Photocycloaddition of Zero-Dimensional Metal Halide Hybrids with Reversible Photochromism.

In this work, two zero-dimensional (0D) metal halide hybrids L2ZnBr4 [1, L = (E)-4-(2-(1H-pyrrol-3-yl)vinyl)-1-methylpyridin-1-ium] and L6Pb3Br12 (2) were prepared, which demonstrated photochromism and photoinduced cracking. Upon irradiation at 450 nm, a single crystal-to-single crystal transformation occurred as a result of the [2 + 2] photocycloaddition of L. Interestingly, compared to the complete photocycloaddition of L in 1, only two-thirds of L monomers could be photodimerized in 2 because of the difference in L orientation. 1 shows reversible photochromic behavior including rapid response time, few cracks, high conversion rate, and good reaction reversibility, while 2 exhibits no significant color change but distinct photoinduced cracking because of the large local lattice strain induced by inhomogeneous and anisotropic deformation. Moreover, the photocycloaddition of L results in the distinct shift of photoluminescence of 1 and 2, attributed to the variation in conjugation of π electrons and distortion of metal halide clusters. As a proof-of-concept, reversible optical writing is demonstrated for 1. These findings provide new insights into the design of stimuli-responsive multifunctional materials.

Ultrafast Exciton Dynamics of CH3NH3PbBr3 Perovskite Nanoclusters.

Exciton dynamics of perovskite nanoclusters has been investigated for the first time using femtosecond transient absorption (TA) and time-resolved photoluminescence (TRPL) spectroscopy. The TA results show two photoinduced absorption signals at 420 and 461 nm and a photoinduced bleach (PB) signal at 448 nm. The analysis of the PB recovery kinetic decay and kinetic model uncovered multiple processes contributing to electron-hole recombination. The fast component (∼8 ps) is attributed to vibrational relaxation within the initial excited state, and the medium component (∼60 ps) is attributed to shallow carrier trapping. The slow component is attributed to deep carrier trapping from the initial conduction band edge (∼666 ps) and the shallow trap state (∼40 ps). The TRPL reveals longer time dynamics, with modeled lifetimes of 6.6 and 93 ns attributed to recombination through the deep trap state and direct band edge recombination, respectively. The significant role of exciton trapping processes in the dynamics indicates that these highly confined nanoclusters have defect-rich surfaces.

Effect of Lattice Disorder on Exciton Dynamics in Copper-Doped InP/ZnSexS1-x Core/Shell Quantum Dots.

InP/ZnSexS1-x core/shell quantum dots (QDs) with varying Cu concentrations were synthesized by a one-pot hot-injection method. X-ray diffraction and high-resolution transmission electron microscopy results indicate that Cu doping did not alter the crystal structure or particle size of the QDs. The optical shifts in UV-visible absorption and photoluminescence (PL) suggest changes in the electronic structure and induction of lattice disorder due to Cu doping. Ultrafast transient absorption spectroscopy (TAS) reveled that a higher Cu-doping level leads to faster charge carrier recombination, likely due to increased nonradiative decay from defect states. Time-resolved PL (TRPL) studies show longer average lifetimes of charge carriers with increased Cu doping. These findings informed the development of a kinetic model to better understand how Cu-induced disorder affects charge carrier dynamics in the QDs, which is important for emerging applications of Cu-doped InP/ZnSexS1-x QDs in optoelectronics.

Photocatalytic CO2 Reduction Coupled with Oxidation of Benzyl Alcohol over CsPbBr3@PANI Nanocomposites.

Herein, we successfully prepare conductive polyaniline (PANI)-encapsulated CsPbBr3 perovskite nanocrystals (PNCs) that demonstrate much improved photocatalytic performance and stability toward the CO2 reduction reaction (CRR) coupled with oxidation of benzyl alcohol (BA) to benzaldehyde. Due to the acid-base interaction between CO2 and PANI, CO2 molecules are selectively adsorbed on PANI in the form of carbamate. As a result, the rate of production of CO (rCO) reaches 26.1 µmol g-1 h-1 with a selectivity of 98.1%, which is in good agreement with the rate of oxidation (∼27.0 µmol g-1 h-1) of BA. Such a high reduction/oxidation rate is enabled by the fast electron transfer (∼2.2 ps) from PNCs to PANI, as revealed by femtosecond transient absorption spectroscopy. Moreover, because of the benefit of the encapsulation of PANI, no significant decrease in rCO is observed in a 10 h CRR test. This work offers insight into how to simultaneously achieve improved photocatalytic performance and stability of CsPbX3 PNCs.

Novel Chiral CsPbBr3 Metal Halide Perovskite Magic-Sized Clusters and Metal Halide Molecular Clusters with Achiral Ligands.

We have synthesized inherently chiral cesium lead halide perovskite magic-sized clusters (PMSCs) and ligand-assisted metal halide molecular clusters (MHMCs) using the achiral ligands octanoic acid (OCA) and octylamine (OCAm). UV-vis electronic absorption was used to confirm characteristic absorption bands while circular dichroism (CD) spectroscopy was utilized to determine their chiroptical activity in the 412-419 and 395-405 nm regions, respectively. In contrast, the larger sized counterpart of PMSCs, namely, perovskite quantum dots (PQDs), do not show chirality. The inherent chirality of the clusters is tentatively attributed to a twisted chiral layered structure, defect-induced chiral structure, or twisted Pb-Br octahedra.

Ultrafast Study of Excited State Dynamics of Amino Metal Halide Molecular Clusters.

The excited state dynamics of ligand-passivated PbBr2 molecular clusters (MCs) in solution have been investigated for the first time using femtosecond transient absorption spectroscopy. The results uncover a transient bleach (TB) feature peaked around 404 nm, matching the ground state electronic absorption band peaked at 404 nm. The TB recovery signal can be fitted with a triple exponential with fast (10 ps), medium (350 ps), and long (1.8 ns) time constants. The medium and long time constants are very similar to those observed in the time-resolved photoluminescence (TRPL) decay monitored at 412 nm. The TB fast component is attributed to vibrational relaxation in the excited electronic state while the medium component with dominant amplitude is attributed to recombination between the relaxed electron and hole. The small amplitude slow component is assigned to electrons in a relatively long-lived excited electronic state, e.g., triplet state, or shallow trap state due to defects. This study provides new insights into the excited state dynamics of metal halide MCs.

Octahedral Distortions Generate a Thermally Activated Phonon-Assisted Radiative Recombination Pathway in Cubic CsPbBr3 Perovskite Quantum Dots.

Exciton-phonon interactions elucidate structure-function relationships that aid in the control of color purity and carrier diffusion, which is necessary for the performance-driven design of solid-state optical emitters. Temperature-dependent steady-state photoluminescence (PL) and time-resolved PL (TRPL) reveal that thermally activated exciton-phonon interactions originate from structural distortions related to vibrations in cubic CsPbBr3 perovskite quantum dots (PQDs) at room temperature. Exciton-phonon interactions cause performance-degrading PL line width broadening and slower electron-hole recombination. Structural distortions in cubic PQDs at room temperature exist as the bending and stretching of the PbBr6 octahedra subunit. The PbBr6 octahedral distortions cause symmetry breaking, resulting in thermally activated longitudinal optical (LO) phonon coupling to the photoexcited electron-hole pair that manifests as inhomogeneous PL line width broadening. At cryogenic temperatures, the line width broadening is minimized due to a decrease in phonon-assisted recombination through shallow traps. A fundamental understanding of these intrinsic exciton-phonon interactions gives insight into the polymorphic nature of the cubic phase and the origins of performance degradation in PQD optical emitters.

Molecularly imprinted fluorescence assay based on lead halide perovskite quantum dots for determination of benzo(a)pyrene.

Molecularly imprinted polymers with methylammonium lead halide perovskite quantum dots (MIP@MAPbBr3 PQDs) have been prepared and applied to the determination of benzo(a)pyrene (BaP) for the first time. The photoluminescence (PL) of MIP@MAPbBr3 PQDs was enhanced due to the surface passivation of defects by BaP. PL excitation and emission spectra, X-ray diffraction, Fourier transform infrared, and time-resolved PL studies suggest that the interaction between MIP@MAPbBr3 PQDs and BaP is a dynamic process. After MIP@MAPbBr3 PQDs were incubated with BaP, the benzene ring in the molecular structure of BaP can interact with MIP@MAPbBr3 PQDs through π electrons, which reduces non-radiative recombination of MIP@MAPbBr3 PQDs and lengthens excited state lifetime. The PL intensity of the MIP@MAPbBr3 PQDs-BaP system was monitored at 520 nm with 375 nm excitation. Under optimized conditions, the PL intensity of MIP@MAPbBr3 PQDs is linear with the concentration of BaP in the 10 to 100 ng·mL-1 range, with a detection limit of 1.6 ng·mL-1. The imprinting factor was 3.9, indicating excellent specificity of MIP@MAPbBr3 PQDs for BaP. The MIP@MAPbBr3 PQDs were subsequently applied to the PL analysis of BaP in sunflower seed oil, cured meat, and grilled fish samples, achieving recoveries from 79.3 to 107%, and relative standard deviations below 10%. This molecularly imprinted fluorescence assay improves the selectivity of BaP in complex mixtures and could be extended to other analytes.

Origin of the near 400 nm Absorption and Emission Band in the Synthesis of Cesium Lead Bromide Nanostructures: Metal Halide Molecular Clusters Rather Than Perovskite Magic-Sized Clusters.

In the synthesis of cesium lead bromide (CsPbBr3) perovskite quantum dots, with an electronic absorption and emission band around 510 nm, and perovskite magic-sized clusters (PMSCs), with an electronic absorption and emission band around 430 nm, another distinct absorption and emission around 400 nm is often observed. While many would attribute this band to small perovskite particles, here we show strong evidence that this band is a result of the formation of lead bromide molecular clusters (PbBr2 MCs) passivated with ligands, which do not contain the A component of the ABX3 perovskite structure. This evidence comes from a systematic comparative study of the reaction products with and without the A component under otherwise identical experimental conditions. The results support that the near 400 nm band originates from ligand-passivated PbBr2 MCs. This observation seems to be quite general and is significant in understanding the nature of the reaction products in the synthesis of metal halide perovskite nanostructures.

Impact of Molecular Ligands in the Synthesis and Transformation between Metal Halide Perovskite Quantum Dots and Magic Sized Clusters.

Metal halide perovskite quantum dots (PQDs) and perovskite magic sized clusters (PMSCs) exhibit interesting size- and composition-dependent optoelectronic properties that are promising for emerging applications including photovoltaic solar cells and light-emitting diodes (LEDs). Much work has focused on developing new synthesis strategies to improve their structural stability and property tunability. In this paper, we review recent progress in the synthesis and characterization of PQDs and PMSCs, with a focus on the impact of different molecular ligands on their surface passivation and interconversion. Moreover, the effect of capping ligands on ion exchange during synthesis and doping is discussed. Finally, we present some perspectives on challenges and opportunities in fundamental studies and potential applications of both PQDs and PMSCs.

Hollow Gold Nanosphere Templated Synthesis of PEGylated Hollow Gold Nanostars and Use for SERS Detection of Amyloid Beta in Solution.

Hollow gold nanospheres (HGNs) have been used as the template for seed-mediated growth of multibranched hollow gold nanostars (HNS). The HGNs were synthesized via anerobic reduction of cobalt chloride to cobalt nanoparticles and then formation of a gold shell via galvanic replacement followed by the oxidation of the cobalt core. We obtained control of the inner core size of the HGNs by increasing the size of the sacrificial cobalt core and by varying the ratio of B(OH)3/BH4 using boric acid rather than 48 h aged borohydride. We synthesized the HNS by reducing Au3+ ions in the presence of Ag+ ions using ascorbic acid, creating a spiky morphology that varied with the Au3+/Ag+ ratio. A broadly tunable localized surface plasmon resonance was achieved through control of both the inner core and the spike length. Amyloid beta (Aß) was conjugated to the HNS by using a heterobifunctional PEG linker and identified by the vibrational modes associated with the conjugated ring phenylalanine side chain. A bicinchoninic acid assay was used to determine the concentration of Aß conjugated to HNS as 20 nM, which is below the level of Aß that negatively affects long-term potentiation. Both the core size and spike length were shown to affect the optical properties of the resulting nanostructures. This HGN templated method introduced a new parameter for enhancing the plasmonic properties of gold nanostars, namely, the addition of a hollow core. Hollow gold nanostars are highly desirable for a wide range of applications, including high sensitivity disease detection and monitoring.

Ultrafast Study of Exciton Transfer in Sb(III)-Doped Two-Dimensional [NH3(CH2)4NH3]CdBr4 Perovskite.

Antimony-based metal halide hybrids have attracted enormous attention due to the stereoactive 5s2 electron pair that drives intense triplet broadband emission. However, energy/charge transfer has been rarely achieved for Sb3+-doped materials. Herein, Sb3+ ions are homogeneously doped into 2D [NH3(CH2)4NH3]CdBr4 perovskite (Cd-PVK) using a wet-chemical method. Compared to the weak singlet exciton emission of Cd-PVK at 380 nm, 0.01% Sb3+-doped Cd-PVK exhibits intense triplet emission located at 640 nm with a near-unity quantum yield. Further increasing the doping concentration of Sb3+ completely quenches singlet exciton emission of Cd-PVK, concurrently with enhanced Sb3+ triplet emission. Delayed luminescence and femtosecond-transient absorption studies suggest that Sb3+ emission originates from exciton transfer (ET) from Cd-PVK host to Sb3+ dopant, while such ET cannot occur with Pb2+-doped Cd-PVK because of the mismatch of energy levels. In addition, density function theory calculations indicate that the introduced Sb3+ likely replace the Cd2+ ions along with the deprotonation of butanediammonium for charge balance, instead of generating Cd2+ vacancies. This work provides a deeper understanding of the ET of Sb3+-doped Cd-PVK and suggests an effective strategy to achieve efficient triplet Sb3+ emission beyond 0D Cl-based hybrids.

Indole Alkaloids from a Soil-Derived Clonostachys rosea.

Clonorosins A (1) and B (2), two novel indole alkaloids featuring unprecedented 6/5/6/6/5 and 6/5/5 cores, together with seven known indole-linked 2,5-diketopiperazine alkaloids (3-9), were isolated from the soil-derived fungus Clonostachys rosea YRS-06. The new structures were proposed through HR-MS, NMR, and ECD spectroscopic data. They were established by comparing the calculated NMR, ECD, and specific rotation data with the experimental. To assist in determining the absolute configuration of the chiral carbon in the side chain of 2,5-diketopiperazine derivatives, flexible analogues 3i-3iv were synthesized and analyzed. 1 was active against Fusarium oxysporum with an MIC value of 50 µg/mL. 7 and 8 showed excellent activity against human HeLa and HepG2 cells with IC50 values of 0.12-0.60 µM.

Synthesis and Optical Properties of Mn2+-Doped Amino Lead Halide Molecular Clusters Assisted by Chloride Ion.

Mn2+-doped amino lead halide molecular clusters (MCs) are synthesized using amine (e.g., n-octylamine, or butylamine) as passivating ligand and MnX2 (X = Cl or Br) as the Mn2+ doping source at room temperature. Their optical properties are investigated with UV-visible absorption, photoluminescence (PL), and PL excitation spectroscopy. The Mn2+ precursor plays a vital role in the synthesis of Mn2+-doped MCs. MnCl2 seems to facilitate the incorporation of Mn. The MnCl2 doping causes electronic absorption blue shift and leads to a spin-forbidden 4T1 → 6A1 Mn d-electron emission. With the help of time-resolved PL, Fourier transform infrared, and electron paramagnetic resonance results, a model is proposed to explain the formation mechanism. We suggest that Mn2+ doping replaces Pb2+ is assisted by Cl- ions that replace Br- ions. This study demonstrates the possibility of doping MCs and has important implications in gaining new fundamental insight into the growth mechanisms of perovskite nanostructures.

Enhancing Defect Tolerance with Ligands at the Surface of Lead Halide Perovskites.

High defect tolerance has been considered a primary reason for the long charge carrier lifetime and high photoluminescence quantum yield in bulk lead halide perovskites (LHPs). On the other hand, surface defects play a critical role in determining charge carrier dynamics and optical properties, especially for LHP nanocrystals and quantum dots. Understanding the nature of surface defects and developing strategy for their effective passivation are thus of strong interest. Focusing on a prototypical LHP, CsPbBr3, our work uses first-principles calculations to reveal that interstitial sites and antisites can have lower formation energies when they form at the surface while simultaneously creating deep trap states within the bandgap. Meanwhile, the formation of halide vacancies is energetically less favorable. On the basis of a new surface defect model, we demonstrate the explicit role of molecular ligands in passivating these defects, which eliminate trap states in favor of shallow states and enhance photoluminescence.

Diverse anti-inflammation and anti-cancer polyketides isolated from the endophytic fungi Alternaria sp. MG1.

Six new polyketides, alternaritins A-D [(±)-1-4] and isoxanalteric acid I (8), and 25 known Alternaria toxins were isolated from the culture of an endophytic fungi Alternaria sp. MG1. 3 is a rare fungal metabolite. 6 is a new natural product, and 5, 7, and 9 are known previously but their absolute configurations have not been determined. Three enantiomers [(±)-1, (±)-7, and (±)-15] were separated via chiral HPLC resolution. The structures of those polyketides (1-9) were elucidated by spectrometric analysis using MS and NMR. The absolute configurations were established using X-ray diffraction analysis and statistical comparative analysis of the experimental ECD and OR data, in conjunction with quantum mechanical calculations. All of the compounds were evaluated for their bioactivities. Known compound 27 exerted the most potent cytotoxic activities against HT-1080 and NCI-H1299 cell lines. The new compounds, 2 and 3, showed moderate inhibition on COX-2, while a pair of isomers, 8 and 9, exhibited medium activity on COX-2 and uropathogenic Escherichia coli.

State of the Art and Prospects for Halide Perovskite Nanocrystals.

Metal-halide perovskites have rapidly emerged as one of the most promising materials of the 21st century, with many exciting properties and great potential for a broad range of applications, from photovoltaics to optoelectronics and photocatalysis. The ease with which metal-halide perovskites can be synthesized in the form of brightly luminescent colloidal nanocrystals, as well as their tunable and intriguing optical and electronic properties, has attracted researchers from different disciplines of science and technology. In the last few years, there has been a significant progress in the shape-controlled synthesis of perovskite nanocrystals and understanding of their properties and applications. In this comprehensive review, researchers having expertise in different fields (chemistry, physics, and device engineering) of metal-halide perovskite nanocrystals have joined together to provide a state of the art overview and future prospects of metal-halide perovskite nanocrystal research.

Interplay between Perovskite Magic-Sized Clusters and Amino Lead Halide Molecular Clusters.

Recent progress has been made on the synthesis and characterization of metal halide perovskite magic-sized clusters (PMSCs) with ABX 3 composition (A = CH3NH3 + or Cs+, B = Pb2+, and X = Cl-, Br-, or I-). However, their mechanism of growth and structure is still not well understood. In our effort to understand their structure and growth, we discovered that a new species can be formed without the CH3NH3 + component, which we name as molecular clusters (MCs). Specifically, CH3NH3PbBr3 PMSCs, with a characteristic absorption peak at 424 nm, are synthesized using PbBr2 and CH3NH3Br as precursors and butylamine (BTYA) and valeric acid (VA) as ligands, while MCs, with an absorption peak at 402 nm, are synthesized using solely PbBr2 and BTYA, without CH3NH3Br. Interestingly, PMSCs are converted spontaneously overtime into MCs. An isosbestic point in their electronic absorption spectra indicates a direct interplay between the PMSCs and MCs. Therefore, we suggest that the MCs are precursors to the PMSCs. From spectroscopic and extended X-ray absorption fine structure (EXAFS) results, we propose some tentative structural models for the MCs. The discovery of the MCs is critical to understanding the growth of PMSCs as well as larger perovskite quantum dots (PQDs) or nanocrystals (PNCs).

Structural control and biomedical applications of plasmonic hollow gold nanospheres: A mini review.

Hollow gold nanospheres (HGNs) are core/shell structures with a dielectric material core, usually composed of solvent, and a gold metal shell. Such structures have two metal/dielectric interfaces to allow interaction between the gold metal with the interior and external dielectric environment. Upon illumination by light, HGNs exhibit unique surface plasmon resonance (SPR) properties compared to solid gold nanoparticles. Their SPR absorption/scattering can be tuned by changing their diameter, shell thicknesses, and surface morphologies. In addition to the low toxicity, easy functionalization, resistance to photobleaching, and sensitivity to changes in surrounding medium of gold, the enhanced surface-to-volume ratio and tunable SPR of HGNs make them highly attractive for different applications in the fields of sensing, therapy, and theranostics. In this article, we review recent progress on the synthesis and structural control of HGNs and applications of their SPR properties in biomedical sensing and theranostics. This article is categorized under: Diagnostic Tools > Biosensing Diagnostic Tools > in vitro Nanoparticle-Based Sensing Diagnostic Tools > in vivo Nanodiagnostics and Imaging.