Influence of the stabilizing ligand on the quality, signal-relevant optical properties, and stability of near-infrared emitting Cd1₁₋ₓHgₓTe nanocrystals

Bright and stable near-infrared (NIR) and infrared (IR) emitting chromophores are in high demand for applications in telecommunication, solar cells, security barcodes, and as fluorescent reporters in bioimaging studies. The best choice for wavelengths >750 nm are semiconductor nanocrystals, especially ternary or alloy nanocrystals like CdHgTe, which enable size and composition control of their optical properties. Here, we report on the influence of growth time and surface chemistry on the composition and optical properties of colloidal CdHgTe. Up to now, these are the only NIR and IR emissive quantum dots, which can be synthesized in high quality in water, using a simple one-pot reaction. For this study we utilized and compared three different thiol ligands, thioglycolic acid (TGA), 3-mercaptopropionic acid (MPA), and glutathione (GSH). Aiming at the rational design of bright NIR- and IR-emissive alloy materials, special emphasis was dedicated to a better understanding of the role of the surface ligand and adsorption–desorption equilibria on the photoluminescence quantum yield and stability. In this respect, dilution and protonation studies were performed. Our results show that with this simple synthetic procedure, strongly fluorescent CdHgTe colloids can be obtained with MPA as stabilizing ligand revealing quantum yields as high as 45% independent of particle concentration

Penetration of amphiphilic quantum dots through model and cellular plasma membranes

In this work we demonstrate progress in the colloidal synthesis of amphiphilic CdTe nanocrystals stabilized by thiolated PEG oligomers with the aim of facilitating cellular uptake of the particles. High-boiling, good coordinating solvents such as dimethylacetamide and dimethylformamide accelerate the growth of the nanoparticles yielding stable colloids of which photoluminescence maxima can be tuned to cover the region of 540-640 nm with quantum yields of up to 30%. The CdTe nanocrystals capped by thiolated methoxypolyethylene glycol are shown to penetrate through the lipid bilayer of giant unilamellar vesicles and giant plasma membrane vesicles which constitute basic endocytosis-free model membrane systems. Moreover, the penetration of amphiphilic particles through live cell plasma membranes and their ability to escape the endocytic pathway have been demonstrated

Penetration of amphiphilic quantum dots through model and cellular plasma membranes

In this work we demonstrate progress in the colloidal synthesis of amphiphilic CdTe nanocrystals stabilized by thiolated PEG oligomers with the aim of facilitating cellular uptake of the particles. High-boiling, good coordinating solvents such as dimethylacetamide and dimethylformamide accelerate the growth of the nanoparticles yielding stable colloids of which photoluminescence maxima can be tuned to cover the region of 540-640 nm with quantum yields of up to 30%. The CdTe nanocrystals capped by thiolated methoxypolyethylene glycol are shown to penetrate through the lipid bilayer of giant unilamellar vesicles and giant plasma membrane vesicles which constitute basic endocytosis-free model membrane systems. Moreover, the penetration of amphiphilic particles through live cell plasma membranes and their ability to escape the endocytic pathway have been demonstrated

Influence of the stabilizing ligand on the quality, signal-relevant optical properties, and stability of near-infrared emitting Cd1₁₋ₓHgₓTe nanocrystals

Bright and stable near-infrared (NIR) and infrared (IR) emitting chromophores are in high demand for applications in telecommunication, solar cells, security barcodes, and as fluorescent reporters in bioimaging studies. The best choice for wavelengths >750 nm are semiconductor nanocrystals, especially ternary or alloy nanocrystals like CdHgTe, which enable size and composition control of their optical properties. Here, we report on the influence of growth time and surface chemistry on the composition and optical properties of colloidal CdHgTe. Up to now, these are the only NIR and IR emissive quantum dots, which can be synthesized in high quality in water, using a simple one-pot reaction. For this study we utilized and compared three different thiol ligands, thioglycolic acid (TGA), 3-mercaptopropionic acid (MPA), and glutathione (GSH). Aiming at the rational design of bright NIR- and IR-emissive alloy materials, special emphasis was dedicated to a better understanding of the role of the surface ligand and adsorption–desorption equilibria on the photoluminescence quantum yield and stability. In this respect, dilution and protonation studies were performed. Our results show that with this simple synthetic procedure, strongly fluorescent CdHgTe colloids can be obtained with MPA as stabilizing ligand revealing quantum yields as high as 45% independent of particle concentration

Versatile H2O2-driven mixed aerogel synthesis from CdTe and bimetallic noble metal nanoparticles

Mixed aerogels from semiconductor and metal nanoparticles represent an outstanding hybrid material with exceptional properties due to two striking advantages: the creation of a huge quantity of semiconductor-metal interfaces combined with a highly porous three-dimensional nanostructured network. We present a versatile synthetic pathway towards hybrid aerogels built up by joint gelation of CdTe and noble metal nanoparticles (Au, Pd and bimetallic Au/Pd). A straightforward HO treatment inducing gel formation is developed as a more elegant alternative compared to the established photooxidation approach. The use of HO allows a reproducible, simple and mild gel formation which can be easily upscaled. The tremendous influence of the HO concentration on gelation mechanism and gelation kinetics is revealed by photoluminescence quantum yield (PLQY) determinations. Resulting gels are extensively characterized via transmission electron microscopy (TEM), scanning TEM (STEM), energy dispersive X-ray analysis (EDX) as well as photoluminescence (PL) spectroscopy and PL lifetime measurements. By varying the composition of the herein presented noble metal nanoparticles in a controlled fashion the range of semiconductor-metal hybrid aerogels is widened, which demonstrates the versatility and consistency of our approach. This synthetic flexibility grants access to a variety of different mixed hybrid aerogels which are of high significance for catalytic, sensing and photonic applications.Parts of TEM investigations have been carried out at the Leibniz-Institut für Polymerforschung Dresden e.V. Access to their TEM facility is gratefully acknowledged. AD thanks the Government of the Russian Federation (Grant 074-U01) through ITMO Post-Doctoral Fellowship.Peer Reviewe

Versatile H2O2 driven mixed aerogel synthesis from CdTe and bimetallic noble metal nanoparticles

Mixed aerogels from semiconductor and metal nanoparticles represent an outstanding hybrid material with exceptional properties due to two striking advantages the creation of a huge quantity of semiconductor metal interfaces combined with a highly porous three dimensional nanostructured network. We present a versatile synthetic pathway towards hybrid aerogels built up by joint gelation of CdTe and noble metal nanoparticles Au, Pd and bimetallic Au Pd . A straightforward H2O2 treatment inducing a gel formation is developed as a more elegant alternative compared to the established photooxidation approach. The use of H2O2 allows a reproducible, simple and mild gel formation which can be easily upscaled. The tremendous influence of the H2O2 concentration on gelation mechanism and gelation kinetics is revealed by photoluminescence quantum yield PLQY determinations. Resulting gels are extensively characterized via transmission electron microscopy TEM , scanning TEM STEM , energy dispersive X ray analysis EDX as well as photoluminescence PL spectroscopy and PL lifetime measurements. By varying the composition of the herein presented noble metal nanoparticles in a controlled fashion the range of semiconductor metal hybrid aerogels is widened, which demonstrates the versatility and consistency of our approach. This synthetic flexibility grants access to a ariety of different mixed hybrid aerogels which are of high significance for catalytic, sensing and photonic application

Immobilization of pH-sensitive CdTe Quantum Dots in a Poly(acrylate) Hydrogel for Microfluidic Applications

Abstract Microfluidic devices present the basis of modern life sciences and chemical information processing. To control the flow and to allow optical readout, a reliable sensor material that can be easily utilized for microfluidic systems is in demand. Here, we present a new optical readout system for pH sensing based on pH sensitive, photoluminescent glutathione capped cadmium telluride quantum dots that are covalently immobilized in a poly(acrylate) hydrogel. For an applicable pH sensing the generated hybrid material is integrated in a microfluidic sensor chip setup. The hybrid material not only allows in situ readout, but also possesses valve properties due to the swelling behavior of the poly(acrylate) hydrogel. In this work, the swelling property of the hybrid material is utilized in a microfluidic valve seat, where a valve opening process is demonstrated by a fluid flow change and in situ monitored by photoluminescence quenching. This discrete photoluminescence detection (ON/OFF) of the fluid flow change (OFF/ON) enables upcoming chemical information processing

Immobilization of pH-sensitive CdTe quantum dots in a poly(acrylate) hydrogel for microfluidic applications

Microfluidic devices present the basis of modern life sciences and chemical information processing. To control the flow and to allow optical readout, a reliable sensor material that can be easily utilized for microfluidic systems is in demand. Here, we present a new optical readout system for pH sensing based on pH sensitive, photoluminescent glutathione capped cadmium telluride quantum dots that are covalently immobilized in a poly(acrylate) hydrogel. For an applicable pH sensing the generated hybrid material is integrated in a microfluidic sensor chip setup. The hybrid material not only allows in situ readout, but also possesses valve properties due to the swelling behavior of the poly(acrylate) hydrogel. In this work, the swelling property of the hybrid material is utilized in a microfluidic valve seat, where a valve opening process is demonstrated by a fluid flow change and in situ monitored by photoluminescence quenching. This discrete photoluminescence detection (ON/OFF) of the fluid flow change (OFF/ON) enables upcoming chemical information processing.MF and SL gratefully acknowledge the cluster of Excellence “Center for Advancing Electronics Dresden (CfAED) for financial and assistant support. AD thanks the Government of the Russian Federation (Grant 074-U01) through ITMO Post-Doctoral Fellowship and the European Social Fund (ESF) for financing within the project “ChemIT”.Peer Reviewe