Structure-Activity Relationships of Natural C-9-Methyl-Substituted 10-Membered Lactones and Their Semisynthetic Derivatives.

Fungal 10-membered lactones (TMLs), such as stagonolide A, herbarumin I, pinolidoxin, and putaminoxin, are promising candidates for the development of nature-derived herbicides. The aim of this study was to analyze the structure-activity relationships (SAR) of C-9-methyl-substituted TMLs with a multitarget bioassay approach to reveal compounds with useful (phytotoxic, entomotoxic, antimicrobial) or undesirable (cytotoxic) bioactivities. A new TML, stagonolide L (1), along with five known compounds (stagonolides D (2) and E (3), curvulides A (4) and B1/B2 (5a,b), and pyrenolide C (6)), were purified from cultures of the phytopathogenic fungus Stagonospora cirsii, and five semisynthetic derivatives of 3 and 4 (7-11) were obtained. The absolute configuration of 4 was revised to 2Z, 4S, 5S, 6R, and 9R. The identity of 5a,b and stagonolide H is discussed. The phytotoxicity of compound 4, the entomotoxicity of 5a,b, and nonselective toxicity of compound 6 are demonstrated. The latter confirms the hypothesis that the α,ß-unsaturated carbonyl group is associated with the high general toxicity of TML, regardless of its position in the ring and other substituents. The epoxide in compound 4 is important for phytotoxicity. The revealed SAR patterns will be useful for further rational design of TML-based herbicides including curvulide A analogs with a 4,5-epoxy group.

PbSe/PbS Core/Shell Nanoplatelets with Enhanced Stability and Photoelectric Properties.

Lead chalcogenide nanoplatelets (NPLs) have emerged as a promising material for devices operating in the near IR and IR spectrum region. Here, we first apply the cation exchange method to PbSe/PbS core/shell NPL synthesis. The shell growth enhances NPL colloidal and environmental stability, and passivates surface trap states, preserving the main core physical properties. To prove the great potential for optoelectrical applications, we fabricate a photoconductor using PbSe/PbS NPLs. The device demonstrates enhanced conductivity and responsivity with fast rise and fall times, resulting in a 13 kHz bandwidth. The carrier transport was investigated with the field effect transistor method, showing p-type conductivity with charge mobility of 1.26 × 10-2 cm2·V-1·s-1.

Colloidal 2D Lead Chalcogenide Nanocrystals: Synthetic Strategies, Optical Properties, and Applications.

Lead chalcogenide nanocrystals (NCs) are an emerging class of photoactive materials that have become a versatile tool for fabricating new generation photonics devices operating in the near-IR spectral range. NCs are presented in a wide variety of forms and sizes, each of which has its own unique features. Here, we discuss colloidal lead chalcogenide NCs in which one dimension is much smaller than the others, i.e., two-dimensional (2D) NCs. The purpose of this review is to present a complete picture of today's progress on such materials. The topic is quite complicated, as a variety of synthetic approaches result in NCs with different thicknesses and lateral sizes, which dramatically change the NCs photophysical properties. The recent advances highlighted in this review demonstrate lead chalcogenide 2D NCs as promising materials for breakthrough developments. We summarized and organized the known data, including theoretical works, to highlight the most important 2D NC features and give the basis for their interpretation.

Carbon Dot Emission Enhancement in Covalent Complexes with Plasmonic Metal Nanoparticles.

Carbon dots can be used for the fabrication of colloidal multi-purpose complexes for sensing and bio-visualization due to their easy and scalable synthesis, control of their spectral responses over a wide spectral range, and possibility of surface functionalization to meet the application task. Here, we developed a chemical protocol of colloidal complex formation via covalent bonding between carbon dots and plasmonic metal nanoparticles in order to influence and improve their fluorescence. We demonstrate how interactions between carbon dots and metal nanoparticles in the formed complexes, and thus their optical responses, depend on the type of bonds between particles, the architecture of the complexes, and the degree of overlapping of absorption and emission of carbon dots with the plasmon resonance of metals. For the most optimized architecture, emission enhancement reaching up to 5.4- and 4.9-fold for complexes with silver and gold nanoparticles has been achieved, respectively. Our study expands the toolkit of functional materials based on carbon dots for applications in photonics and biomedicine to photonics.

Near-Infrared Emission of HgTe Nanoplatelets Tuned by Pb-Doping.

Doping the semiconductor nanocrystals is one of the most effective ways to obtain unique materials suitable for high-performance next-generation optoelectronic devices. In this study, we demonstrate a novel nanomaterial for the near-infrared spectral region. To do this, we developed a partial cation exchange reaction on the HgTe nanoplatelets, substituting Hg cations with Pb cations. Under the optimized reaction conditions and Pb precursor ratio, a photoluminescence band shifts to ~1100 nm with a quantum yield of 22%. Based on steady-state and transient optical spectroscopies, we suggest a model of photoexcitation relaxation in the HgTe:Pb nanoplatelets. We also demonstrate that the thin films of doped nanoplatelets possess superior electric properties compared to their pristine counterparts. These findings show that Pb-doped HgTe nanoplatelets are new perspective material for application in both light-emitting and light-detection devices operating in the near-infrared spectral region.

Engineering the Optical Properties of CsPbBr3 Nanoplatelets through Cd2+ Doping.

Lead halide perovskite nanoplatelets (NPls) attract significant attention due to their exceptional and tunable optical properties. Doping is a versatile strategy for modifying and improving the optical properties of colloidal nanostructures. However, the protocols for B-site doping have been rarely reported for 2D perovskite NPls. In this work, we investigated the post-synthetic treatment of CsPbBr3 NPls with different Cd2+ sources. We show that the interplay between Cd2+ precursor, NPl concentrations, and ligands determines the kinetics of the doping process. Optimization of the treatment allows for the boosting of linear and nonlinear optical properties of CsPbBr3 NPls via doping or/and surface passivation. At a moderate doping level, both the photoluminescence quantum yield and two-photon absorption cross section increase dramatically. The developed protocols of post-synthetic treatment with Cd2+ facilitate further utilization of perovskite NPls in nonlinear optics, photonics, and lightning.

Revealing the nature of optical activity in carbon dots produced from different chiral precursor molecules.

Carbon dots (CDs) are light-emitting nanoparticles that show great promise for applications in biology and medicine due to the ease of fabrication, biocompatibility, and attractive optical properties. Optical chirality, on the other hand, is an intrinsic feature inherent in many objects in nature, and it can play an important role in the formation of artificial complexes based on CDs that are implemented for enantiomer recognition, site-specific bonding, etc. We employed a one-step hydrothermal synthesis to produce chiral CDs from the commonly used precursors citric acid and ethylenediamine together with a set of different chiral precursors, namely, L-isomers of cysteine, glutathione, phenylglycine, and tryptophan. The resulting CDs consisted of O,N-doped (and also S-doped, in some cases) carbonized cores with surfaces rich in amide and hydroxyl groups; they exhibited high photoluminescence quantum yields reaching 57%, chiral optical signals in the UV and visible spectral regions, and two-photon absorption. Chiral signals of CDs were rather complex and originated from a combination of the chiral precursors attached to the CD surface, hybridization of lower-energy levels of chiral chromophores formed within CDs, and intrinsic chirality of the CD cores. Using DFT analysis, we showed how incorporation of the chiral precursors at the optical centers induced a strong response in their circular dichroism spectra. The optical characteristics of these CDs, which can easily be dispersed in solvents of different polarities, remained stable during pH changes in the environment and after UV exposure for more than 400 min, which opens a wide range of bio-applications.

Carbon Dots with an Emission in the Near Infrared Produced from Organic Dyes in Porous Silica Microsphere Templates.

Carbon dots (CDs) with an emission in the near infrared spectral region are attractive due to their promising applications in bio-related areas, while their fabrication still remains a challenging task. Herein, we developed a template-assisted method using porous silica microspheres for the formation of CDs with optical transitions in the near infrared. Two organic dyes, Rhodamine 6G and IR1061 with emission in the yellow and near infrared spectral regions, respectively, were used as precursors for CDs. Correlation of morphology and chemical composition with optical properties of obtained CDs revealed the origin of their emission, which is related to the CDs' core optical transitions and dye-derivatives within CDs. By varying annealing temperature, different kinds of optical centers as derivatives of organic dyes are formed in the microsphere's pores. The template-assisted method allows us to synthesize CDs with an emission peaked at 1085 nm and photoluminescence quantum yield of 0.2%, which is the highest value reported so far for CDs emitting at wavelengths longer than 1050 nm.

Structure-Activity Relationship of Phytotoxic Natural 10-Membered Lactones and Their Semisynthetic Derivatives.

Ten-membered lactones (nonenolides) demonstrate phytotoxic, antimicrobial, and fungicidal activity promising for the development of natural product-derived pesticides. The fungus Stagonospora cirsii is able to produce phytotoxic stagonolides A (1), J (2), K (3) and herbarumin I (4) with high yield. The aim of this study was to create a set of structurally related nonenolides and to reveal the structural features that affect their biological activity. Stagonolide A (1) and C-7 oxidized stagonolide K (11) showed the highest phytotoxicity in leaf puncture assay and agar seedlings assay. The oxidation of C-7 hydroxyl group (as in 1, acetylstagonolide A (10) and (11) led to the manifestation of toxicity to microalgae, Bacillus subtilis and Sf9 cells regardless of the configuration of C-9 propyl chains (R in 1 and 10, S in 11). C-7 non-oxidized nonenolides displayed none or little non-target activity. Notably, 7S compounds were more phytotoxic than their 7R analogues. Due to the high inhibitory activity against seedling growth and the lack of side toxicity, mono- and bis(acetyl)- derivatives of herbarumin I were shown to be potent for the development of pre-emergent herbicides. The identified structural features can be used for the rational design of new herbicides.

Beyond Charge Transfer: The Impact of Auger Recombination and FRET on PL Quenching in an rGO-QDs System.

PL intensity quenching and the PL lifetime reduction of fluorophores located close to graphene derivatives are generally explained by charge and energy transfer processes. Analyzing the PL from PbS QDs in rGO/QD systems, we observed a substantial reduction in average PL lifetimes with an increase in rGO content that cannot be interpreted solely by these two processes. To explain the PL lifetime dependence on the rGO/QD component ratio, we propose a model based on the Auger recombination of excitations involving excess holes left in the QDs after the charge transfer process. To validate the model, we conducted additional experiments involving the external engineering of free charge carriers, which confirmed the role of excess holes as the main QD PL quenching source. A mathematical simulation of the model demonstrated that the energy transfer between neighboring QDs must also be considered to explain the experimental data carefully. Together, Auger recombination and energy transfer simulation offers us an excellent fit for the average PL lifetime dependence on the component ratio of the rGO/QD system.

Chiral carbon dots based on L/D-cysteine produced via room temperature surface modification and one-pot carbonization.

Since chirality is one of the phenomena often occurring in nature, optically active chiral compounds are important for applications in the fields of biology, pharmacology, and medicine. With this in mind, chiral carbon dots (CDs), which are eco-friendly and easy-to-obtain light-emissive nanoparticles, offer great potential for sensing, bioimaging, enantioselective synthesis, and development of emitters of circularly polarized light. Herein, chiral CDs have been produced via two synthetic approaches using a chiral amino acid precursor l/d-cysteine: (i) surface modification treatment of achiral CDs at room temperature and (ii) one-pot carbonization in the presence of chiral precursor. The chiral signal in the absorption spectra of synthesized CDs originates not only from the chiral precursor but from the optical transitions attributed to the core and surface states of CDs. The use of chiral amino acid molecules in the CD synthesis through carbonization results in a substantial (up to 8 times) increase in their emission quantum yield. Moreover, the synthesized CDs show two-photon absorption which is an attractive feature for their potential bioimaging and sensing applications.

The influence of thermal treatment conditions (solvothermal versus microwave) and solvent polarity on the morphology and emission of phloroglucinol-based nitrogen-doped carbon dots.

The optical properties of chemically synthesized carbon dots (CDs) can be widely tuned via doping and surface modification with heteroatoms such as nitrogen, which results in a range of potential applications. Herein, two most commonly used synthesis approaches, namely, solvothermal and microwave-assisted thermal treatments, have been used for the preparation of CDs from phloroglucinol using three different nitrogen containing solvents, namely, ethylenediamine, dimethylformamide, and formamide. Based on the analysis of the morphology and optical properties, we demonstrate the tenability of the CD appearance from amorphous or well-carbonized spherical particles to onion-like ones, which is controlled by solvent polarity, whereas the thermal treatment conditions mostly influence the degree of N-doping and the nature of emissive centers of CDs formed. The findings of this study expand the toolkit of the available CDs with variable morphology and energy structure.

Applications of Carbon Dots in Optoelectronics.

Carbon dots (CDs) are an attractive class of nanomaterials due to the ease of their synthesis, biocompatibility, and superior optical properties. The electronic structure of CDs and hence their optical transitions can be controlled and tuned over a wide spectral range via the choice of precursors, adjustment of the synthetic conditions, and post-synthetic treatment. We summarize recent progress in the synthesis of CDs emitting in different colors in terms of morphology and optical properties of the resulting nanoparticles, with a focus on the synthetic approaches allowing to shift their emission to longer wavelengths. We further consider formation of CD-based composite materials, and review approaches used to prevent aggregation and self-quenching of their emission. We then provide examples of applications of CDs in optoelectronic devices, such as solar cells and light-emitting diodes (LEDs) with a focus on white LEDs.

Lab-on-Microsphere-FRET-Based Multiplex Sensor Platform.

Here we report on the development and investigation of a novel multiplex assay model based on polymer microspheres (PMS) encoded with ternary AIS/ZnS quantum dots (QDs). The system was prepared via layer-by-layer deposition technique. Our studies of Förster resonance energy transfer (FRET) between the QD-encoded microspheres and two different cyanine dyes have demonstrated that the QD photoluminescence (PL) quenching steadily increases with a decrease in the QD-dye distance. We have found that the sensitized dye PL intensity demonstrates a clear maximum at two double layers of polyelectrolytes between QDs and Dye molecules on the polymer microspheres. Time resolved PL measurements have shown that the PL lifetime decreases for the QDs and increases for the dyes due to FRET. The designed system makes it possible to record spectrally different bands of FRET-induced dye luminescence with different decay times and thereby allows for the multiplexing by wavelength and photoluminescence lifetimes of the dyes. We believe that PMS encoded with AIS/ZnS QDs have great potential for the development of new highly selective and sensitive sensor systems for multiplex analysis to detect cell lysates and body fluids' representative biomarkers.

Temperature-Dependent Photoluminescent Properties of PbSe Nanoplatelets.

Semiconductor colloidal nanoplatelets (NPLs) are a promising new class of nanostructures that can bring much impact on lightning technologies, light-emitting diodes (LED), and laser fabrication. Indeed, great progress has been made in optimizing the optical properties of the NPLs for the visible spectral range, which has already made the implementation of a number of effective devices on their basis possible. To date, state-of-the-art near-infrared (NIR)-emitting NPLs are significantly inferior to their visible-range counterparts, although it would be fair to say that they received significantly less research attention so far. In this study, we report a comprehensive analysis of steady-state and time-dependent photoluminescence (PL) properties of four monolayered (ML) PbSe NPLs. The PL measurements are performed in a temperature range of 78-300 K, and their results are compared to those obtained for CdSe NPLs and PbSe quantum dots (QDs). We show that multiple emissive states, both band-edge and trap-related, are responsible for the formation of the NPLs' PL band. We demonstrate that the widening of the PL band is caused by the inhomogeneous broadening rather than homogeneous one, and analyze the possible contributions to PL broadening.

FRET-Based Analysis of AgInS2/ZnAgInS/ZnS Quantum Dot Recombination Dynamics.

Ternary quantum dots (QDs) are very promising nanomaterials with a range of potential applications in photovoltaics, light-emitting devices, and biomedicine. Despite quite intensive studies of ternary QDs over the last years, the specific relaxation channels involved in their emission mechanisms are still poorly understood, particularly in the corresponding core-shell nanostructures. In the present work, we have studied the recombination pathways of AgInS2 QDs stabilized with the ZnAgInS alloy layer and the ZnS shell (AIS/ZAIS/ZnS QDs) using time-resolved fluorescence spectroscopy. We have also investigated FRET in complexes of AIS/ZAIS/ZnS QDs and cyanine dyes with the absorption bands overlapping in the different regions of the QD emission spectrum, which allowed us to selectively quench the radiative transitions of the QDs. Our studies have demonstrated that FRET from QDs to dyes results in decreasing of all QD PL decay components with the shortest lifetime decreasing the most and the longest one decreasing the least. This research presents important approaches for the investigation of ternary QD luminescence mechanisms by the selective quenching of recombination pathways. These studies are also essential for potential applications of ternary QDs in photodynamic therapy, multiplex analysis, and time-resolved FRET sensing.

Magneto-Fluorescent Hybrid Sensor CaCO3-Fe3O4-AgInS2/ZnS for the Detection of Heavy Metal Ions in Aqueous Media.

Heavy metal ions are not subject to biodegradation and could cause the environmental pollution of natural resources and water. Many of the heavy metals are highly toxic and dangerous to human health, even at a minimum amount. This work considered an optical method for detecting heavy metal ions using colloidal luminescent semiconductor quantum dots (QDs). Over the past decade, QDs have been used in the development of sensitive fluorescence sensors for ions of heavy metal. In this work, we combined the fluorescent properties of AgInS2/ZnS ternary QDs and the magnetism of superparamagnetic Fe3O4 nanoparticles embedded in a matrix of porous calcium carbonate microspheres for the detection of toxic ions of heavy metal: Co2+, Ni2+, and Pb2+. We demonstrate a relationship between the level of quenching of the photoluminescence of sensors under exposure to the heavy metal ions and the concentration of these ions, allowing their detection in aqueous solutions at concentrations of Co2+, Ni2+, and Pb2+ as low as ≈0.01 ppm, ≈0.1 ppm, and ≈0.01 ppm, respectively. It also has importance for application of the ability to concentrate and extract the sensor with analytes from the solution using a magnetic field.

Toward Bright Red-Emissive Carbon Dots through Controlling Interaction among Surface Emission Centers.

Relatively weak red photoluminescence of carbon dots (CDots) is a major challenge on the way to their successful implementation in biological and optoelectronic devices. We present a theoretical analysis of the interaction among the surface emission centers of CDots, showing that it may determine efficiency of the red photoluminescence of CDots. Based on the previous experimental studies, it is assumed that the optical response of the CDots is determined by the molecule-like subunits of polycyclic aromatic hydrocarbons (PAHs) attached to the CDots' surface. Three characteristic types of coupling of these PAH subunits are considered: non-interacting monomers, noncovalently bound dimers, and covalently bound dimers with two, three, or four carbon linkers. We demonstrate that the CDots' photoluminescence broadens, redshifts, and weakens by 2 orders of magnitude when the free monomers are substituted by the covalently bridged centers. These and other results of our study show that the realization of CDots with many weakly interacting surface emission centers may constitute an efficient way to achieve their efficient red photoluminescence, which is highly desirable for biological and optoelectronic applications.

Spectral-Time Multiplexing in FRET Complexes of AgInS2/ZnS Quantum Dot and Organic Dyes.

Nowadays, multiplex analysis is very popular, since it allows to detect a large number of biomarkers simultaneously. Traditional multiplex analysis is usually based on changes of photoluminescence (PL) intensity and/or PL band spectral positions in the presence of analytes. Using PL lifetime as an additional parameter might increase the efficiency of multiplex methods. Quantum dots (QDs) can be used as luminescent markers for multiplex analysis. Ternary in-based QDs are a great alternative to the traditional Cd-based one. Ternary QDs possess all advantages of traditional QDs, including tunable photoluminescence in visible range. At the same time ternary QDs do not have Cd-toxicity, and moreover they possess long spectral dependent lifetimes. This allows the use of ternary QDs as a donor for time-resolved multiplex sensing based on Förster resonance energy transfer (FRET). In the present work, we implemented FRET from AgInS2/ZnS ternary QDs to cyanine dyes absorbing in different spectral regions of QD luminescence with different lifetimes. As the result, FRET-induced luminescence of dyes differed not only in wavelengths but also in lifetimes of luminescence, which can be used for time-resolved multiplex analysis in biology and medicine.

Strongly Luminescent Composites Based on Carbon Dots Embedded in a Nanoporous Silicate Glass.

Luminescent composites based on entirely non-toxic, environmentally friendly compounds are in high demand for a variety of applications in photonics and optoelectronics. Carbon dots are a recently developed kind of luminescent nanomaterial that is eco-friendly, biocompatible, easy-to-obtain, and inexpensive, with a stable and widely tunable emission. Herein, we introduce luminescent composites based on carbon dots of different chemical compositions and with different functional groups at the surface which were embedded in a nanoporous silicate glass. The structure and optical properties of these composites were comprehensively examined using electron microscopy, Fourier transform infrared transmission, UV-Vis absorption, and steady-state and time-resolved photoluminescence. It is shown that the silicate matrix efficiently preserved, and even enhanced the emission of different kinds of carbon dots tested. The photoluminescence quantum yield of the fabricated nanocomposite materials reached 35-40%, which is comparable to or even exceeds the values for carbon dots in solution.