Cu-Catalyzed Amination of Base-Sensitive Aryl Bromides and the Chemoselective N- and O-Arylation of Amino Alcohols.

We report a general and functional-group-tolerant method for the Cu-catalyzed amination of base-sensitive aryl bromides including substrates possessing acidic functional groups and small five-membered heteroarenes. The results presented herein substantially expand the scope of Cu-catalyzed C-N coupling reactions. The combination of L8, an anionic N1,N2-diarylbenzene-1,2-diamine ligand, along with the mild base NaOTMS leads to the formation of a stable yet reactive catalyst that resists deactivation from coordination to heterocycles or charged intermediates. This system enables the use of low catalyst and ligand loadings. Exploiting the differences in nucleophile deprotonation in C-O and C-N coupling reactions catalyzed by Cu·L8 we developed a method to chemoselectively N- and O-arylate a variety of amino alcohol substrates. Employing NaOt-Bu as the base resulted exclusively in C-O coupling when the amino alcohols featured primary alcohols and more hindered amines or aniline groups. Utilizing NaOTMS enabled the ability to override the steric-based selectivity of these reactions completely and exclusively promoted C-N coupling regardless of the structure of the amino alcohol. The ability to invert the observed chemoselectivity is distinct from previously described methods that require protecting group manipulations or rely entirely on steric effects to control reactivity. These results substantially improve the scope of Cu-catalyzed C-N coupling reactions using N1,N2-diarylbenzene-1,2-diamine ligands and introduce a new chemoselective method to arylate amino alcohols.

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.

Tuning Phonon Energies in Lanthanide-doped Potassium Lead Halide Nanocrystals for Enhanced Nonlinearity and Upconversion.

Optical applications of lanthanide-doped nanoparticles require materials with low phonon energies to minimize nonradiative relaxation and promote nonlinear processes like upconversion. Heavy halide hosts offer low phonon energies but are challenging to synthesize as nanocrystals. Here, we demonstrate the size-controlled synthesis of low-phonon-energy KPb2 X5 (X=Cl, Br) nanoparticles and the ability to tune nanocrystal phonon energies as low as 128 cm-1 . KPb2 Cl5 nanoparticles are moisture resistant and can be efficiently doped with lighter lanthanides. The low phonon energies of KPb2 X5 nanoparticles promote upconversion luminescence from higher lanthanide excited states and enable highly nonlinear, avalanche-like emission from KPb2 Cl5 : Nd3+ nanoparticles. The realization of nanoparticles with tunable, ultra-low phonon energies facilitates the discovery of nanomaterials with phonon-dependent properties, precisely engineered for applications in nanoscale imaging, sensing, luminescence thermometry and energy conversion.

Phosphine-Stabilized Hidden Ground States in Gold Clusters Investigated via a Aun(PH3)m Database.

Nanoclusters are promising materials for catalysis and sensing due to their large surface areas and unique electronic structures which can be tailored through composition, geometry, and chemistry. However, relationships correlating synthesis parameters directly to outcomes are limited. While previous computational studies have mapped the potential energy surface of specific systems of bare nanoclusters by generating and calculating the energies of reasonable structures, it is known that environmental ions and ligands crucially impact the final shape and size. In this work, phosphine-stabilized gold is considered as a test system and DFT calculations are performed for clusters with and without ligands, producing a database containing >10000 structures for Aun(PH3)m (n ≤ 12). We find that the ligation of phosphines affects the thermodynamic stability, bonding, and electronic structure of Au nanoclusters, specifically such that "hidden" ground state cluster geometries are stabilized that are dynamically unstable in the pure gold system. Further, the addition of phosphine introduces steric effects that induce a transition from planar to nonplanar structures at 4-5 Au atoms rather than up to 13-14 Au atoms, as previously predicted for bare clusters. This work highlights the importance of considering the ligand environment in the prediction of nanocluster morphology and functionality, which adds complexity as well as a rich opportunity for tunability.

Inverse size-dependent Stokes shift in strongly quantum confined CsPbBr3 perovskite nanoplates.

Colloidal semiconductor nanocrystals (NCs) are used as bright chromatic fluorophores for energy-efficient displays. We focus here on the size-dependent Stokes shift for CsPbBr3 nanocrystals. The Stokes shift, i.e., the difference between the wavelengths of absorption and emission maxima, is crucial for display application, as it controls the degree to which light is reabsorbed by the emitting material reducing the energetic efficiency. One major impediment to the industrial adoption of NCs is that slight deviations in manufacturing conditions may result in a wide dispersion of the product's properties. A data-driven analysis of over 2000 reactions comparing two data sets, one produced via standard colloidal synthesis and the other via high-throughput automated synthesis is discussed. We show that differences in the reaction conditions of colloidal CsPbBr3 nanocrystals yield nanocrystals with opposite Stokes shift size-dependent trends. These match the morphologies of two-dimensional nanoplatelets (NPLs) and nanocrystal cubes. The Stokes shift size dependence trend of NPLs and nanocubes is non-monotonic indicating different physics is at play for the two nanocrystal morphologies. For nanocrystals with cubic shape, with the increase of edge length, there is a significant decrease in Stokes shift values. However, for NPLs with the increase of thickness (1-4 ML), Stokes shift values will increase. The study emphasizes the transition from a spectroscopic point of view and relates the two Stokes shift trends to 2D and 0D exciton dimensionalities for the two morphologies. Our findings highlight the importance of CsPbBr3 nanocrystal morphology for Stokes shift prediction.

Using Machine Learning to Predict and Understand Complex Self-Assembly Behaviors of a Multicomponent Nanocomposite.

Blends of nanoparticles, polymers, and small molecules can self-assemble into optical, magnetic, and electronic devices with structure-dependent properties. However, the relationship between a multicomponent nanocomposite's formulation and its assembled structure is complex and cannot be predicted by theory. The blends can be strongly influenced by processing conditions, which can introduce non-equilibrium states. Currently, nanocomposite devices are designed through cycles of experimental trial and error. Machine learning (ML) methods are a compelling alternative because they can use existing datasets to map high-dimensional spaces. These methods do not rely on known relationships between parameters, so they are suited to complex systems without a solid theoretical foundation. Here, a dataset of 595 microscopy images of nanocomposite thin films is used to train a series of ML models. Correlations between the input and output parameters are examined, providing new insights into the system. Finally, the most successful ML model is used to predict the structures of new nanocomposite compositions. The results confirm that ML techniques can be used to improve the efficiency of nanocomposite device design. More broadly, the current study suggests some of the advantages and challenges associated with applying ML to complex systems.

AutoDetect-mNP: An Unsupervised Machine Learning Algorithm for Automated Analysis of Transmission Electron Microscope Images of Metal Nanoparticles.

The synthesis quality of artificial inorganic nanocrystals is most often assessed by transmission electron microscopy (TEM) for which high-throughput advances have dramatically increased both the quantity and information richness of metal nanoparticle (mNP) characterization. Existing automated data analysis algorithms of TEM mNP images generally adopt a supervised approach, requiring a significant effort in human preparation of labeled data that reduces objectivity, efficiency, and generalizability. We have developed an unsupervised algorithm AutoDetect-mNP for automated analysis of TEM images that objectively extracts morphological information on convex mNPs from TEM images based on their shape attributes, requiring little to no human input in the process. The performance of AutoDetect-mNP is tested on two data sets of bright field TEM images of Au nanoparticles with different shapes and further extended to palladium nanocubes and cadmium selenide quantum dots, demonstrating that the algorithm is quantitatively reliable and can thus serve as a generalizable measure of the morphology distributions of any mNP synthesis. The AutoDetect-mNP algorithm will aid in future developments of high-throughput characterization of mNPs and the future advent of time-resolved TEM studies that can investigate reaction mechanisms of mNP synthesis and reactivity.

Multilayer Diffraction Reveals That Colloidal Superlattices Approach the Structural Perfection of Single Crystals.

Colloidal superlattices are fascinating materials made of ordered nanocrystals, yet they are rarely called "atomically precise". That is unsurprising, given how challenging it is to quantify the degree of structural order in these materials. However, once that order crosses a certain threshold, the constructive interference of X-rays diffracted by the nanocrystals dominates the diffraction pattern, offering a wealth of structural information. By treating nanocrystals as scattering sources forming a self-probing interferometer, we developed a multilayer diffraction method that enabled the accurate determination of the nanocrystal size, interparticle spacing, and their fluctuations for samples of self-assembled CsPbBr3 and PbS nanomaterials. The multilayer diffraction method requires only a laboratory-grade diffractometer and an open-source fitting algorithm for data analysis. The average nanocrystal displacement of 0.33 to 1.43 Å in the studied superlattices provides a figure of merit for their structural perfection and approaches the atomic displacement parameters found in traditional crystals.

Elucidating the Weakly Reversible Cs-Pb-Br Perovskite Nanocrystal Reaction Network with High-Throughput Maps and Transformations.

Advances in automation and data analytics can aid exploration of the complex chemistry of nanoparticles. Lead halide perovskite colloidal nanocrystals provide an interesting proving ground: there are reports of many different phases and transformations, which has made it hard to form a coherent conceptual framework for their controlled formation through traditional methods. In this work, we systematically explore the portion of Cs-Pb-Br synthesis space in which many optically distinguishable species are formed using high-throughput robotic synthesis to understand their formation reactions. We deploy an automated method that allows us to determine the relative amount of absorbance that can be attributed to each species in order to create maps of the synthetic space. These in turn facilitate improved understanding of the interplay between kinetic and thermodynamic factors that underlie which combination of species are likely to be prevalent under a given set of conditions. Based on these maps, we test potential transformation routes between perovskite nanocrystals of different shapes and phases. We find that shape is determined kinetically, but many reactions between different phases show equilibrium behavior. We demonstrate a dynamic equilibrium between complexes, monolayers, and nanocrystals of lead bromide, with substantial impact on the reaction outcomes. This allows us to construct a chemical reaction network that qualitatively explains our results as well as previous reports and can serve as a guide for those seeking to prepare a particular composition and shape.

Cutaneous Lesions in Freshwater Turtles (Emydura macquarii krefftii and Myuchelys latisternum) in a Rainforest Creek in North Queensland, Australia.

Freshwater turtles inhabit most rivers and creeks on the east coast of Australia, but some species are only found in specific catchments, which makes them vulnerable to extinction. During annual fieldtrips to Alligator Creek, North Queensland, the resident population of Myuchelys latisternum and Emydura macquarii krefftii in a natural pond, just outside Bowling Green National Park, have been surveyed for a number of years and demographic data recorded against tagged turtles. Rounded, cutaneous lesions on individual animals were first noted in August 2016, three years after the first survey of the population. Turtles living in the upstream sections of the creek were not affected. An initial investigation into the cause of the lesions ruled out pollutants and although the bacterial communities appeared to be different on turtles with lesions, a causative agent was not identified. Attempts to isolate virus in culture was not successful and specific PCRs for ranavirus, papillomavirus, adenovirus and herpesvirus did not identify their presence. Blood biochemical parameters, body condition and activity levels were not significantly different between affected turtles and those without lesions. The turtles in this pond were monitored regularly over the following three years with 249 M. latisternum and 192 E. m. krefftii captured, tagged and released. The prevalence of the lesions fluctuated with season from 0 to 77 and 68% respectively, but did not vary significantly between species or sex in adults. There was a tendency for larger animals to be more likely to have lesions. The position of the lesions on the turtles was mostly on dorsal surfaces, distally on the legs and proximal on the tales of males, indicating that the initial lesion may have been associated with a behaviourally induced trauma. Recaptured animals (n = 43) during this period, provided records of lesion progression over time and while some healed up between capture events, others persisted for up to 24 months. Some turtles were repeatedly captured without lesions. Intra-species aggression associated with seasonal behaviours could potentially be the primary cause of skin trauma, followed by a secondary invasion of an unusual pathogen present in the environment.

Photoexcited Small Polaron Formation in Goethite (α-FeOOH) Nanorods Probed by Transient Extreme Ultraviolet Spectroscopy.

Small polaron formation limits the mobility and lifetimes of photoexcited carriers in metal oxides. As the ligand field strength increases, the carrier mobility decreases, but the effect on the photoexcited small polaron formation is still unknown. Extreme ultraviolet transient absorption spectroscopy is employed to measure small polaron formation rates and probabilities in goethite (α-FeOOH) crystalline nanorods at pump photon energies from 2.2 to 3.1 eV. The measured polaron formation time increases with excitation photon energy from 70 ± 10 fs at 2.2 eV to 350 ± 30 fs at 2.6 eV, whereas the polaron formation probability (85 ± 10%) remains constant. By comparison to hematite (α-Fe2O3), an oxide analogue, the role of ligand composition and metal center density in small polaron formation time is discussed. This work suggests that incorporating small changes in ligands and crystal structure could enable the control of photoexcited small polaron formation in metal oxides.

The Making and Breaking of Lead-Free Double Perovskite Nanocrystals of Cesium Silver-Bismuth Halide Compositions.

Replacing lead in halide perovskites is of great interest due to concerns about stability and toxicity. Recently, lead free double perovskites in which the unit cell is doubled and two divalent lead cations are substituted by a combination of mono- and trivalent cations have been synthesized as bulk single crystals and as thin films. Here, we study stability and optical properties of all-inorganic cesium silver(I) bismuth(III) chloride and bromide nanocrystals with the double perovskite crystal structure. The cube-shaped nanocrystals are monodisperse in size with typical side lengths of 8 to 15 nm. The absorption spectrum of the nanocrystals presents a sharp peak, which we assign to a direct bismuth s-p transition and not to a quantum confined excitonic transition. Using this spectroscopic handle combined with high-resolution transmission electron microscopy (TEM) based elemental analysis, we conduct stoichiometric studies at the single nanocrystal level as well as decomposition assays in solution and observe that Ag+ diffusion and coalescence is one of the pathways by which this material degrades. Drying the nanocrystals leads to self-assembly into ordered nanocrystal solids, and these exhibit less degradation than nanocrystals in solution. Our results demonstrate that Cs2AgBiX6 (X = Cl, Br) nanocrystals are a useful model system to study structure-function relationships in the search for stable nontoxic halide perovskites.

The role of intact oleosin for stabilization and function of oleosomes.

Lipid storage in plants is achieved among all plant species by formation of oleosomes, enclosing oil (triacylglycerides) in small subcellular droplets. Seeds are rich in this pre-emulsified oil to provide a sufficient energy reservoir for growing. The triacylglyceride core of the oleosomes is surrounded by a phospholipid monolayer containing densely packed proteins called oleosins. They are anchored in the triacylglycerides core with a hydrophobic domain, while the hydrophilic termini remain on the surface. These specialized proteins are expressed during seed development and maturation. Particularly, they play a major role in the stabilization and function of oleosomes. To better understand the importance of oleosins for oleosome stabilization, enzymatic digestion of oleosins was performed. This made it possible to compare and correlate changes in the molecular structure of oleosins and changing macroscopic properties of oleosomes. Tryptic digestion cleaves the hydrophilic part of the oleosins, which is accompanied by a loss of secondary structures as evidenced by Fourier-transform infrared and sum frequency generation spectra. After digestion, the ability of oleosins to stabilize oil-water or air-water interfaces was lost. The surface charge and the associated aggregation behavior of oleosomes are governed by interactions typical of proteins before digestion and by interactions typical of phospholipids after digestion.