Local Structure in Crystalline, Glass and Melt States of a Hybrid Metal Halide Perovskite.

The pursuit of structure-property relationships in crystalline metal halide perovskites (MHPs) has yielded an unprecedented combination of advantageous characteristics for wide-ranging optoelectronic applications. While crystalline MHP structures are readily accessible through diffraction-based structure refinements, providing a clear view of associated long-range ordering, the local structures in more recently discovered glassy MHP states remain unexplored. Herein, we utilize a combination of Raman spectroscopy, solid-state nuclear magnetic resonance (NMR), Fourier transform infrared spectroscopy, in situ X-ray diffraction (XRD) and pair distribution function (PDF) analysis to investigate the coordination environment in crystalline, glass and melt states of the 2D MHP [(S)-(-)-1-(1-naphthyl)ethylammonium]2PbBr4. While crystalline SNPB shows polarization-dependent Raman spectra, the glassy and melt states exhibit broad features and lack polarization dependence. Solid-state NMR reveals disordering at the organic-inorganic interface of the glass due to significant spatial disruption in the tethering ammonium groups and the corresponding dihedral bond angles connecting the naphthyl and ammonium groups, while still preserving substantial naphthyl group registry and remnants of the layering from the crystalline state (deduced from XRD analysis). Moreover, PDF analysis demonstrates the persistence of corner-sharing PbBr6 octahedra in the inorganic framework of the melt/glass phases, but with a loss of structural coherence over length scales exceeding approximately one octahedron due to disorder in the inter- and intraoctahedra bond angles/lengths. These findings deepen our understanding of diverse MHP structural motifs and how structural alterations within the MHP glass affect properties, offering potential for advancing next-generation phase change materials and devices.

Structural Evolution and Photoluminescence Quenching across the FASnI3-xBrx (x = 0-3) Perovskites.

One of the primary methods for band gap tuning in metal halide perovskites has been halide (I/Br) mixing. Despite widespread usage of this type of chemical substitution in perovskite photovoltaics, there is still little understanding of the structural impacts of halide alloying, with the assumption being the formation of ideal solid solutions. The FASnI3-xBrx (x = 0-3) family of compounds provides the first example where the assumption breaks down, as the composition space is broken into two unique regimes (x = 0-2.9; x = 2.9-3) based on their average structure with the former having a 3D and the latter having an extended 3D (pseudo 0D) structure. Pair distribution function (PDF) analyses further suggest a dynamic 5s2 lone pair expression resulting in increasing levels of off-centering of the central Sn as the Br concentration is increased. These antiferroelectric distortions indicate that even the x = 0-2.9 phase space behaves as a nonideal solid-solution on a more local scale. Solid-state NMR confirms the difference in local structure yielding greater insight into the chemical nature and local distributions of the FA+ cation. In contrast to the FAPbI3-xBrx series, a drastic photoluminescence (PL) quenching is observed with x ≥ 1.9 compounds having no observable PL. Our detailed studies attribute this quenching to structural transitions induced by the distortions of the [SnBr6] octahedra in response to stereochemically expressed lone pairs of electrons. This is confirmed through density functional theory, having a direct impact on the electronic structure.

An enumerative pre-processing approach for retinopathy severity grading using an interpretable classifier: a comparative study.

BACKGROUND: Diabetic retinopathy (DR) is a serious eye complication that results in permanent vision damage. As the number of patients suffering from DR increases, so does the delay in treatment for DR diagnosis. To bridge this gap, an efficient DR screening system that assists clinicians is required. Although many artificial intelligence (AI) screening systems have been deployed in recent years, accuracy remains a metric that can be improved. METHODS: An enumerative pre-processing approach is implemented in the deep learning model to attain better accuracies for DR severity grading. The proposed approach is compared with various pre-trained models, and the necessary performance metrics were tabulated. This paper also presents the comparative analysis of various optimization algorithms that are utilized in the deep network model, and the results were outlined. RESULTS: The experimental results are carried out on the MESSIDOR dataset to assess the performance. The experimental results show that an enumerative pipeline combination K1-K2-K3-DFNN-LOA shows better results when compared with other combinations. When compared with various optimization algorithms and pre-trained models, the proposed model has better performance with maximum accuracy, precision, recall, F1 score, and macro-averaged metric of 97.60%, 94.60%, 98.40%, 94.60%, and 0.97, respectively. CONCLUSION: This study focussed on developing and implementing a DR screening system on color fundus photographs. This artificial intelligence-based system offers the possibility to enhance the efficacy and approachability of DR diagnosis.

Chemical Behavior and Local Structure of the Ruddlesden-Popper and Dion-Jacobson Alloyed Pb/Sn Bromide 2D Perovskites.

The alloyed lead/tin (Pb/Sn) halide perovskites have gained significant attention in the development of tandem solar cells and other optoelectronic devices due to their widely tunable absorption edge. To gain a better understanding of the intriguing properties of Pb/Sn perovskites, such as their anomalous bandgap's dependence on stoichiometry, it is important to deepen the understanding of their chemical behavior and local structure. Herein, we investigate a series of two-dimensional Ruddlesden-Popper (RP) and Dion-Jacobson (DJ) phase alloyed Pb/Sn bromide perovskites using butylammonium (BA) and 3-(aminomethyl)pyridinium (3AMPY) as the spacer cations: (BA)2(MA)n-1PbxSnn-xBr3n+1 (n = 1-3) and (3AMPY)(MA)n-1PbxSnn-xBr3n+1 (n = 1-3) through a solution-based approach. Our results show that the ratio and site preference of Pb/Sn atoms are influenced by the layer thickness (n) and spacer cations (A'), as determined by single-crystal X-ray diffraction. Solid-state 1H, 119Sn, and 207Pb NMR spectroscopy analysis shows that the Pb atoms prefer the outer layers in n = 3 members: (BA)2(MA)PbxSnn-xBr10 and (3AMPY)(MA)PbxSnn-xBr10. Layered 2D DJ alloyed Pb/Sn bromide perovskites (3AMPY)(MA)n-1PbxSnn-xBr3n+1 (n = 1-3) demonstrate much narrower optical band gaps, lower energy PL emission peaks, and longer carrier lifetimes compared to those of RP analogs. Density functional theory calculations suggest that Pb-rich alloys (Pb:Sn ∼4:1) for n = 1 compounds are thermodynamically favored over 50:50 (Pb:Sn ∼1:1) compositions. From grazing-incidence wide-angle X-ray scattering (GIWAXS), we see that films in the RP phase orient parallel to the substrate, whereas for DJ cases, random orientations are observed relative to the substrate.

Boron Adsorption Kinetics of Microcrystalline Cellulose and Polymer Resin.

Tailoring boron-polysaccharide interactions is an important strategy for developing functional soft materials such as hydrogels, fire retardants, and sorbents for environmental remediation, for example, using lignocellulosic biomass. For such applications to be realized, it is paramount to understand the adsorption kinetics of borate anions on cellulose and their local structures. Here, the kinetic aspects of boron adsorption by microcrystalline cellulose, lignin, and polymeric resin are investigated and compared. Borate anions interact with the vicinal diols in the glucopyranoside moieties of cellulose to yield chemisorbed boron chelate complexes. In contrast to cellulose, technical lignin contains fewer cis-vicinal diols, and it does not have a tendency to form such chelate complexes upon treatment with the aqueous boric acid solution. The formation kinetics and stability of these chelate complexes strongly depend on nanoscale structures, as well as reaction conditions such as pH and concentration of the sorbate and sorbent. Specifically, insights into the distinct boron adsorption sites were obtained by solid-state one-dimensional (1D) 11B magic-angle spinning NMR and the local structures and intermolecular interactions in the vicinities of boron chelate complexes are elucidated by analyzing two-dimensional (2D) 1H-13C and 11B-1H heteronuclear correlation NMR spectra. The total boron adsorption capacity of cellulose is estimated to be in the 1.3-3.0 mg range per gram of sorbent, which is lower than the boron adsorption capacity of a polystyrene-based resin, ∼17.2 mg of boron per gram of Amberlite IRA 743. Our study demonstrates that the local backbone and side chain flexibility as well as the structures of polyol groups play a significant role in determining the kinetic and thermodynamic stability of chelate complexes, yielding to different boron adsorption capabilities of lignocellulosic polymers.

Porous and Water Stable 2D Hybrid Metal Halide with Broad Light Emission and Selective H2 O Vapor Sorption.

In this work we report a strategy for generating porosity in hybrid metal halide materials using molecular cages that serve as both structure-directing agents and counter-cations. Reaction of the [2.2.2] cryptand (DHS) linker with PbII in acidic media gave rise to the first porous and water-stable 2D metal halide semiconductor (DHS)2 Pb5 Br14 . The corresponding material is stable in water for a year, while gas and vapor-sorption studies revealed that it can selectively and reversibly adsorb H2 O and D2 O at room temperature (RT). Solid-state NMR measurements and DFT calculations verified the incorporation of H2 O and D2 O in the organic linker cavities and shed light on their molecular configuration. In addition to porosity, the material exhibits broad light emission centered at 617 nm with a full width at half-maximum (FWHM) of 284 nm (0.96 eV). The recorded water stability is unparalleled for hybrid metal halide and perovskite materials, while the generation of porosity opens new pathways towards unexplored applications (e.g. solid-state batteries) for this class of hybrid semiconductors.

Combining heteronuclear correlation NMR with spin-diffusion to detect relayed Cl-H-H and N-H-H proximities in molecular solids.

Analysis of short-to-intermediate range intermolecular interactions offers a great way of characterizing the solid-state organization of small molecules and materials. This can be achieved by two-dimensional (2D) homo- and heteronuclear correlation NMR spectroscopy, for example, by carrying out experiments at high magnetic fields in conjunction with fast magic-angle spinning (MAS) techniques. But, detecting 2D peaks for heteronuclear dipolar coupled spin pairs separated by greater than 3 Å is not always straightforward, particularly when low-gamma quadrupolar nuclei are involved. Here, we present a 2D correlation NMR experiment that combines the advantages of heteronuclear-multiple quantum coherence (HMQC) and proton-based spin-diffusion (SD) pulse sequences using radio-frequency-driven-recouping (RFDR) to probe inter and intramolecular 1H-X (X = 14N, 35Cl) interactions. This experiment can be used to acquire 2D 1H{X}-HMQC filtered 1H-1H correlation as well as 2D 1H-X HMQC spectra. Powder forms of dopamine·HCl and l-histidine·HCl·H2O are characterized at high fields (21.1 T and 18.8 T) with fast MAS (60 kHz) using the 2D HMQC-SD-RFDR approach. Solid-state NMR results are complemented with NMR crystallography analyses using the gauge-including projector augmented wave (GIPAW) approach. For histidine·HCl·H2O, 2D peaks associated with 14N-1H-1H and 35Cl-1H-1H distances of up to 4.4 and 3.9 Å have been detected. This is further corroborated by the observation of 2D peaks corresponding to 14N-1H-1H and 35Cl-1H-1H distances of up to 4.2 and 3.7 Å in dopamine·HCl, indicating the suitability of the HMQC-SD-RFDR experiments for detecting medium-range proximities in molecular solids.

Tunable Broad Light Emission from 3D "Hollow" Bromide Perovskites through Defect Engineering.

Hybrid halide perovskites consisting of corner-sharing metal halide octahedra and small cuboctahedral cages filled with counter cations have proven to be prominent candidates for many high-performance optoelectronic devices. The stability limits of their three-dimensional perovskite framework are defined by the size range of the cations present in the cages of the structure. In some cases, the stability of the perovskite-type structure can be extended even when the counterions violate the size and shape requirements, as is the case in the so-called "hollow" perovskites. In this work, we engineered a new family of 3D highly defective yet crystalline "hollow" bromide perovskites with general formula (FA)1-x(en)x(Pb)1-0.7x(Br)3-0.4x (FA = formamidinium (FA+), en = ethylenediammonium (en2+), x = 0-0.44). Pair distribution function analysis shed light on the local structural coherence, revealing a wide distribution of Pb-Pb distances in the crystal structure as a consequence of the Pb/Br-deficient nature and en inclusion in the lattice. By manipulating the number of Pb/Br vacancies, we finely tune the optical properties of the pristine FAPbBr3 by blue shifting the band gap from 2.20 to 2.60 eV for the x = 0.42 en sample. A most unexpected outcome was that at x> 0.33 en incorporation, the material exhibits strong broad light emission (1% photoluminescence quantum yield (PLQY)) that is maintained after exposure to air for more than a year. This is the first example of strong broad light emission from a 3D hybrid halide perovskite, demonstrating that meticulous defect engineering is an excellent tool for customizing the optical properties of these semiconductors.

Selective detection of active pharmaceutical ingredients in tablet formulations using solid-state NMR spectroscopy.

Atomic-level characterization of active pharmaceutical ingredients (API) is crucial in pharmaceutical industry because APIs play an important role in physicochemical properties of drug formulations. However, the analysis of targeted APIs in intact tablet formulations is less straightforward due to the coexistence of excipients as major components and different APIs at dilute concentrations (often below 10 â€‹wt% loading). Although solid-state (ss) NMR spectroscopy is widely used to investigate short-range order, polymorphism, and pseudo-polymorphism in neat pharmaceutical compounds, the analysis of complex drug formulations is often limited by overlapped signals that originate from structurally different APIs and excipients. In particular, such examples are frequently encountered in the analysis of 1H ssNMR spectra of pharmaceutical formulations. While the high-resolution in 1H ssNMR spectra can be attained by, for example, high magnetic fields accompanied by fast magic-angle spinning (MAS) approaches, the spectral complexity associated with the mixtures of compounds hinders the accurate determination of chemical shifts and through-space proximities. Here we propose a fast MAS (70 â€‹kHz) NMR experiment for the selective detection of 1H signals associated with an API from a severely overlapped NMR spectrum of a tablet formulation. Spectral simplification is achieved by combining (i) symmetry-based dipolar recoupling (SR412) rotational-echo saturation-pulse double-resonance (RESPDOR) with phase-modulate (PM) saturation pulses, (ii) radio frequency-driven recoupling (RFDR), and (iii) double-quantum excitation using Back-to-Back (BaBa) pulse sequence elements. First, 1H sites in close proximities to 14N nuclei of an API are excited using a PM-S-RESPDOR sequence, and simultaneously, the other unwanted 1H signals of excipients are suppressed. Then, 1H magnetization transfer to adjacent 1H sites in the API is achieved by spin diffusion process using a RFDR sequence, which polarizes to 1H sites within the crystalline API regions of the drug formulation. Next, a PM-S-RESPDOR-RFDR sequence is combined with a Back-to-Back (BaBa) sequence to elucidate local-structures and 1H-1H proximities of the API in a dosage form. The PM-S-RESPDOR-RFDR-BaBa experiment is employed in one- (1D) and two-dimensional (2D) versions to selectively detect the 1H ssNMR spectrum of l-cysteine (10.6 â€‹wt% or 0.11 â€‹mg) in a commercial formulation, and compared with the spectra of neat l-cysteine recorded using a standard BaBa experiment. The 2D 1H double-quantum-single-quantum (DQ-SQ) spectrum of the API (l-cysteine)-detected pharmaceutical tablet is in good agreement with the 2D 1H DQ-SQ spectrum obtained from the pure API molecule. Furthermore, the sensitivity and robustness of the experiment is examined by selectively detecting 1H{14N} signals in an amino acid salt, l-histidine.H2O.HCl.

Direct Observation of the Relationship betweenMolecular Topology and Bulk Morphology for a π-Conjugated Material.

High-performance organic semiconducting materials are reliant upon subtle changes in structure across different length scales. These morphological features control relevant physical properties and ultimately device performance. By combining in situ NMR spectroscopy and theoretical calculations, the conjugated small molecule TT is shown to exhibit distinct temperature-dependent local structural features that are related to macroscopic properties. Specifically, lamellar and melt states are shown to exhibit different molecular topologies associated with planar and twisted conformations of TT, respectively. This topological transformation offers a novel avenue for molecular design and control of solid-state organization.

Nanoscale Surface Compositions and Structures Influence Boron Adsorption Properties of Anion Exchange Resins.

Boron adsorption properties of poly(styrene-co-divinylbenzene) (PSDVB)-based anion-exchange resins with surface-grafted N-methyl-d-glucamine (NMDG) depend strongly on their local surface compositions, structures, and interfacial interactions. Distinct boron adsorption sites have been identified and quantified, and interactions between borate anions and hydroxyl groups of NMDG surface moieties have been established. A combination of X-ray photoelectron spectroscopy (XPS), solid-state nuclear magnetic resonance (NMR), and Fourier-transform infrared (FT-IR) spectroscopy were used to characterize the atomic-level compositions and structures that directly influence the adsorption of borate anions on the NMDG-functionalized resin surface. Surface-enhanced dynamic-nuclear-polarization (DNP)-NMR enabled dilute (3 atom % N) tertiary alkyl amines and quaternary ammonium ions of the NMDG groups to be detected and distinguished with unprecedented sensitivity and resolution at natural abundance 15N (0.4%). Two-dimensional (2D) solid-state 11B{1H}, 13C{1H}, and 11B{11B} NMR analyses provide direct atomic-scale evidence for interactions of borate anions with the NMDG moieties on the resin surfaces, which form stable mono- and bischelate complexes. FT-IR spectra reveal displacements in the stretching vibrational frequencies associated with the O-H and N-H bonds of NMDG groups that corroborate the formation of chelate complexes on the resin surfaces. The atomic-level compositions and structures are related to boron adsorption properties of resin materials synthesized under different conditions, which have important remediation applications.

Co-existence of Distinct Supramolecular Assemblies in Solution and in the Solid State.

The formation of distinct supramolecular assemblies, including a metastable species, is revealed for a lipophilic guanosine (G) derivative in solution and in the solid state. Structurally different G-quartet-based assemblies are formed in chloroform depending on the nature of the cation, anion and the salt concentration, as characterized by circular dichroism and time course diffusion-ordered NMR spectroscopy data. Intriguingly, even the presence of potassium ions that stabilize G-quartets in chloroform was insufficient to exclusively retain such assemblies in the solid state, leading to the formation of mixed quartet and ribbon-like assemblies as revealed by fast magic-angle spinning (MAS) NMR spectroscopy. Distinct N-H⋅⋅⋅N and N-H⋅⋅⋅O intermolecular hydrogen bonding interactions drive quartet and ribbon-like self-assembly resulting in markedly different 2D 1 H solid-state NMR spectra, thus facilitating a direct identification of mixed assemblies. A dissolution NMR experiment confirmed that the quartet and ribbon interconversion is reversible-further demonstrating the changes that occur in the self-assembly process of a lipophilic nucleoside upon a solid-state to solution-state transition and vice versa. A systematic study for complexation with different cations (K+ , Sr2+ ) and anions (picrate, ethanoate and iodide) emphasizes that the existence of a stable solution or solid-state structure may not reflect the stability of the same supramolecular entity in another phase.

Combined maximum-quantum and DOSY 3D experiments provide enhanced resolution for small molecules in mixtures.

We illustrate here as the combination of high-order maximum-quantum (MaxQ) and Diffusion-Ordered SpectroscopY (DOSY) NMR experiments in a 3D layout allows superior resolution for crowded NMR spectra. Non-uniform sampling (NUS) allows compressing the experimental time effectively to reasonable durations. Because diffusion effects were encoded within multiple-quantum coherences, increased sensitivity to magnetic field gradients is observed, requiring compensation for convection effects. The experiment was demonstrated on the spectra of a mix of small polyaromatic molecules. Specifically, in the case analyzed, the experiment provided an extreme simplification through the MaxQDOSY-MaxQ projection plane that presents one peak per molecule. Copyright © 2016 John Wiley & Sons, Ltd.

Fast Magic-Angle Spinning Three-Dimensional NMR Experiment for Simultaneously Probing H-H and N-H Proximities in Solids.

A fast magic-angle spinning (MAS, 70 kHz) solid-state NMR experiment is presented that combines 1H Double-Quantum (DQ) and 14N-1H HMQC (Heteronuclear Multiple-Quantum Coherence) pulse-sequence elements, so as to simultaneously probe H-H and N-H proximities in molecular solids. The proposed experiment can be employed in both two-dimensional (2D) and three-dimensional (3D) versions: first, a 2D 14N HMQC-filtered 1H-DQ experiment provides specific DQ-SQ correlation peaks for proton pairs that are in close proximities to the nitrogen sites, thereby achieving spectral filtration. Second, a proton-detected three-dimensional (3D) 1H(DQ)-14N(SQ)-1H(SQ) experiment correlates 1H(DQ)-1H(SQ) chemical shifts with 14N shifts such that longer range N···H-H correlations are observed between protons and nitrogen atoms with internuclear NH distances exceeding 3 Å. Both 2D and 3D versions of the proposed experiment are demonstrated for an amino acid hydrochloride salt, l-histidine·HCl·H2O, and a DNA nucleoside, guanosine·2H2O. In the latter case, the achieved spectral filtration ensures that DQ cross peaks are only observed for guanine NH and CH8 1H resonances and not ribose and water 1H resonances, thus providing insight into the changes in the solid-state structure of this hydrate that occur over time; significant changes are observed in the NH and NH21H chemical shifts as compared to the freshly recrystallized sample previously studied by Reddy et al., Cryst. Growth Des. 2015, 15, 5945.

Time-optimal excitation of maximum quantum coherence: Physical limits and pulse sequences.

Here we study the optimum efficiency of the excitation of maximum quantum (MaxQ) coherence using analytical and numerical methods based on optimal control theory. The theoretical limit of the achievable MaxQ amplitude and the minimum time to achieve this limit are explored for a set of model systems consisting of up to five coupled spins. In addition to arbitrary pulse shapes, two simple pulse sequence families of practical interest are considered in the optimizations. Compared to conventional approaches, substantial gains were found both in terms of the achieved MaxQ amplitude and in pulse sequence durations. For a model system, theoretically predicted gains of a factor of three compared to the conventional pulse sequence were experimentally demonstrated. Motivated by the numerical results, also two novel analytical transfer schemes were found: Compared to conventional approaches based on non-selective pulses and delays, double-quantum coherence in two-spin systems can be created twice as fast using isotropic mixing and hard spin-selective pulses. Also it is proved that in a chain of three weakly coupled spins with the same coupling constants, triple-quantum coherence can be created in a time-optimal fashion using so-called geodesic pulses.

G4-quartet·M(+) borate hydrogels.

The ability to modulate the physical properties of a supramolecular hydrogel may be beneficial for biomaterial and biomedical applications. We find that guanosine (G 1), when combined with 0.5 equiv of potassium borate, forms a strong, self-supporting hydrogel with elastic moduli >10 kPa. The countercation in the borate salt (MB(OH)4) significantly alters the physical properties of the hydrogel. The gelator combination of G 1 and KB(OH)4 formed the strongest hydrogel, while the weakest system was obtained with LiB(OH)4, as judged by (1)H NMR and rheology. Data from powder XRD, (1)H double-quantum solid-state magic-angle spinning (MAS) NMR and small-angle neutron scattering (SANS) were consistent with a structural model that involves formation of borate dimers and G4·K(+) quartets by G 1 and KB(OH)4. Stacking of these G4·M(+) quartets into G4-nanowires gives a hydrogel. We found that the M(+) cation helps stabilize the anionic guanosine-borate (GB) diesters, as well as the G4-quartets. Supplementing the standard gelator mixture of G 1 and 0.5 equiv of KB(OH)4 with additional KCl or KNO3 increased the strength of the hydrogel. We found that thioflavin T fluoresces in the presence of G4·M(+) precursor structures. This fluorescence response for thioflavin T was the greatest for the K(+) GB system, presumably due to the enhanced interaction of the dye with the more stable G4·K(+) quartets. The fluorescence of thioflavin T increased as a function of gelator concentration with an increase that correlated with the system's gel point, as measured by solution viscosity.

An NMR crystallography study of the hemihydrate of 2', 3'-O-isopropylidineguanosine.

An NMR crystallography study of the hemihydrate of 2', 3'-O-isopropylidineguanosine (Gace) is presented, together with powder X-ray diffraction and thermogravimetric analysis. (1)H double-quantum and (14)N-(1)H HMQC spectra recorded at 850MHz and 75kHz MAS (using a JEOL 1mm probe) are presented together with a (1)H-(13)C refocused INEPT spectrum recorded at 500MHz and 12.5kHz MAS using eDUMBO-122(1)H homonuclear decoupling. NMR chemical shieldings are calculated using the GIPAW (gauge-including projector augmented wave) method; good two-dimensional agreement between calculation and experiment is observed for (13)C and (1)H chemical shifts for directly bonded CH and CH3 peaks. There are two Gace molecules in the asymmetric unit cell: differences in specific (1)H chemical shifts are rationalised in terms of the strength of CH-π and intermolecular hydrogen bonding interactions.

A G4·K⁺ hydrogel stabilized by an anion.

Supramolecular hydrogels derived from natural products have promising applications in diagnostics, drug delivery, and tissue engineering. We studied the formation of a long-lived hydrogel made by mixing guanosine (G, 1) with 0.5 equiv of KB(OH)4. This ratio of borate anion to ligand is crucial for gelation as it links two molecules of 1, which facilitates cation-templated assembly of G4·K(+) quartets. The guanosine-borate (GB) hydrogel, which was characterized by cryogenic transmission electron microscopy and circular dichroism and (11)B magic-angle-spinning NMR spectroscopy, is stable in water that contains physiologically relevant concentrations of K(+). Furthermore, non-covalent interactions, such as electrostatics, π-stacking, and hydrogen bonding, enable the incorporation of a cationic dye and nucleosides into the GB hydrogel.

High-Performance Wearable Organic Photodetectors by Molecular Design and Green Solvent Processing for Pulse Oximetry and Photoplethysmography.

White-light detection from the visible to the near-infrared region is central to many applications such as high-speed cameras, autonomous vehicles, and wearable electronics. While organic photodetectors (OPDs) are being developed for such applications, several challenges must be overcome to produce scalable high-detectivity OPDs. This includes issues associated with low responsivity, narrow absorption range, and environmentally friendly device fabrication. Here, an OPD system processed from 2-methyltetrahydrofuran (2-MeTHF) sets a record in light detectivity, which is also comparable with commercially available silicon-based photodiodes is reported. The newly designed OPD is employed in wearable devices to monitor heart rate and blood oxygen saturation using a flexible OPD-based finger pulse oximeter. In achieving this, a framework for a detailed understanding of the structure-processing-property relationship in these OPDs is also developed. The bulk heterojunction (BHJ) thin films processed from 2-MeTHF are characterized at different length scales with advanced techniques. The BHJ morphology exhibits optimal intermixing and phase separation of donor and acceptor moieties, which facilitates the charge generation and collection process. Benefitting from high charge carrier mobilities and a low shunt leakage current, the newly developed OPD exhibits a specific detectivity of above 1012  Jones over 400-900 nm, which is higher than those of reference devices processed from chlorobenzene and ortho-xylene.

Two-dimensional perovskite templates for durable, efficient formamidinium perovskite solar cells.

We present a design strategy for fabricating ultrastable phase-pure films of formamidinium lead iodide (FAPbI3) by lattice templating using specific two-dimensional (2D) perovskites with FA as the cage cation. When a pure FAPbI3 precursor solution is brought in contact with the 2D perovskite, the black phase forms preferentially at 100°C, much lower than the standard FAPbI3 annealing temperature of 150°C. X-ray diffraction and optical spectroscopy suggest that the resulting FAPbI3 film compresses slightly to acquire the (011) interplanar distances of the 2D perovskite seed. The 2D-templated bulk FAPbI3 films exhibited an efficiency of 24.1% in a p-i-n architecture with 0.5-square centimeter active area and an exceptional durability, retaining 97% of their initial efficiency after 1000 hours under 85°C and maximum power point tracking.