.

Selective detection of fast and thermal neutrons in mixed-radiation fields using tungsten–silica and gold–iodine–silica nanoparticles and their boron-loaded aqueous dispersions

Tungsten–silica and gold–iodine–silica nanoparticles and their boron-loaded aqueous dispersions were used to selectively detect fast and thermal neutrons in mixed-radiation fields generated by a cyclotron on the order of mSv at a neutron flux of 1.0 ×106(neutron/sec∙cm2). The photo-image intensity, fluorescence spectra, absorption spectra, and XRD of their aqueous dispersions were measured immediately and eighteen days after irradiation. The immediate measurements of photo-image intensity and fluorescence spectral area ratios for gold–iodine–silica nanoparticle aqueous dispersions indicated the dose dependence of photo-image intensity and fluorescence spectral area ratios. Measurements of the relative fluorescence and absorption spectral areas of gold–iodine–silica nanoparticle aqueous dispersions 18 days after irradiation also showed similar dose dependences. The precipitates of gold–iodine–silica nanoparticles showed a linear relationship between the XRD peak ratio and the dose with a correlation coefficient of 0.9. The photo-image intensities, fluorescence spectral area, absorption spectral area, and XRD peak ratios were found to be affected by fast and thermal neutrons. Simple methods of fluorescence, absorption, and XRD measurements are proposed for the selective detection of fast and thermal neutrons in mixed-radiation fields.

Ethanol-water motifs-A re-interpretation of the double-difference pair distribution functions of aqueous iron oxide nanoparticle dispersions.

In dispersion, nanoparticles can interact with the surrounding dispersion medium, such that an interfacial region with a structure differing from that of the bulk exists. Distinct nanoparticulate surfaces induce specific degrees of interfacial phenomena, and the availability of surface atoms is a crucial prerequisite for interfacial restructuring. Here, we investigate the nanoparticle-water interface of 0.5-10 wt. % aqueous iron oxide nanoparticle dispersions of 6nm diameter in the presence of 6 vol. % ethanol with x-ray absorption spectroscopy (XAS) and atomic pair distribution function (PDF) analysis. The absence of surface hydroxyl-groups in XAS spectra is in accordance with the double-difference PDF (dd-PDF) analysis, due to a fully covered surface from the capping agent. The previously observed dd-PDF signal is not stemming from a hydration shell, as postulated in Thomä et al. [Nat Commun. 10, 995 (2019)], but from the residual traces of ethanol from nanoparticle purification. With this article, we provide an insight into the arrangement of EtOH solutes in water at low concentration.

Spectra and photorelaxation of tris-biphenyl-triazine-type UV absorbers: from monomers to nanoparticles

Water-insoluble organic UV filters like tris-biphenyl-triazine (TBPT) can be prepared as aqueous dispersions of nanoparticles. The particles consist of the respective UV absorber molecules and show strong UV absorbance. Since there is a certain solubility of such UV absorbers in organic solvents, it is possible to measure the absorbance spectrum also in solution, for instance in ethanol or dioxane. The UV spectrum of the aqueous dispersion shows a slight hypsochromic shift of the original band with an additional shoulder at longer wavelengths. For the understanding of the observed changes of UV–Vis spectra of this UV absorber, either dissolved in an organic solvent or dispersed as nanoparticles in water, DFT calculations were carried out with the respective monomer and aggregates of TBPT molecules in the different media. The calculated UV–Vis spectra of isolated, that means dissolved, TBPT molecules in ethanol and in dioxane agree well with experimentally observed ones. The observed changes in the shape of experimental UV–Vis spectra in aqueous dispersion cannot be explained with a solvent effect only. It was found that the studied molecules could form stable energetically favorable π-stacked aggregates, which show UV–Vis spectra in reasonable agreement with those experimentally observed in aqueous dispersion. Such aggregates of TBPT are most likely the reason for the observed additional shoulder in the UV/vis absorbance spectrum. In addition, the mechanism of the photochemical deactivation of excited TBPT molecules was studied in detail with TD DFT in dioxane and in water.Graphical abstract

Nanoparticle Assembly at the Water-Oil Interface Induced by Spontaneous Emulsification for Microdroplet Immunoassay.

Micron-sized water-in-oil droplets (microdroplets) have been used for various biochemical analyses. Many studies have been reported on immunoassays using microdroplets because of their high versatility. A selective enrichment method using spontaneous emulsification was developed as a pretreatment method for analytical systems of microdroplets. In this study, a one-step immunoassay for microdroplets using nanoparticle assembly at the interface by spontaneous emulsification is proposed. At the interface of the microdroplet, with aqueous nanoparticle dispersion, it was found that nanoparticles with diameters less than 50 nm were uniformly adsorbed to the microdroplet interface as a Pickering emulsion, whereas larger nanoparticles tended to aggregate in the bulk part of the microdroplet. Based on this phenomenon, a proof of concept of the one-step immunoassay was demonstrated using rabbit IgG as the analyte. This method is expected to be a powerful tool for trace biochemical analyses.

Effect of the Preparation Methodology of Polydopamine-Containing Systems over Light-to-Thermal Energy Conversion Performance

Polydopamine (PDA) is an attractive material utilized for a wide range of scientific purposes, including light-to-thermal energy conversion, because of presenting plenty of advantages. The proper integration way of PDA into a system is critical to benefit from the PDA content in maximum. Here, the two main PDA-containing composite preparation methods were compared in terms of fundamental material properties and the light-to-thermal energy conversion ability of the final product. For this purpose, the classical emulsion polymerization method first synthesized an aqueous dispersion of polystyrene nanoparticles (PS). PDA was then integrated into the system via two different preparation methods: coating the surfaces of polystyrene nanoparticles with a PDA layer while PS is in a dispersion state (PS@PDA) and adding separately synthesized PDA nanoparticles into the PS dispersion medium (PS–PDA). Two prepared composite systems were fundamentally characterized by dynamic light scattering (DLS), ultraviolet–visible (UV–vis) spectroscopy, and scanning electron microscopy (SEM) while in their dispersion state, and by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), Fourier-transform infrared (FTIR) spectroscopy, and X-ray diffraction (XRD) while in their solid state, which was obtained after the water evaporated. As the targeted property, the solid forms of these were investigated in terms of light-to-thermal energy conversion performance with solar and laser light exposure under 1 SUN and at 808 nm, respectively. The results showed that the composite system prepared by coating surfaces of PS nanoparticles with the PDA layer had higher light-to-thermal energy conversion under both conditions than those prepared by separately added PDA nanoparticles into the dispersion system. To show one of the possible applications of the prepared composites, in addition to the main target, the solid form of the composite system, which was prepared by coating surfaces of PS nanoparticles with the PDA layer, was also evaluated in detail concerning the latent heat-storage ability with incorporation of PEG 4000 as a phase-change material (PCM) into the system. It was found that the prepared shape-stable phase-change composite with a ratio of 1:3 between PS@PDA and PEG 4000 resulted in a latent heat of 126.9 J/g.