Size-dependent Optical Properties Research Articles

Zero-dimensional quantum dot-modified membrane materials for the effective treatment of industrial wastewater: A comprehensive review

The efficient treatment and recycling of industrial wastewater is an important way to improve water resource utilization. Membrane separation technology has been widely used in the field of industrial wastewater treatment due to its high separation efficiency, low energy consumption, good scalability, and other advantages. A recent breakthrough in membrane technologies is the emergence of various nanocomposite membranes, which not only breaks the trade-off between membrane selectivity and permeability, but also enhances the anti-fouling ability and multi-scale separation effects of membranes. Among the nanomaterials used for membrane fabrication, zero-dimensional quantum dots (QDs) with size-dependent optical properties and excellent photocatalytic potential have become promising candidates for novel nanocomposite membrane construction. Significant improvements in membrane surface hydrophilicity, anti-fouling property, and permeability can be achieved by incorporating QDs during the membrane formation process or through membrane post-modification. This review focuses on recent advances in QD-modified membranes for industrial wastewater treatment. The synthesis methods of QDs were summarized firstly, especially for carbon-based and semiconductor QDs. Based on the blending modification and surface modification, the research progress in the modification strategies of QD-modified membranes is presented. Subsequently, the state-of-the-art studies of QD-modified membranes in the application of industrial wastewater treatment are reviewed. Finally, the current challenges and opportunities in QD-modified membranes are discussed.

(Invited) Semiconductor Nanostructures for Light Energy Conversion

This talk will review some of the key developments of semiconductor quantum dots based light energy conversion. Semiconductor nanostructures are finding new ways to design light energy conversion devices (e.g., thin film solar cells and light emitting devices). The decreased consumption of energy during the manufacture and the lessened use of semiconductor materials lowers the overall carbon footprint with energy payback time less than a year for such devices. The early studies which focused on the synthesis of various semiconductor nanostructures and exploration of their size dependent optical and electronic properties have led to their their integration in high efficiency thin film solar cells.. Unlike solar cell devices, photocatalytic processes are yet to deliver conversion efficiencies and stability that can make them compatible for practical applications. Understanding the limitations imposed by interfacial charge transfer processes remains a key to further advance photocatalytic systems for chemical energy storage. Recent developments in utilizing semiconductor nanostructures for light energy conversion and storage will be discussed.

(Invited) Photoluminescence Dynamics in PbS/CdS Core/Shell Nanocrystal Films: Carrier Recombination and Energy Transfer

Colloidal semiconductor nanocrystals (NCs) exhibit highly controllable size-dependent optical properties due to the quantum confinement effect. Among other semiconductor NCs, the lead chalcogenides, especially PbS, are one of the most studied and promising NC systems. They are the material of choice for studies of fundamental phenomena as well as for the development of solution processed infrared optoelectronic devices including LEDs, lasers, solar cells, and photodetectors. Compared to organically passivated NCs, the core-shell approach (more specifically PbS/CdS core-shell NCs) offers not only the improved stability and higher photoluminescence (PL) quantum efficiency but also an opportunity of the core/shell interface nano-engineering resulting in suppression of Auger recombination, reduction of the exciton radiative lifetime and an improved lasing threshold. However, despite more than a decade of detailed studies there are conflicting reports on PL dynamics in PbS/CdS core-shell NCs, and there is no accepted model explaining the observed PL lifetimes ranging from hundred nanoseconds to tens of microseconds. In this work we use time-resolved PL measurements and demonstrate that low-temperature PL dynamics in PbS/CdS core shell NCs show strong dependence on the PL detection wavelengths. The presented experimental results allow us to distinguish between processes of energy transfer and exciton recombination. We propose a model, which considers energy transfer between NCs and various mechanisms of exciton recombination (non-radiative, radiative, spin-flip, diffusion limited, etc.).

Confinement of excited states in two-dimensional, in-plane, quantum heterostructures

Two-dimensional (2D) semiconductors are promising candidates for optoelectronic application and quantum information processes due to their inherent out-of-plane 2D confinement. In addition, they offer the possibility of achieving low-dimensional in-plane exciton confinement, similar to zero-dimensional quantum dots, with intriguing optical and electronic properties via strain or composition engineering. However, realizing such laterally confined 2D monolayers and systematically controlling size-dependent optical properties remain significant challenges. Here, we report the observation of lateral confinement of excitons in epitaxially grown in-plane MoSe2 quantum dots (~15-60 nm wide) inside a continuous matrix of WSe2 monolayer film via a sequential epitaxial growth process. Various optical spectroscopy techniques reveal the size-dependent exciton confinement in the MoSe2 monolayer quantum dots with exciton blue shift (12-40 meV) at a low temperature as compared to continuous monolayer MoSe2. Finally, single-photon emission (g2(0) ~ 0.4) was also observed from the smallest dots at 1.6 K. Our study opens the door to compositionally engineered, tunable, in-plane quantum light sources in 2D semiconductors.

Gold Nanoparticles in Nanobiotechnology: From Synthesis to Biosensing Applications.

Nanobiotechnology has ushered in a new era of scientific discovery where the unique properties of nanomaterials, such as gold nanoparticles, have been harnessed for a wide array of applications. This review explores gold nanoparticles' synthesis, properties, and multidisciplinary applications, focusing on their role as biosensors. Gold nanoparticles possess exceptional physicochemical attributes, including size-dependent optical properties, biocompatibility, and ease of functionalization, making them promising candidates for the development of biosensing platforms. The review begins by providing a comprehensive overview of gold nanoparticle synthesis techniques, highlighting the advantages and disadvantages of various approaches. It then delves into the remarkable properties that underpin their success in biosensing, such as localized surface plasmon resonance and enhanced surface area. The discussion also includes the functionalization strategies that enable specific binding to biomolecules, enhancing the sensitivity and selectivity of gold-nanoparticle-based biosensors. Furthermore, this review surveys the diverse applications of gold nanoparticles in biosensing, encompassing diagnostics, environmental monitoring, and drug delivery. The multidisciplinary nature of these applications underscores the versatility and potential of gold nanoparticles in addressing complex challenges in healthcare and environmental science. The review emphasizes the pressing need for further exploration and research in the field of nanobiotechnology, particularly regarding the synthesis, properties, and biosensing applications of gold nanoparticles. With their exceptional physicochemical attributes and versatile functionalities, gold nanoparticles present a promising avenue for addressing complex challenges in healthcare and environmental science, making it imperative to advance our understanding of their synthesis, properties, and applications for enhanced biosensing capabilities and broader scientific innovation.

Facile colorimetric sensor development for sequential detection of coralyne and calf-thymus DNA via tannic acid-assisted silver nanoparticles

Owning to unique size dependent optical properties, plasmonic nanoparticles have been explored as chemical read-outs for assaying various biological and chemical analytes. We propose colorimetric sensing strategy based on tannic acid mediated silver nanoparticles (TA-AgNPs) for the detection of Coralyne (COR) and calf thymus DNA (CT-DNA). Aggregation of TA-AgNPs is observed on addition of COR molecule because of electrostatic interaction between them, which is established by change in color from yellow to brown. TA-AgNPs/COR based colorimetric probe was then employed for CT-DNA detection, utilizing anti-aggregation of nanoparticles. Formation of intercalated complex between CT-DNA and COR prevents the aggregation of nanoparticles and color of TA-AgNPs solution remains yellow. Under optimum sensing conditions, extent of aggregation and anti-aggregation of TA-AgNPs was studied. A linear correlation between absorbance value at 437 nm and COR concentration is obtained in the range of 0 to 1.2 μM with detection limit of 0.44 μM. TA-AgNPs/COR based detection probe exhibited linear response to CT-DNA in concentration range of 0 to 7.62 μM with a limit of detection down to 1.63 μM. The applicability of sensing strategy verified by analysis of COR and CT-DNA in human urine samples, which demonstrated the practical utility of method in biomedical applications.

Biosynthesis of Platinum Nanoparticles PlNPs by Bacterial Strain Rhodococcus erythropolis

The biosynthesis of platinum nanoparticles (PlNPs) using the bacterial strain Rhodococcus erythropolis offers a greener alternative to conventional chemical and physical synthesis methods. This study explores the potential of R. erythropolis to produce PlNPs by leveraging its biological machinery to reduce platinum ions and stabilize the resulting nanoparticles. The biosynthesis was conducted under varying conditions of pH, temperature, and sodium platinite concentrations to optimize yield and particle characteristics. The nanoparticles were characterized. The outcome reflects that PlNPs exhibit distinct size-dependent optical properties and crystallinity, with extracellular proteins from R. erythropolis playing a crucial role in nanoparticle stabilization. The optimized biosynthesis process produced PlNPs with high colloidal stability and significant potential for applications in catalysis and environmental remediation. This study advances the understanding of microbial nanoparticle production, highlighting a sustainable pathway for the synthesis of biocompatible and catalytically active platinum nanoparticles.

Development of Stable Water-Soluble Supratomic Silver Clusters Utilizing A Polyoxoniobate-Protected Strategy: Giant Core-Shell-Type Ag8@Nb162 Fluorescent Nanocluster.

Atomically precise low-nuclearity (n<10) silver nanoclusters (AgNCs) have garnered significant interest due to their size-dependent optical properties and diverse applications. However, their synthesis has remained challenging, primarily due to their inherent instability. The present study introduces a new feasible approach for clustering silver ions utilizing highly negative and redox-inert polyoxoniobates (PONbs) as all-inorganic ligands. This strategy not only enables the creation of novel Ag-PONb composite nanoclusters but also facilitates the synthesis of stable low-nuclearity AgNCs. Using this method, we have successfully synthesized a small octanuclear rhombic [Ag8]6+ AgNC stabilized by six highly negative [LiNb27O75]14- polyoxoanions. This marks the first PONb-protected superatomic AgNC, designated as {Ag8@(LiNb27O75)6} (Ag8@Nb162), with an aesthetically spherical core-shell structure. The crystalline Ag8@Nb162 is stable under ambient conditions, What's more, it is water-soluble and able to maintain its molecular cluster structure intact in water. Further, the stable small [Ag8]6+ AgNC has interesting temperature- and pH-dependent reversible fluorescence response, based on which a multiple optical encryption mode for anti-counterfeit technology was demonstrated. This work offers a promising avenue for the synthesis of fascinating and stable PONb-protected AgNCs and sheds light on the development of new-type optical functional materials.

Electronic and optical properties of MgTe quantum dots: size effect

The size-dependent electronic and optical properties of magnesium telluride quantum dots are investigated using a pseudopotential scheme. The emphasis is focused on the effect of the size of the quantum dots on the undertaken properties. The quantum dot radius is considered to be varying in between 1 and 10 nm. It is found that the direct- and indirect band gaps as well as the electron and hole effective masses decrease non-linearly as the quantum dot radius is increased. However, the refractive index, the static- and high frequency dielectric as well as the transverse effective charge increase as the quantum dot size is augmented. The quantum confinement is found to play a major role for the studied physical quantities as long as the quantum dot radius remains less than 5 nm. This permits to tailor the electronic and optical properties of our material according to the desired application.

Green synthesis of Nyctanthes arbor-tristis flower-decorated gold nanoparticles: Sustainable approaches for enhancing antimicrobial and supercapacitor performance

The physiochemical and electrochemical characteristics of gold nanoparticles (AuNPs) produced by phytosynthesis technique at varying concentrations of Nyctanthes arbor-tristis flower (NAF) are presented in this study. The final porous carbon decorated AuNPs have possible applications in antibacterial research as well as energy storage field. Transmission electron microscopy (TEM) studies revealed tiny spherical shaped nanoparticles, and UV–visible spectroscopy showed size-dependent optical properties. Significant antibacterial efficacy against Pseudomonas aeruginosa was shown by the NAF-derived AuNPs. A symmetric supercapacitor with 64 F g−1 specific capacitance at 1 A g−1 and 97% cycling stability after 5000 charge-discharge cycles was produced using the as-synthesized electrode. This study provides a sustainable method for producing multifunctional nanomaterials by highlighting the potential of NAF-derived AuNPs for dual applications in the antibacterial and supercapacitor areas.

Size-dependent optical properties of [6]-, [8]- and [10]Cycloparaphenylene dications: the role of degenerate states

Size-dependent optical properties of [6]-, [8]- and [10]Cycloparaphenylene dications: the role of degenerate states

A Systematic Approach toward Enabling Maximal Targeting Efficiency of Cell Surface Proteins with Actively Targeted SERS Nanoparticles.

With their intricate design, nanoparticles (NPs) have become indispensable tools in the quest for precise cellular targeting. Among various NPs, gold NPs stand out with unique features such as chemical stability, biocompatibility, adjustable shape, and size-dependent optical properties, making them particularly promising for molecular detection by leveraging the surface-enhanced Raman scattering (SERS) effect. Their multiplexing abilities for the simultaneous identification of multiple biomarkers are important in the rapidly evolving landscape of diverse cellular phenotypes and biomolecular profiling. However, the challenge is ensuring that SERS NPs can effectively target specific cells and biomarkers among intricate cell types and biomolecules with high specificity. In this study, we improve the functionalization of SERS NPs, optimizing their targeting efficiency in cellular applications for ca. 160 nm NP-based probes. Spherical SERS NPs, conjugated with antibodies targeting epidermal growth factor receptor and human epidermal growth factor receptor 2, were incubated with cells overexpressing these proteins, and their specific binding potential was quantified at each stage by using flow cytometry to achieve optimal targeting efficiency. We determined that maintaining an average of 3.5 × 105 thiols per NP, 300 antibodies per NP, 18,000 NPs per cell, conducting a 15 min staining incubation at 4 °C in a shaker, and using SM(PEG)12 as a cross-linker for the NP conjugation were crucial to achieve the highest targeting efficiency. Fluorescence and Raman imaging were used with these parameters to observe the maximum ability of these NPs to efficiently target suspended cells. These highly sensitive contrast agents demonstrate their pivotal role in effective active targeting, making them invaluable for multiplexing applications across diverse biological environments.

Silapillar[n]arenes: Their Enhanced Electronic Conjugation and Conformational Versatility.

During recent decades, methylene-bridged macrocyclic arenes have been widely used in supramolecular chemistry. However, their π-conjugations are very weak, as the methylene bridges disrupt the electronic communication between π orbitals of the aromatic units. Herein, we successfully synthesized a series of silapillar[n]arenes (n = 4, 6, and 8) using silylene bridging. These showed enhanced electronic conjugation compared with the parent pillar[n]arenes because of σ*-π* conjugation between σ* (Si-C) orbitals and π* orbitals of the benzenes. Owing to the longer Si-C bond compared with the C-C bond, silylene-bridging provides additional structural flexibility into the pillar[n]arene scaffolds; a strained silapillar[4]arene was formed, which is unavailable in the parent pillar[n]arenes because of the steric requirements. Furthermore, silapillar[n]arenes displayed interesting size-dependent structural and optical properties.

Spatial-Arrangement-Assisted Emission Energy Fine Tuning of CdSe Quantum Dots (QDs) in QD–Block Copolymer Complexes

Quantum dots (QDs) exhibit size-dependent optical properties, where both the absorption and fluorescence energy levels vary with QD size. However, this dependence results in a discontinuity of intrinsically accessible energy levels for the bandgap, posing challenges in achieving precise energy tuning within a specific range. Herein, we demonstrate emission energy control of QDs with identical absorption energy levels by manipulating the spatial arrangement of QDs within QD–polymer complexes through hydrophobic interactions. The phase behavior of the QD–polymer complexes was modulated by adjusting the mass fraction of hydrophilic and hydrophobic blocks in the block copolymer, utilizing two types of amphiphilic block copolymers and varying temperatures. The QDs were spontaneously trapped within the hydrophobic region of the polymer template in water, resulting in spherical, cylindrical, and vesicle structures of QD–polymer complexes, corresponding to spherical, cylindrical, and layered assemblies of QDs, respectively. Depending on the QDs’ location within the QD–polymer complex, the surface area in contact with water varied, leading to different degrees of oxidation and, consequently, a change in the fluorescence energy level of QDs. This study introduces a novel method to fine tune the emission energy (&lt;15 eV) of QDs by adjusting the polymer form factor without complicated procedures.

Chemical transformation mechanism for blue-to-green emitting CsPbBr3 nanocrystals.

Recently, metal-halide perovskites have rapidly emerged as efficient light emitters with near-unity quantum yield and size-dependent optical and electronic properties, which have attracted considerable attention from researchers. However, the ultrafast nucleation rate of ionic perovskite counterparts severely limits the in-depth exploration of the growth mechanism of colloidal nanocrystals (NCs). Herein, we used an inorganic ligand nitrosonium tetrafluoroborate (NOBF4) to trigger a slow post-synthesis transformation process, converting non-luminescent Cs4PbBr6 NCs into bright green luminescent CsPbBr3 NCs to elucidate the concrete transformation mechanism via four stages: (i) the dissociation of pristine NCs, (ii) the formation of Pb-Br intermediates, (iii) low-dimensional nanoplatelets (NPLs) and (iv) cubic CsPbBr3 NCs, corresponding to the blue-to-green emission process. The desorption and reorganization of organic ligands induced by NO+ and the involvement of BF4- in the ligand exchange process played pivotal roles in this dissolution-recrystallization of NCs. Moreover, controlled shape evolution from anisotropic NPLs to NCs was investigated through variations in the amount of NOBF4. This further validates that additives exert a decisive role in the symmetry and growth of nanostructured perovskite crystals during phase transition based on the ligand-exchange mechanism. This finding serves as a source of inspiration for the synthesis of highly luminescent CsPbBr3 NCs, providing valuable insights into the chemical mechanism in post-synthesis transformation.

Sensitization Strategies of Lateral Flow Immunochromatography for Gold Modified Nanomaterials in Biosensor Development.

Gold nanomaterials have become very attractive nanomaterials for biomedical research due to their unique physical and chemical properties, including size dependent optical, magnetic and catalytic properties, surface plasmon resonance (SPR), biological affinity and structural suitability. The performance of biosensing and biodiagnosis can be significantly improved in sensitivity, specificity, speed, contrast, resolution and so on by utilizing multiple optical properties of different gold nanostructures. Lateral flow immunochromatographic assay (LFIA) based on gold nanoparticles (GNPs) has the advantages of simple, fast operation, stable technology, and low cost, making it one of the most widely used in vitro diagnostics (IVDs). However, the traditional colloidal gold (CG)-based LFIA can only achieve qualitative or semi-quantitative detection, and its low detection sensitivity cannot meet the current detection needs. Due to the strong dependence of the optical properties of gold nanomaterials on their shape and surface properties, gold-based nanomaterial modification has brought new possibilities to the IVDs: people have attempted to change the morphology and size of gold nanomaterials themselves or hybrid with other elements for application in LFIA. In this paper, many well-designed plasmonic gold nanostructures for further improving the sensitivity and signal output stability of LFIA have been summarized. In addition, some opportunities and challenges that gold-based LFIA may encounter at present or in the future are also mentioned in this paper. In summary, this paper will demonstrate some feasible strategies for the manufacture of potential gold-based nanobiosensors of post of care testing (POCT) for faster detection and more accurate disease diagnosis.

Scientific Machine Learning of 2D Perovskite Nanosheet Formation.

We apply a scientific machine learning (ML) framework to aid the prediction and understanding of nanomaterial formation processes via a joint spectral-kinetic model. We apply this framework to study the nucleation and growth of two-dimensional (2D) perovskite nanosheets. Colloidal nanomaterials have size-dependent optical properties and can be observed in situ, all of which make them a good model for understanding the complex processes of nucleation, growth, and phase transformation of 2D perovskites. Our results demonstrate that this model nanomaterial can form through two processes at the nanoscale: either via a layer-by-layer chemical exfoliation process from lead bromide nanocrystals or via direct nucleation from precursors. We utilize a phenomenological kinetic analysis to study the exfoliation process and scientific machine learning to study the direct nucleation and growth and discuss the circumstances under which it is more appropriate to use phenomenological or more complex machine learning models. Data for both analysis techniques are collected through in situ spectroscopy in a stopped flow chamber, incorporating over 500,000 spectra taken under more than 100 different conditions. More broadly, our research shows that the ability to utilize and integrate traditional kinetics and machine learning methods will greatly assist in the understanding of complex chemical systems.

Guilty as Charged: The Role of Undercoordinated Indium in Electron-Charged Indium Phosphide Quantum Dots.

Quantum dots (QDs) are known for their size-dependent optical properties, narrow emission bands, and high photoluminescence quantum yield (PLQY), which make them interesting candidates for optoelectronic applications. In particular, InP QDs are receiving a lot of attention since they are less toxic than other QD materials and are hence suitable for consumer applications. Most of these applications, such as LEDs, photovoltaics, and lasing, involve charging QDs with electrons and/or holes. However, charging of QDs is not easy nor innocent, and the effect of charging on the composition and properties of InP QDs is not yet well understood. This work provides theoretical insight into electron charging of the InP core and InP/ZnSe QDs. Density functional theory calculations are used to show that charging of InP-based QDs with electrons leads to the formation of trap states if the QD contains In atoms that are undercoordinated and thus have less than four bonds to neighboring atoms. InP core-only QDs have such atoms at the surface, which are responsible for the formation of trap states upon charging with electrons. We show that InP/ZnSe core-shell models with all In atoms fully coordinated can be charged with electrons without the formation of trap states. These results show that undercoordinated In atoms should be avoided at all times for QDs to be stably charged with electrons.

Electrochemical Approach for the Synthesis of Ultrasmall Cu13 Clusters and Their Application in the Detection of Endotoxin.

Ultrasmall metal nanoclusters are attractive for their size-dependent optical and electrochemical properties. Here, blue-emitting copper clusters stabilized with cetyltrimethylammonium bromide (CTAB) are synthesized using an electrochemical approach. The electrospray ionization (ESI) analysis reveals that the cluster has 13 copper atoms in the core. The clusters are then used for the electrochemical detection of endotoxin─a bacterial toxin in Gram-negative bacteria. Differential pulse voltammetry (DPV) is used to detect endotoxins with high selectivity and sensitivity. It shows a lower detection limit of 100 ag mL-1 with a linear range of 100 ag mL-1 to 10 ng mL-1. The sensor is efficient for detecting endotoxins from human blood serum samples.

An Experimental Introduction to Colloidal Nanocrystals through InP and InP/ZnS Quantum Dots

Quantum dots are colloidal semiconductor nanocrystals that display size-dependent electronic and optical properties. These materials are a visual demonstration of a quantum-mechanical effect. Here we present a laboratory exercise for undergraduate/Bachelor students as an introduction to colloidal nanocrystals and quantum dots. The students synthesize three sizes of indium phosphide (InP) nanocrystals and perform one core/shell synthesis of indium phosphide cores shelled with zinc sulfide (InP/ZnS). The obtained quantum dots are characterized by quantitative UV–vis, photoluminescence, and 1H NMR spectroscopy. Students are acquainted with several concepts: nanocrystal synthesis, colloids, Beer–Lambert law, quantum confinement, photoluminescence, and surface chemistry. For each concept, background information is provided, rendering this report a comprehensive introduction for students and teachers. Indium phosphide is a safer material to handle in the undergraduate lab compared to cadmium selenide (CdSe), cesium lead bromide (CsPbBr3), or lead sulfide (PbS) nanocrystals.