Tuning the Chirality Evolution in Achiral Subnanometer Systems by Judicious Control of Molecule Interactions.

Chirality evolution from molecule levels to the nanoscale in an achiral system is a fundamental issue that remains undiscovered. Here, we report the assembly of polyoxometalate (POM) clusters into chiral subnanostructures in achiral systems by programmable single-molecule interactions. Driven by the competing binding of Ca2+ and surface ligands, POM assemblies would twist into helical nanobelts, nanorings, and nanotubes with tunable helicity. Chiral molecules can be used to differentiate the formation energies of chiral isomers and immobilize the homochiral isomer, where strong circular dichroism (CD) signals are obtained in both solutions and films. Chiral helical nanobelts can be used as circularly polarized light (CPL) photodetectors due to their distinct chiroptic responsivity for right and left CPL. By the fine-tuning of interactions at single-molecule levels, the morphology and CD spectra of helical assemblies can be precisely controlled, providing an atomic precision model for investigation of the structure-chirality relationship and chirality manipulation at the nanoscale.

Phase-Controlled Synthesis of Nickel-Iron Nitride Nanocrystals Armored with Amorphous N-Doped Carbon Nanoparticles Nanocubes for Enhanced Overall Water Splitting.

Transition metal nitrides (TMNs) nanostructures possess distinctive electronic, optical, and catalytic properties, showing great promise to apply in clean energy, optoelectronics, and catalysis fields. Nonetheless, phase-regulation of NiFe-bimetallic nitrides nanocrystals or nanohybrid architectures confronts challenges and their electrocatalytic overall water splitting (OWS) performances are underexplored. Herein, novel pure-phase Ni2+ x Fe2- x N nanocrystals armored with amorphous N-doped carbon (NC) nanoparticles nanocubes (NPNCs) are obtained by controllable nitridation of NiFe-Prussian-blue analogues derived oxides/NC NPNCs under Ar/NH3 atmosphere. Such Ni2+ x Fe2- x N/NC NPNCs possess mesoporous structures and show enhanced electrocatalytic activity in 1 m KOH electrolyte with the overpotential of 101 and 270 mV to attain 10 and 50 mA cm-2 current toward hydrogen and oxygen evolution reactions, outperforming their counterparts (mixed-phase NiFe2 O4 /Ni3 FeN/NC and NiFe oxides/NC NPNCs). Remarkably, utilizing them as bifunctional catalysts, the assembled Ni2+ x Fe2- x N/NC||Ni2+ x Fe2- x N/NC electrolyzer only needs 1.51 V cell voltage for driving OWS to approach 10 mA cm-2 water-splitting current, exceeding their counterparts and the-state-of-art reported bifunctional catalysts-based devices, and Pt/C||IrO2 couples. Additionally, the Ni2+ x Fe2- x N/NC||Ni2+ x Fe2- x N/NC manifests excellent durability for OWS. The findings presented here may spur the development of advanced TMNs nanostructures by combining phase, structure engineering, and hybridization strategies and stimulate their applications toward OWS or other clean energy fields.

CsPbX3 -ITO (X = Cl, Br, I) Nano-Heterojunctions: Voltage Tuned Positive to Negative Photoresponse.

All-Inorganic perovskite CsPbX3 (X = Cl, Br, I) quantum dots (QDs) have attracted tremendous attention in the past few years for their appealing performance in optoelectronic applications. Major properties of CsPbX3 QDs include the positive photoconductivity (PPC) and the defect tolerance of the in-band trap states. Here it is reported that when hybridizing CsPbX3 QDs with indium tin oxide (ITO) nanocrystals to form CsPbX3 -ITO nano-heterojunctions (NHJs), a voltage tuned photoresponse-from PPC to negative photoconductivity (NPC) transform-is achieved in lateral drain-source structured ITO/CsPbX3 -ITO-NHJs/ITO devices. A model combining exciton, charge separation, transport, and most critical the voltage driven electron filling of the in-band trap states with drain-source voltage (VDS ) above a threshold, is proposed to understand this unusual PPC-NPC transform mechanism, which is different from that of any known nanomaterial system. This finding exhibits potentials for developing devices such as photodetectors, optoelectronic switches, and memories.

Heterostructural CsPbX3-PbS (X = Cl, Br, I) Quantum Dots with Tunable Vis-NIR Dual Emission.

Perovskite and chalcogenide quantum dots (QDs) are important nano semiconductors. It has been a challenge to synthesize heterostructural QDs combining perovskite and chalcogenide with tailorable photoelectronic properties. In this report, heterostructural CsPbX3-PbS (X = Cl, Br, I) QDs were successfully synthesized via a room temperature in situ transformation route. The CsPbX3-PbS QDs show a tunable dual emission feature with the visible and near-infrared (NIR) photoluminescence (PL) corresponding to CsPbX3 and PbS, respectively. Typically, the formation and evolution of the heterostructural CsPbBr3-PbS QDs with reaction time was investigated. Femtosecond transient absorption spectroscopy (TAS) was applied to illuminate the exciton dynamics in CsPbBr3-PbS QDs. The mild synthetic method and TAS proved perovskite to PbS energy transfer may pave the way toward highly efficient QD photovoltaic and optoelectronic devices.

Comparison of quantum dot-binding protein tags: affinity determination by ultracentrifugation and FRET.

BACKGROUND: Hybrid complexes of proteins and colloidal semiconductor nanocrystals (quantum dots, QDs) are of increasing interest in various fields of biochemistry and biomedicine, for instance for biolabeling or drug transport. The usefulness of protein-QD complexes for such applications is dependent on the binding specificity and strength of the components. Often the binding properties of these components are difficult and time consuming to assess. METHODS: In this work we characterized the interaction between recombinant light harvesting chlorophyll a/b complex (LHCII) and CdTe/CdSe/ZnS QDs by using ultracentrifugation and fluorescence resonance energy transfer (FRET) assay experiments. Ultracentrifugation was employed as a fast method to compare the binding strength between different protein tags and the QDs. Furthermore the LHCII:QD stoichiometry was determined by separating the protein-QD hybrid complexes from unbound LHCII via ultracentrifugation through a sucrose cushion. RESULTS: One trimeric LHCII was found to be bound per QD. Binding constants were evaluated by FRET assays of protein derivatives carrying different affinity tags. A new tetra-cysteine motif interacted more strongly (Ka=4.9±1.9nM(-1)) with the nanoparticles as compared to a hexahistidine tag (His6 tag) (Ka~1nM(-1)). CONCLUSION: Relative binding affinities and binding stoichiometries of hybrid complexes from LHCII and quantum dots were identified via fast ultracentrifugation, and binding constants were determined via FRET assays. GENERAL SIGNIFICANCE: The combination of rapid centrifugation and fluorescence-based titration will be useful to assess the binding strength between different types of nanoparticles and a broad range of proteins.

Exciton coupling of surface complexes on a nanocrystal surface.

Exciton coupling may arise when chromophores are brought into close spatial proximity. Herein the intra-nanocrystal exciton coupling of the surface complexes formed by coordination of 8-hydroxyquinoline to ZnS nanocrystals (NCs) is reported. It is studied by absorption, photoluminescence (PL), PL excitation (PLE), and PL lifetime measurements. The exciton coupling of the surface complexes tunes the PL color and broadens the absorption and PLE windows of the NCs, and thus is a potential strategy for improving the light-harvesting efficiency of NC solar cells and photocatalysts.

Nonsteaming method improves the nutritional value and utilization efficiency of silkworm artificial diets.

Artificial diets for silkworms overcome the seasonal limitations of traditional rearing methods with fresh mulberry leaves. However, the current wet artificial diets, steamed at high temperatures, are not favored by silkworms, and they are cumbersome and challenging to preserve. These conditions adversely affected the development of artificial diet-based sericulture production. In this study, we disinfected dry powder diets with radiation and added distilled water without steaming before use. Then, the nutritional value of finished diets and their impact on silkworm development was assessed. Compared with steamed diets, nonsteamed diets were more attractive to silkworms. Chemical assays showed significantly more essential nutrients for silkworms, including l-ascorbic acid, vitamin B1, vitamin B2, and urease in nonsteamed diets than in steamed diets. Feeding fifth-instar silkworm larvae with nonsteamed diets significantly improved the ammonia utilization efficiency of the diet and increased the cocoon shell rate and diet/silk protein conversion efficiency by 5.9% and 13.3%, respectively. When fed with nonsteamed diets, the abundance of aerobic microorganisms in silkworm intestines increased and the abundance of pathogenic bacteria decreased. Furthermore, the vitality of the silkworm, measured by the dead worm cocoon rate, significantly improved by 16.90%. In summary, preparing sterile wet diets without high-temperature steaming effectively improved the nutritional value of the diet and enhanced silkworm growth.

Nucleation-mediated growth of chiral 3D organic-inorganic perovskite single crystals.

Although their zero- to two-dimensional counterparts are well known, three-dimensional chiral hybrid organic-inorganic perovskite single crystals have remained difficult because they contain no chiral components and their crystal phases belong to centrosymmetric achiral point groups. Here we report a general approach to grow single-crystalline 3D lead halide perovskites with chiroptical activity. Taking MAPbBr3 (MA, methylammonium) perovskite as a representative example, whereas achiral MAPbBr3 crystallized from precursors in solution by inverse temperature crystallization method, the addition of micro- or nanoparticles as nucleating agents promoted the formation of chiral crystals under a near equilibrium state. Experimental characterization supported by calculations showed that the chirality of the 3D APbX3 (where A is an ammonium ion and X is Cl, Br or mixed Cl-Br or Br-I) perovskites arises from chiral patterns of the A-site cations and their interaction with the [PbX6]4- octahedra in the perovskite structure. The chiral structure obeys the lowest-energy principle and thereby thermodynamically stable. The chiral 3D hybrid organic-inorganic perovskites served in a circularly polarized light photodetector prototype successfully.

Bio serves nano: biological light-harvesting complex as energy donor for semiconductor quantum dots.

Light-harvesting complex (LHCII) of the photosynthetic apparatus in plants is attached to type-II core-shell CdTe/CdSe/ZnS nanocrystals (quantum dots, QD) exhibiting an absorption band at 710 nm and carrying a dihydrolipoic acid coating for water solubility. LHCII stays functional upon binding to the QD surface and enhances the light utilization of the QDs significantly, similar to its light-harvesting function in photosynthesis. Electronic excitation energy transfer of about 50% efficiency is shown by donor (LHCII) fluorescence quenching as well as sensitized acceptor (QD) emission and corroborated by time-resolved fluorescence measurements. The energy transfer efficiency is commensurable with the expected efficiency calculated according to Förster theory on the basis of the estimated donor-acceptor separation. Light harvesting is particularly efficient in the red spectral domain where QD absorption is relatively low. Excitation over the entire visible spectrum is further improved by complementing the biological pigments in LHCII with a dye attached to the apoprotein; the dye has been chosen to absorb in the "green gap" of the LHCII absorption spectrum and transfers its excitation energy ultimately to QD. This is the first report of a biological light-harvesting complex serving an inorganic semiconductor nanocrystal. Due to the charge separation between the core and the shell in type-II QDs the presented LHCII-QD hybrid complexes are potentially interesting for sensitized charge-transfer and photovoltaic applications.

UV-vis-IR Broad Spectral Photodetectors Based on VO2-ZnO Nanocrystal Films.

As a narrow band semiconductor at room temperature and a metallic material above ∼68 °C, functional VO2 films are widely investigated for smart windows, whereas their potential for ultraviolet-visible-infrared (UV-vis-IR) broad spectral photodetectors has not been efficiently studied. In this report, photodetectors based on VO2-ZnO nanocrystal composite films were prepared by nanocrystal-mist (NC-mist) deposition. An enhanced photodetection switching ratio was achieved covering the ultraviolet to infrared wavelength. Due to the synergetic effect of nanosize, surface, phase transition, percolation threshold, and the band structure of the heterojunction, the transfer and transport of photogenerated carriers modulate the device performance. This study probes new chances of applying VO2-semiconductor-based nanocomposites for broad spectral photodetectors.

Assembly and separation of semiconductor quantum dot dimers and trimers.

Repeated precipitation of colloidal semiconductor quantum dots (QD) from a good solvent by adding a poor solvent leads to an increasing number of QD oligomers after redispersion in the good solvent. By using density gradient ultracentrifugation we have been able to separate QD monomer, dimer, and trimer fractions from higher oligomers in such solutions. In the corresponding fractions QD dimers and trimers have been enriched up to 90% and 64%, respectively. Besides directly coupled oligomers, QD dimers and trimers were also assembled by linkage with a rigid terrylene diimide dye (TDI) and separated again by ultracentrifugation. High-resolution transmission electron micrographs show that the interparticle distances are clearly larger than those for directly coupled dots proving that the QDs indeed are cross-linked by the dye. Moreover, energy transfer from the QDs to the TDI "bridge" has been observed. Individual oligomers (directly coupled or dye-linked) can be readily deposited on a substrate and studied simultaneously by scanning force and optical microscopy. Our simple and effective scheme is applicable to a wide range of ligand stabilized colloidal nanoparticles and opens the way to a detailed study of electronic coupling in, e.g., QD molecules.

Noncontact evaluation of full elastic constants of perovskite MAPbBr3 via Photoacoustic eigen-spectrum analysis in one test.

Elasticity is one basic property of hybrid organic-inorganic perovskites. It highly relates to many fundamental processes in solid physics. The investigation of elasticity is of interest not only to explore the intrinsic properties of a material, but also to improve their potential application performance. In this study, we predict photoacoustic eigen-spectrum (PAES) of single crystal. Then by solving the inverse problem of the generation of PAES, we propose a noncontact method to determine a complete set of elastic constants of single crystal in one test. Experiments confirm the proposed method accurately determines all elastic constants of MAPbBr3. Since this method is totally noncontact and does not require multiple specimens cutting along different crystal axes, it could be more competent for rare, tiny and brittle specimen, or when the specimen is immersed in turbid or opaque medium. Benefitting from these superiorities, the proposed method might be found prominent values in materials science and applications.

Continuous preparation of antimony nanocrystals with near infrared photothermal property by pulsed laser ablation in liquids.

Antimony nanocrystals (Sb NCs) are of interest in energy storage, catalysis and cancer therapy for its special physical, chemical and biomedical properties. However, methodology challenges still remain in preparation of colloidal Sb NCs, due to the restricted reaction solution systems, high temperature and time costing for common routes. Herein, size controllable colloidal Sb NCs were continuously prepared by pulsed laser ablation of Sb target in different solvents, owning to the metal nanodroplet explosive ejection and thermal evaporation mechanisms. These well dispersed and stable Sb NCs showed excellent photothermal property in the near-infrared-II window.

Size- and surface-determined transformations: from ultrathin InOOH nanowires to uniform c-In2O3 nanocubes and rh-In2O3 nanowires.

Ultrathin InOOH nanowires with a diameter of approximately 2 nm and a length up to approximately 200 nm have been synthesized by a hydrolysis reaction in a solution system. Their transformations to c-In(2)O(3) nanocrystals and rh-In(2)O(3) nanowires have been investigated. A dissolution-recrystallization (in solution) or size-related decomposition-recrystallization (in air) mechanism is indicated for the former transformation; the size- and surface-determined transformation is proposed for the latter. These results will help to understand and control the phase stability and transformation concerning the nanodimension and surface restrictions, especially for ultrathin nanowires.

Monodisperse F-substituted hydroxyapatite single-crystal nanotubes with amphiphilic surface properties.

Uniform F-substituted HAp nanotubes with different aspect ratios and surface properties have been successfully prepared via a hydrothermal synthetic route. A small amount of 3% F doping into HAp can lead to the formation of nanotubes. This study will provide not only novel building blocks for the construction of artificial bones or other composites with novel mechanical properties but also a new strategy for the controlled growth of inorganic nanotubes.

Size effects in the oriented-attachment growth process: the case of Cu nanoseeds.

Size effects in the oriented-attachment (OA) growth process of Cu nanoseeds were found. Monodispersed Cu nanoseeds with average diameters of 2.2, 3.4, and 5.2 nm were controllably synthesized by the reduction of copper acetate in a boiling solvent and using dodecanethiol (DT) as a stabilizer and sulfur source of sulfide. These Cu nanoseeds were then treated under solvothermal conditions. When the diameters of Cu nanoseeds were smaller than 5 nm, Cu(2)S nanorods with lengths of approximately 30-100 nm and diameters of approximately 2-4 nm were obtained at lower temperatures, and Cu(2)S nanodisks with diameters of approximately 6-13 nm and thicknesses of approximately 2-4 nm were obtained at higher temperatures. Once the diameter of Cu nanoseeds was larger than 5 nm, only irregular particles were obtained, regardless of other conditions. The uniformity, which related to the density of DT on the surface of Cu nanoseeds, was the key for success of self-assembly of the final nanocrystals. High-resolution transmission electron microscopy images demonstrated that these nanorods, nanodisks, and particles were formed by an OA process of Cu nanoseeds into 1D, 2D, and 3D aggregates, which recrystallized into single crystals.

Shape-control of CeF3 nanocrystals by doping polyoxometalates: syntheses, characterization and tunable photoluminescence.

A series of CeF3 nanocrystals with uniform morphologies have been synthesized by introducing various polyoxometalates as dopants and shape modifiers. The results indicate that the shape and photoluminescence of the CeF3 nanocrystals could be finely tuned by changing the component and amount of the polyoxometalates.

SnO2 quantum dots and quantum wires: controllable synthesis, self-assembled 2D architectures, and gas-sensing properties.

SnO2 quantum dots (QDs) and ultrathin nanowires (NWs) with diameters of approximately 0.5-2.5 and approximately 1.5-4.5 nm, respectively, were controllably synthesized in a simple solution system. They are supposed to be ideal models for studying the continuous evolution of the quantum-confinement effect in SnO2 1D --> 0D systems. The observed transition from strong to weak quantum confinement in SnO2 QDs and ultrathin NWs is interpreted through the use of the Brus effective-mass approximation and the Nosaka finite-depth well model. Photoluminescence properties that were coinfluenced by size effects, defects (oxygen vacancies), and surface capping are discussed in detail. With the SnO2 QDs as building blocks, various 2D porous structures with ordered hexagonal, distorted hexagonal, and square patterns were prepared on silicon-wafer surfaces and exhibited optical features of 2D photonic crystals and enhanced gas sensitivity.

Synthesis and spectroscopic properties of silver-fluorescein co-doped phosphotungstate hollow spheres.

Herein, silver-fluorescein co-doped phosphotungstate hollow spheres have been successfully synthesized using a chemical precipitation method by introducing silver ions and fluorescein at room temperature. This hybrid nanomaterial possesses a uniform structure, exhibiting a strong emission spectrum with a peak centered at 517 nm. It is anticipated that silver and fluorescein as functionalized dopants for the phosphotungstate hollow sphere structure would provide this material with multiple properties. The control experiments indicate that fluorescein plays a key role in the formation of the hollow sphere structure. Hence, the co-doping strategy is proposed to be a general method to endow polyoxometalate nanomaterials with new structures, new functions and potential applications in bioimaging, fluorescent chemical sensors, and antibacterial or optoelectronic devices.

Low Power Consumption Red Light-Emitting Diodes Based on Inorganic Perovskite Quantum Dots under an Alternating Current Driving Mode.

Inorganic perovskites have emerged as a promising candidate for light-emitting devices due to their high stability and tunable band gap. However, the power consumption and brightness have always been an issue for perovskite light-emitting diodes (PeLEDs). Here, we improved the luminescence intensity and decreased the current density of the PeLEDs based on CsPbI3 quantum dots (QDs) and p-type Si substrate through an alternating current (AC) driving mode. For the different driving voltage modes (under a sine pulsed bias or square pulsed bias), a frequency-dependent electroluminescent (EL) behavior was observed. The devices under a square pulsed bias present a stronger EL intensity under the same voltage due to less thermal degradation at the interface. The red PeLEDs under a square pulsed bias driving demonstrate that the EL intensity drop-off phenomenon was further improved, and the integrated EL intensity shows the almost linear increase with the increasing driving voltage above 8.5 V. Additionally, compared to the direct current (DC) driving mode, the red PeLEDs under the AC condition exhibit higher operating stability, which is mainly due to the reducing accumulated charges in the devices. Our work provides an effective approach for obtaining strong brightness, low power consumption, and high stability light-emitting devices, which will exert a profound influence on coupling LEDs with household power supplies directly.