Self-Powered and Broadband Photodetectors Based on High-performance Mixed Dimensional Sb2O3/PdTe2/Si Heterojunction for Multiplex Environmental Monitoring.

Solar-blind ultraviolet (SBUV) to near-infrared (NIR) broadband photodetectors (BB-PD) have important applications in environmental monitoring and other applications. However, it is challenging to prepare SBUV-IR photosensitive materials via simple steps and to construct SBUV-IR broadband devices for multiplex detection with high sensitivity at different wavelengths. Here, self-powered and broadband photodetectors using a high-performance mixed dimensional Sb2O3 nanorod 1-dimension (1D)/monodisperse microdiamond-like PdTe2 3-dimension (3D)/Si (3D) heterojunction for multiplex detection of environmental pollutants with high sensitivity at broadband wavelength are developed. The 1D/3D mixed dimensional Sb2O3/PdTe2/Si structure combines the advantages of strong light absorption, high carrier transport efficiency of 1D Sb2O3 nanorods, and expansion of interface barrier caused by 3D microdiamond-like PdTe2 interlayer to improve the photocurrent density and self-powered ability. The efficient photogenerated charge separation enables anon/off ratio of more than 5 × 106. The device exhibits excellent photoelectric properties from 255 to 980 nm with the responsivity from 4.56 × 10-2 to 6.55 × 10-1 AW-1, the detectivity from 2.36 × 1012 to 3.39 × 1013 Jones, and the sensitivity from 3.90 × 107 to 1.10 × 1010 cm2 W-1 without external bias. Finally, the proposed device is applied for the multiplex monitoring of environmental pollution gases NO2 with the detection limit of 200 ppb and PM2.5 particles at mild pollution at broadband wavelength. The proposed BB-PD has great potential for multiplex detection of environmental pollutants and other analytes at broadband wavelength.

Gelothermal Synthesis of Monodisperse MIL-88A Nanoparticles with Tunable Sizes and Metal Centers for Potential Bioapplications.

Developing novel synthetic strategies to downsize metal-organic frameworks (MOFs) from polydisperse crystals to monodisperse nanoparticles is of great importance for their potential bioapplications. In this work, a novel synthetic strategy termed gelothermal synthesis is proposed, in which coordination polymer gel is first prepared and followed by a thermal reaction to give the monodisperse MOF nanoparticles. This novel synthetic strategy successfully leads to the isolation of Materials of Institute Lavoisier (MIL-88), Cu(II)-fumarate MOFs (CufumDMF), and Zeolitic Imidazolate Frameworks (ZIF-8) nanoparticles. Focused on MIL-88A, the studies reveal that the size can be well-tuned from nanoscale to microscale without significant changes in polydispersity index (PDI) even in the case of in situ metal substitution. A possible mechanism is consequently proposed based on extensive studies on the gelothermal condition including sol-gel chemistry, thermal condition, kinds of solvents, and so on. The unique advantages of monodisperse MIL-88A nanoparticles over polydisperse ones are further demonstrated in terms of in vitro magnetic resonance imaging (MRI), cellular uptake, and drug-carrying properties.

Quantification of monodisperse and biocompatible gold nanoparticles by single-particle ICP-MS.

Bioanalytical and biomedical applications often require nanoparticles that exhibit narrow size distributions and biocompatibility. Here, we demonstrate how different synthesis methods affect gold nanoparticle (AuNPs) monodispersity and cytotoxicity. Using single particle inductively coupled plasma mass spectrometry (SP-ICP-MS), we found that the size distribution of AuNPs synthesized with a cetyltrimethylammonium chloride (CTAC) cap was significantly improved compared to AuNPs synthesized with citrate capping agents. We determined an up to 4× decrease in the full width at half maximum (FWHM) value of the normal distributions of AuNP diameter and up to a 12% decrease in relative standard deviation (RSD). While the CTAC-capped AuNPs exhibit narrow nanoparticle size distributions, they are cytotoxic, which limits safe and effective bioanalytical and biomedical applications. We sought to impart biocompatibility to CTAC-capped AuNPs through a PEGylation-based surface ligand exchange. We developed a unique ligand exchange method driven by physical force. We demonstrated the successful PEGylation using various PEG derivatives and used these PEGylated nanoparticles to further bioconjugate nucleic acids and peptides. Using cell viability quantification, we confirmed that the monodisperse PEGylated AuNPs were biocompatible. Our monodisperse and biocompatible nanoparticles may advance safe and effective bioanalytical and biomedical applications of nanomaterials.

A test strip constructed by molecular imprinting for ratiometric fluorescence with ultra-low limit of detection for selective monitoring of Sudan I in chili powder.

An up-conversion molecularly imprinted ratiometric fluorescent probe with a monodisperse nuclear-satellite structure and its test strip are designed which can avoid fluorescent background interference to detect Sudan I in chili powder highly selective and sensitive. The detection mechanism is based on the selective recognition of Sudan I by imprinted cavities on the surface of ratiometric fluorescent probe and the inner filter effect between Sudan I molecules and the emission of up-conversion materials (NaYF4:Yb,Tm). Under optimized experimental conditions, the response of fluorescent ratio signals (F475/F645) of this test strip show a good linear relationship in the range 0.02-50 µM Sudan I. The limits of detection and quantitation are as low as 6 nM and 20 nM, respectively. Sudan I is selectively detected in the presence of fivefold higher concentrations of interfering substances (imprinting factor up to 4.4). Detection of Sudan I in chili powder samples show ultra-low LOD (44.7 ng/g), satisfactory recoveries (94.99-105.5%) and low relative standard deviation (≤ 2.0%). This research offers a reliable strategy and promising scheme for highly selective and sensitive detection of illegal additives in complex food matrix via an up-conversion molecularly imprinted ratiometric fluorescent test strip.

Spheroidal Cesium Lead Chloride-Bromide Quantum Dots and a Fast Determination of Their Size and Halide Content.

Lead halide perovskite (LHP) quantum dots (QDs), with their bright and narrow emission, are promising candidates for LEDs, lasers, and quantum light sources. However, current methods to synthesize monodisperse CsPb(Cl:Br)3 and CsPbCl3 QDs exhibiting multiple sharp absorption resonances are not as well developed compared to CsPbBr3. Furthermore, both quantum confinement and the halide ratio in CsPb(Cl:Br)3 QDs strongly influence the bandgap, making it impossible to optically determine their size. In this work, monodisperse spheroidal CsPb(Cl:Br)3 QDs are synthesized in the 4-10 nm range, at any Cl:Br ratio, with up to five excitonic absorption transitions. Furthermore, in situ spectroscopy was used to cross-correlate the size and composition of these QDs directly to the energy of the first two excitonic absorption transitions. This work therefore provides not only a method for monodisperse CsPb(Cl:Br)3 QDs but also a protocol to determine their size, concentration, and halide ratio, circumventing conventional expensive and time-consuming techniques.

Monodisperse Adducts-Induced Homogeneous Nucleation Towards High-Quality Tin-Based Perovskite Film.

The classic solvent system can't sufficiently separate one-dimensional edge-sharing SnI2 crystals in solution, which severely restricts the fabrication of high-quality tin-based perovskite film. Herein, a strong Lewis base (hexamethylphosphoramide, HMPA) has been introduced to coordinate Sn2+ to modulate solvation behaviours on perovskite precursor and regulate crystallization kinetics. The large molecular volume of HMPA and stronger bind energy of SnI2 ⋅ 2HMPA (-0.595 eV vs -0.118 eV for SnI2 ⋅ 2DMSO) change the solvation structure of SnI2 from edge-sharing cluster to monodisperse adduct, which contributes to uniform nucleation sites and prolongs crystal growth process. Delightfully, a fully-covered perovskite film is formed on the large-area substrate and tin-based perovskite solar cells processed with HMPA exhibit an excellent efficiency of 13.46 %. This research provides novel insights and directions for the solution preparation of smooth and uniform large-area tin-based perovskite film.

Confinement Assembly of Terpolymer-Based Janus Nanoparticles.

While the confinement assembly of block copolymers into functional microparticles has been extensively studied, little is known about the behavior of Janus nanoparticles (JNPs) in spherical confinement. Here, the confinement self-assembly of JNPs in drying emulsion droplets is investigated and their behavior compared to their ABC triblock terpolymer precursors. Emulsions of both materials are prepared using Shirasu Porous Glass membranes leading to narrow size distributions of the microparticles with average hydrodynamic radii in the range of Rh  = 250-500 nm (depending on the membrane pore radius, Rpore ). The internal structure of the microparticles is verified with transmission electron microscopy (TEM) on ultrathin cross sections and compared to the corresponding bulk morphologies. While the confinement assembly of terpolymers results in microparticles with ordered inner morphologies, order for JNPs diminishes when the Janus balance deviates from parity.

Magnetic phenolic resin core-shell structure derived carbon microspheres for ultrafast magnetic solid-phase extraction of triazine herbicides.

In this study, monodisperse magnetic carbon microspheres were successfully synthesized through the carbonization of phenolic resin encapsulated Fe3 O4 core-shell structures. The magnetic carbon microspheres showed high performance in ultrafast extraction and separation of trace triazine herbicides from environmental water samples. Under optimized conditions, both the adsorption and desorption processes could be achieved in 2 min, and the maximum adsorption capacity for simazine and prometryn were 387.6 and 448.5 µg/g. Coupled with high-performance liquid chromatography-ultraviolet detection technology, the detection limit of triazine herbicides was in the range of 0.30-0.41 ng/mL. The mean recoveries ranged from 81.44 to 91.03% with relative standard deviations lower than 7.47%. The excellent magnetic solid-phase extraction performance indicates that magnetic carbon microspheres are promising candidate adsorbents for the fast analysis of environmental contaminants.

Improved Sensitivity of Ultrasound-Based Subharmonic Aided Pressure Estimation Using Monodisperse Microbubbles.

OBJECTIVES: Subharmonic aided pressure estimation (SHAPE) has been shown effective for noninvasively measuring hydrostatic fluid pressures in a variety of clinical applications. The objective of this study was to explore potential improvements in SHAPE sensitivity using monodisperse microbubbles. METHODS: Populations of monodisperse microbubbles were created using a commercially available microfluidics device (Solstice Pharmaceuticals). Size distributions were assessed using a Coulter Counter and stability of the distribution following fabrication was evaluated over 24 hours. Attenuation of the microbubble populations from 1 to 10 MHz was then quantified using single element transducers to identify each formulation's resonance frequency. Frequency spectra over increasing driving amplitudes were investigated to determine the nonlinear phases of subharmonic signal generation. SHAPE sensitivity was evaluated in a hydrostatic pressure-controlled water bath using a Logiq E10 scanner (GE Healthcare). RESULTS: Monodisperse lipid microbubble suspensions ranging from 2.4 to 5.3 µm in diameter were successfully created and they showed no discernable change in size distribution over 24 hours following activation. Calculated resonance frequencies ranged from 2.1 to 6.3 MHz and showed excellent correlation with microbubble diameter (R2 > 0.99). When investigating microbubble frequency response, subharmonic signal occurrence was shown to begin at 150 kPa peak negative pressure, grow up to 225 kPa, and saturate at approximately 250 kPa. Using the Logiq E10, monodisperse bubbles demonstrated a SHAPE sensitivity of -0.17 dB/mmHg, which was nearly twice the sensitivity of the commercial polydisperse microbubble currently being used in clinical trials. CONCLUSIONS: Monodisperse microbubbles have the potential to greatly improve the sensitivity of SHAPE for the noninvasive measurement of hydrostatic pressures.

Extended Nucleation and Superfocusing in Colloidal Semiconductor Nanocrystal Synthesis.

Hot-injection synthesis is renowned for producing semiconductor nanocolloids with superb size dispersions. Burst nucleation and diffusion-controlled size focusing during growth have been invoked to rationalize this characteristic yet experimental evidence supporting the pertinence of these concepts is scant. By monitoring a CdSe synthesis in-situ with X-ray scattering, we find that nucleation is an extended event that coincides with growth during 15-20% of the reaction time. Moreover, we show that size focusing outpaces predictions of diffusion-limited growth. This observation indicates that nanocrystal growth is dictated by the surface reactivity, which drops sharply for larger nanocrystals. Kinetic reaction simulations confirm that this so-called superfocusing can lengthen the nucleation period and promote size focusing. The finding that narrow size dispersions can emerge from the counteracting effects of extended nucleation and reaction-limited size focusing ushers in an evidence-based perspective that turns hot injection into a rational scheme to produce monodisperse semiconductor nanocolloids.

Monodisperse Gold Nanoparticles: A Review on Synthesis and Their Application in Modern Medicine.

Gold nanoparticles (AuNPs) are becoming increasingly popular as drug carriers due to their unique properties such as size tenability, multivalency, low toxicity and biocompatibility. AuNPs have physical features that distinguish them from bulk materials, small molecules and other nanoscale particles. Their unique combination of characteristics is just now being fully realized in various biomedical applications. In this review, we focus on the research accomplishments and new opportunities in this field, and we describe the rising developments in the use of monodisperse AuNPs for diagnostic and therapeutic applications. This study addresses the key principles and the most recent published data, focusing on monodisperse AuNP synthesis, surface modifications, and future theranostic applications. Moving forward, we also consider the possible development of functionalized monodisperse AuNPs for theranostic applications based on these efforts. We anticipate that as research advances, flexible AuNPs will become a crucial platform for medical applications.

Homogeneous Synthesis of Monodisperse Sequence-Defined Conjugated Oligomers by Temperature Cycling.

Sequence-defined synthetic oligomers and polymers provide unprecedented opportunities for polymer chemists to finely control properties such as chain folding, self-assembly, and optoelectronic performance of materials. However, absolute control over both chain-length and monomer sequence has been a long-standing "grand challenge" for decades. Herein, we report a novel strategy to synthesize monodisperse sequence-defined conjugated oligomers in a homogeneous manner by temperature cycling, thereby achieving single-monomer precision in conjugated polyheterocycles. A series of sequence-defined oligomers with up to twelve repeating units, four different monomers, and various sequences were successfully synthesized. Monomer sequence was also proved to affect optical properties. We believe this strategy not only exhibits general applicability to the synthesis of group 16 conjugated oligomers and polymers, but also has far-reaching potential for other polymer systems.

Optimization of PEGylated KL4 Peptide for siRNA Delivery with Improved Pulmonary Tolerance.

Pulmonary delivery of small interfering RNA (siRNA) is a promising therapeutic strategy for treating various respiratory diseases but an effective carrier for the delivery of siRNA into the cells of the lungs and a robust gene-silencing effect is still lacking. Previously, we reported that the KL4 peptide, a synthetic cationic peptide with a repeating KLLLL sequence, can mediate effective siRNA transfection in lung epithelial cells but its high hydrophobic leucine content, and hence poor water solubility, limits its application as a delivery vector. Here, we show that the covalent attachment of monodisperse poly(ethylene glycol) (PEG) improves the solubility of KL4 and the uptake of its complex with siRNA into lung epithelial cells, such that very robust silencing is produced. All PEGylated KL4 peptides, with PEG length varying between 6 and 24 monomers, could bind and form nanosized complexes with siRNA, but the interaction between siRNA and peptides became weaker as the PEG chain length increased. All PEGylated KL4 peptides exhibited satisfactory siRNA transfection efficiency on three human lung epithelial cell lines, including A549 cells, Calu-3 cells, and BEAS-2B cells. The PEG12KL4 peptide, which contains 12 monomers of PEG, was optimal for siRNA delivery and also demonstrated a low risk of inflammatory response and toxicity in vivo following pulmonary administration.

Synthesis of Monodispersedly Sized ZnO Nanowires from Randomly Sized Seeds.

We demonstrate the facile, rational synthesis of monodispersedly sized zinc oxide (ZnO) nanowires from randomly sized seeds by hydrothermal growth. Uniformly shaped nanowire tips constructed in ammonia-dominated alkaline conditions serve as a foundation for the subsequent formation of the monodisperse nanowires. By precisely controlling the sharp tip formation and the nucleation, our method substantially narrows the distribution of ZnO nanowire diameters from σ = 13.5 nm down to σ = 1.3 nm and controls their diameter by a completely bottom-up method, even initiating from randomly sized seeds. The proposed concept of sharp tip based monodisperse nanowires growth can be applied to the growth of diverse metal oxide nanowires and thus paves the way for bottom-up grown metal oxide nanowires-integrated nanodevices with a reliable performance.

Core-shell nanostructures: a simplest two-component system with enhanced properties and multiple applications.

With the pace of time, synthesis of nanomaterials has paved paths to blend two or more materials having different properties into hybrid nanoparticles. Therefore, it has become possible to combine two different functionalities in a single nanoparticle and their properties can be enhanced or modified by coupling of two different components. Core-shell technology has now represented a new trend in analytical sciences. Core-shell nanostructures are in demand due to their specific design and geometry. They have internal core of one component (metal or biomolecules) surrounded by a shell of another component. Core-shell nanoparticles have great importance due to their high thermal stability, high solubility and lower toxicity. In this review, recent progress in development of new and sophisticated core-shell nanostructures has been explored. The first section covers introduction throwing light on basics of core-shell nanoparticles. Following section classifies core-shell nanostructures into single core/shell, multicore/single shell, single core/multishell and multicore/multishell nanostructures. Next main section gives a brief description on types of core-shell nanomaterials followed by processes for the synthesis of core-shell nanostructures. Ultimately, the final section focuses on the application areas such as drug delivery, bioimaging, solar cell applications etc.

Stepwise PEG synthesis featuring deprotection and coupling in one pot.

The stepwise synthesis of monodisperse polyethylene glycols (PEGs) and their derivatives usually involves using an acid-labile protecting group such as DMTr and coupling the two PEG moieties together under basic Williamson ether formation conditions. Using this approach, each elongation of PEG is achieved in three steps - deprotection, deprotonation and coupling - in two pots. Here, we report a more convenient approach for PEG synthesis featuring the use of a base-labile protecting group such as the phenethyl group. Using this approach, each elongation of PEG can be achieved in two steps - deprotection and coupling - in only one pot. The deprotonation step, and the isolation and purification of the intermediate product after deprotection using existing approaches are no longer needed when the one-pot approach is used. Because the stepwise PEG synthesis usually requires multiple PEG elongation cycles, the new PEG synthesis method is expected to significantly lower PEG synthesis cost.

Monodisperse restricted access material with molecularly imprinted surface for selective solid-phase extraction of 17ß-estradiol from milk.

In this study, novel monodisperse restricted access media-molecularly imprinted polymers were successfully prepared by surface initiated reversible addition-fragmentation chain transfer polymerization using monodisperse crosslinked poly (glycidyl methacrylate-co-ethylene glycol dimethacrylate) microspheres as the carrier and acryloyl chloride-modified ß-cyclodextrin as the hydrophilic functional monomer. The surface morphology, protein exclusion, and adsorption properties of the molecularly imprinted polymers were investigated. The results show that the material has excellent monodispersity and hydrophilicity, and simultaneously exhibit high adsorption capacity, fast binding kinetics, high selectivity, and significant thermal stability. The molecularly imprinted polymers as dispersive solid-phase extraction adsorbent combined with reversed-phase high-performance liquid chromatography was used to selectively enrich, separate, and analyze trace 17ß-estradiol in milk samples. The recovery of 17ß-estradiol is 88-95% with relative standard deviation of <4%, and the limits of detection and quantification of this method are 2.08 and 9.29 µg/L, respectively. The novel restricted access media-molecularly imprinted polymer adsorbents provide an effective method for the selective extraction and detection of 17ß-estradiol directly from complex samples.

A high-performance amperometric sensor based on a monodisperse Pt-Au bimetallic nanoporous electrode for determination of hydrogen peroxide released from living cells.

A neotype electrochemical sensor based on a three-dimensional nanoporous gold (3D-NPG) electrode decorated with ultra-thin platinum nanoparticles (Pt NPs) was fabricated for high-performance electrocatalysis and sensitive determination of hydrogen peroxide (H2O2) released from pheochromocytoma (PC12) cells. The monodisperse Pt-Au bimetallic nanoporous (Pt-Au-BNP) electrode prepared by cyclic voltammetry electrodepositing monolayer Pt NPs on the surface of the 3D-NPG electrode was characterized by scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), and energy-dispersive spectroscopy (EDS). Amperometric response for H2O2 measurement was chosen at an applied potential of - 0.4 V. Upon optimal conditions, the wide linear range for the amperometric determination of H2O2 was from 0.05 µM to 7.37 mM, with a limit of detection (S/N = 3) of 1.5 × 10-8 mol/L and a high sensitivity of 1.125 µA µM-1 cm-2, certifying the large electrocatalytic action of the Pt-Au-BNP electrode. The proposed sensor has been successfully applied to the dynamic determination of H2O2 released from PC12 cells (from which the H2O2 generated by each cell was about 52.5 amol) with negligible interference. Thus, the proposed new electrochemical sensor displays potential applications for the dynamic, real-time monitoring of key small molecules secreted by living cells, further deepening the understanding of cell behavior stimulated by foreign materials. Graphical Abstract .

Protein-Stabilized Palm-Oil-in-Water Emulsification Using Microchannel Array Devices under Controlled Temperature.

Microchannel (MC) emulsification for the preparation of monodisperse oil-in-water (O/W) and water-in-oil-in-water (W/O/W) emulsions containing palm oil as the oil phase was investigated for application as basic material solid/semi-solid lipid microspheres for delivery carriers of nutrients and drugs. Emulsification was characterized by direct observation of droplet generation under various operation conditions, as such, the effects of type and concentration of emulsifiers, emulsification temperature, MC structure, and flow rate of to-be-dispersed phase on droplet generation via MC were investigated. Sodium caseinate (SC) was confirmed as the most suitable emulsifier among the examined emulsifiers, and monodisperse O/W and W/O/W emulsions stabilized by it were successfully obtained with 20 to 40 µm mean diameter (dm) using different types of MCs.

Manipulation of the Size and Phase Composition of Yttrium Iron Garnet Nanoparticles by Pulsed Laser Post-Processing in Liquid.

Modification of the size and phase composition of magnetic oxide nanomaterials dispersed in liquids by laser synthesis and processing of colloids has high implications for applications in biomedicine, catalysis and for nanoparticle-polymer composites. Controlling these properties for ternary oxides, however, is challenging with typical additives like salts and ligands and can lead to unwanted byproducts and various phases. In our study, we demonstrate how additive-free pulsed laser post-processing (LPP) of colloidal yttrium iron oxide nanoparticles using high repetition rates and power at 355 nm laser wavelength can be used for phase transformation and phase purification of the garnet structure by variation of the laser fluence as well as the applied energy dose. Furthermore, LPP allows particle size modification between 5 nm (ps laser) and 20 nm (ns laser) and significant increase of the monodispersity. Resulting colloidal nanoparticles are investigated regarding their size, structure and temperature-dependent magnetic properties.