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TThe photovoltaic properties of binary and ternary blends of a polymer with molecular non-fullerene and fullerene acceptors are systematically investigated to provide morphology-charge dynamics–device performance design rules for future PSC development.

The ability to gradually modify the atomic structures of nanomaterials and directly identify such structural variation is important in nanoscience research. Here, we present the first example of a high-pressure single-crystal X-ray diffraction analysis of atomically precise metal nanoclusters. The pressure-dependent, subangstrom structural evolution of an ultrasmall gold nanoparticle, Au

List of all H4 missense mutations in cBioPortal nad dbSNP analysis

List of all H2B missense mutations in cBioPortal and dbSNP analysis

List of all H3 missense mutations in cBioPortal and dbSNP analysis

Supplemental materials and methods and Supplemental Figures 1-7

List of all H2A missense mutations in cBioPortal and dbSNP analysis

By examination of the cancer genomics database, we identified a new set of mutations in core histones that frequently recur in cancer patient samples and are predicted to disrupt nucleosome stability. In support of this idea, we characterized a glutamate to lysine mutation of histone H2B at amino acid 76 (H2B-E76K), found particularly in bladder and head and neck cancers, that disrupts the interaction between H2B and H4. Although H2B-E76K forms dimers with H2A, it does not form stable histone octamers with H3 and H4 in vitro, and when reconstituted with DNA forms unstable nucleosomes with increased sensitivity to nuclease. Expression of the equivalent H2B mutant in yeast restricted growth at high temperature and led to defective nucleosome-mediated gene repression. Significantly, H2B-E76K expression in the normal mammary epithelial cell line MCF10A increased cellular proliferation, cooperated with mutant PIK3CA to promote colony formation, and caused a significant drift in gene expression and fundamental changes in chromatin accessibility, particularly at gene regulatory elements. Taken together, these data demonstrate that mutations in the globular domains of core histones may give rise to an oncogenic program due to nucleosome dysfunction and deregulation of gene expression.Significance:Mutations in the core histones frequently occur in cancer and represent a new mechanism of epigenetic dysfunction that involves destabilization of the nucleosome, deregulation of chromatin accessibility, and alteration of gene expression to drive cellular transformation.See related commentary by Sarthy and Henikoff, p. 1346.This article is highlighted in the In This Issue feature, p. 1325

Supramolecular-covalent hybrid spiropyran hydrogels are developed to generate robotic functions in response to light. The morphology of supramolecular phases is found to play a critical role in mechanical photo-actuation of these hybrid hydrogels.

Strong coupling between light and matter can produce hybrid eigenstates known as exciton-polaritons. Although polariton dynamics are important photophysical properties, the relaxation pathways of polaritons in different coupling regimes have seen limited attention. This paper reports the dynamics of hybridized states from 2D Ruddlesden-Popper perovskites coupled to plasmonic nanoparticle lattices. The open cavity architecture of Al lattices enables the coupling strength to be modulated by varying either the lead halide perovskite film thickness or the superstrate refractive index. Both experiments and finite-difference time-domain simulations of the optical dispersion diagrams showed avoided crossings that are a signature of strong coupling. Our analytical model also elucidated the correlation between the exciton/plasmon mixing ratio and polariton coupling strength. Using fs-transient absorption spectroscopy, we found that both the upper and lower polaritons have shorter lifetimes than the excitons and that polaritons can show faster excited-state dynamics when they have access to additional energy transfer channels.

The problem this paper addresses is the origin of the hysteretic behavior in two-terminal molecular junctions made from an EGaIn electrode and self-assembled monolayers of alkanethiolates terminated in chelates (transition metal dichlorides complexed with 2,2'-bipyridine; BIPY-MCl

The rapid development of non-fullerene acceptors (NFAs) with strong near-infrared absorption has led to remarkably enhanced short-circuit current density (Jsc) values in organic solar cells (OSCs). NFAs based on the benzotriazole (Bz) fused-ring π-core have great potential in delivering both high Jsc and decent open-circuit voltage values due to their strong intramolecular charge transfer with reasonably low energy loss. In this work, we have designed and synthesized a series of Bz-based NFAs, PN6SBO-4F, AN6SBO-4F and EHN6SEH-4F, via regiospecific N-alkyl engineering based on the high-performance NFA mBzS-4F that was reported previously. The molecular packing of mBzS-4F, AN6SBO-4F, and EHN6SEH-4F single crystals was analyzed using X-ray crystallography in order to provide a comprehensive understanding of the correlation between the molecular structure, the charge-transporting properties, and the solar cell performance. Compared with the typical honeycomb single-crystal structure of Y6 derivatives, these NFAs exhibit distinctly different molecular packing patterns. The strong interactions of terminal indanone groups in mBzS-4F and the J-aggregate-like packing in EHN6SEH-4F lead to the formation of ordered 3D networks in single-crystals with channels for efficient charge transport. Consequently, OSCs based on mBzS-4F and EHN6SEH-4F show efficient photon-to-current conversions, achieving the highest power conversion efficiency of 17.48% with a Jsc of 28.83 mA cm−2.

Excitonic dynamics studies of a 2D COF, its corresponding hexagonal macrocycle, and extended nanotubes comprised of stacked macrocycles reveal that layering of the macrocycle in the assembled COF and nanotube lead to a prolonged exciton lifetime.

Entangled two-photon absorption (ETPA) is known to create photoinduced transitions with extremely low light intensity, reducing the risk of phototoxicity compared to classical two-photon absorption. Previous works have predicted the ETPA cross-section, σe, to vary inversely with the product of entanglement time (Te) and entanglement area (Ae), i.e., σe ∼ 1/AeTe. The decreasing σe with increasing Te has limited ETPA to fs-scale Te, while ETPA applications for ps-scale spectroscopy have been unexplored. However, we show that spectral-spatial coupling, which reduces Ae as the SPDC bandwidth (σf) decreases, plays a significant role in determining σe when Te > ∼100 fs. We experimentally measured σe for zinc tetraphenylporphyrin at several σf values. For type-I ETPA, σe increases as σf decreases down to 0.1 ps-1. For type-II SPDC, σe is constant for a wide range of σf. With a theoretical analysis of the data, the maximum type-I σe would occur at σf = 0.1 ps-1 (Te = 10 ps). At this maximum, σe is 1 order of magnitude larger than fs-scale σe and 3 orders of magnitude larger than previous predictions of ps-scale σe. By utilizing this spectral-spatial coupling, narrowband type-I ETPA provides a new opportunity to increase the efficiency of measuring nonlinear optical signals and to control photochemical reactions requiring ps temporal precision.

Gold nanoclusters with near-infrared (NIR) photoluminescence (PL) have great potential as sensing and imaging materials in biomedical and bioimaging applications. In this work, Au21(S-Adm)15 and Au38S2(S-Adm)20 are used to unravel the underlying mechanisms for the improved quantum yields (QY), large Stokes shifts, and long PL lifetimes in gold nanoclusters. Both nanoclusters show decent PL QY. In particular, the Au38S2(S-Adm)20 nanocluster shows a bright NIR PL at 900 nm with QY up to 15% in normal solvents (such as toluene) at ambient conditions. The relatively lower QY for Au21(S-Adm)15 (4%) compared to that of Au38S2(S-Adm)20 is attributed to the lowest-lying excited state being symmetry-disallowed, as evidenced by the pressure-dependent antispectral shift of the absorption spectra compared to PL, yet Au21(S-Adm)15 maintains some emissive properties due to a nearby symmetry-allowed excited state. Furthermore, our results show that suppression of nonradiative decay due to the surface "lock rings", which encircle the Au kernel and the surface "lock atoms" which bridge the fundamental Au kernel units (e.g., tetrahedra, icosahedra, etc.), is the key to obtaining high QYs in gold nanoclusters. The complicated excited-state processes and the small absorption coefficient of the band-edge transition lead to the large Stokes shifts and the long PL lifetimes that are widely observed in gold nanoclusters.

The understanding and controlled creation of atomic defects in semiconductor transition metal dichalcogenides (TMDs) are highly relevant to their applications in high-performance quantum optics and nanoelectronic devices. Here, we demonstrate a versatile approach in generating single-photon emitters in MoS

Natural materials exhibit emergent mechanical properties as a result of their nanoarchitected, nanocomposite structures with optimized hierarchy, anisotropy, and nanoporosity. Fabrication of such complex systems is currently challenging because high-quality three-dimensional (3D) nanoprinting is mostly limited to simple, homogeneous materials. We report a strategy for the rapid nanoprinting of complex structural nanocomposites using metal nanoclusters. These ultrasmall, quantum-confined nanoclusters function as highly sensitive two-photon activators and simultaneously serve as precursors for mechanical reinforcements and nanoscale porogens. Nanocomposites with complex 3D architectures are printed, as well as structures with tunable, hierarchical, and anisotropic nanoporosity. Nanocluster-polymer nanolattices exhibit high specific strength, energy absorption, deformability, and recoverability. This framework provides a generalizable, versatile approach for the use of photoactive nanomaterials in additive manufacturing of complex systems with emergent mechanical properties.

This paper presents the reaction mechanism, cross sections, and product energy partitioning for the O + CO2 reaction, calculated using Born-Oppenheimer molecular dynamics simulations with the quasiclassical trajectory (BOMD-QCT) method. At collision energies up to 9.5 eV, three reactions, oxygen exchange (above ∼1.5 eV), abstraction (above ∼5.5 eV), and dissociation (above ∼7.5 eV) occur, with abstraction and dissociation involving either an insertion-elimination mechanism or a stripping mechanism. The insertion-elimination mechanism involves the formation of a planar CO3 intermediate which lies 0.52 eV above the ground-state CO2; the energetic barrier for oxygen abstraction via this mechanism is 3.52 eV. Interestingly, the insertion-elimination mechanism predominately contributes to the cross sections at collision energies just above the effective energetic threshold for the abstraction and dissociation reactions; at higher collision energies, the contribution from the stripping mechanism increases and eventually dominates. At a collision energy of 9.5 eV, the cross sections for oxygen exchange, abstraction, and dissociation are 4.17 a02, 1.58 a02, and 0.68 a02, respectively. The lower reaction cross sections, higher effective reaction barrier, and product energy distribution of the stripping mechanism were attributed to the short lifetime (28 fs) of the OCOO species compared with that of the CO3 species (45 fs) that arises in the insertion-elimination mechanism. For the exchange reaction, it is found that roughly 40% of the reactant translational energy ends up in CO2 vibration, which provides a single-collision mechanism to produce highly excited CO2. We also studied intersystem crossing effects using trajectory surface hopping calculations and find no changes compared to single surface (triplet) calculations at energies below 7.5 eV; however, at 7.5 eV and higher the abstraction cross sections are changed by as much as 20%, and the (very small) dissociation cross sections are changed by factors of four or more.

The development of synthetic receptors that recognize carbohydrates in water with high selectivity and specificity is challenging on account of their structural complexity and strong hydrophilicity. Here, we report on the design and synthesis of two pyrene-based, temple-shaped receptors for the recognition of a range of common sugars in water. These receptors rely on the use of two parallel pyrene panels, which serve as roofs and floors, capable of forming multiple [C-H···π] interactions with the axially oriented C-H bonds on glycopyranosyl rings in the carbohydrate-based substrates. In addition, eight polarized pyridinium C-H bonds, projecting from the roofs and floors of the temple receptors toward the binding cavities, form [C-H···O] hydrogen bonds, with the equatorially oriented OH groups on the sugars located inside the hydrophobic cavities. Four para-xylylene pillars play a crucial role in controlling the distance between the roof and floor. These temple receptors are highly selective for the binding of glucose and its derivatives. Furthermore, they show enhanced fluorescence upon binding with glucose in water, a property which is useful for glucose-sensing in aqueous solution.

This Letter describes strong coupling of densely packed molecular emitters in metal-organic frameworks (MOFs) and plasmonic nanoparticle (NP) lattices. Porphyrin-derived ligands with small transition dipole moments in an ordered MOF film were grown on Ag NP arrays. Angle-resolved optical measurements of the MOF-NP lattice system showed the formation of a polariton that is lower in energy and does not cross the uncoupled MOF Q1 band. Modeling predicted the upper polariton energy and a calculated Rabi splitting of 110 meV. The coupling strength was systematically controlled by detuning the plasmon energy by changing the refractive index of the solvents infiltrating the MOF pores. Through transient absorption spectroscopy, we found that the lower polariton decays quickly at shorter time scales (

It is critical to assemble nanoparticles (NPs) into superlattices with controlled symmetries and spacings on substrates for metamaterials applications, where such structural parameters dictate their properties. Here, we use DNA to assemble anisotropic NPs of three shapes-cubes, octahedra, and rhombic dodecahedra-on substrates and investigate their thermally induced reorganization into two-dimensional (2D) crystalline films. We report two new low-density 2D structures, including a honeycomb lattice based on octahedral NPs. The low-density lattices favored here are not usually seen when particles are crystallized via other bottom-up assembly techniques. Furthermore, we show that, consistent with the complementary contact model, a primary driving force for crystallization is the formation of directional, face-to-face DNA bonds between neighboring NPs and between NPs and the substrate. Our results can be used to deliberately prepare crystalline NP films with novel morphologies.

Motivated by recent advances in the development of single photon emitters for quantum information sciences, here we design and formulate a quantum cascade model that describes cascade emission by a quantum dot (QD) in a cavity structure while preserving entanglement that stores information needed for single photon emission. The theoretical approach is based on a photonic structure that consists of two orthogonal cavities in which resonance with either the first or second of the two emitted photons is possible, leading to amplification and rerouting of the entangled light. The cavity–QD scheme uses a four-level cascade emitter that involves three levels for each polarization, leading to two spatially entangled photons for each polarization. By solving the Schrodinger equation, we identify the characteristic properties of the system, which can be used in conjunction with optimization techniques to achieve the “best” design relative to a set of prioritized criteria or constraints in our optical system. The theoretical investigations include an analysis of emission spectra in addition to the joint spectral density profile, and the results demonstrate the ability of the cavities to act as frequency filters for the photons that make up the entanglements and to modify entanglement properties. The results provide new opportunities for the experimental design and engineering of on-demand single photon sources.

Since anions are vital for many chemical, biological and environmental processes, their recognition and separation continue to attract attention from chemists, materials scientists and engineers. Employing exo-binding of artificial macrocycles to recognize selectively anions remains a challenge in supramolecular chemistry. Herein, we report the instantaneous co-crystallization and concomitant co-precipitation between hexachloroplatinate dianions and cucurbit[6]uril, a phenomenon which relies on the selective recognition of these dianions through the noncovalent bonding interactions on the outer surface of cucurbit[6]uril. The selective hexachloroplatinate dianion recognition is driven by the weak [Pt-Cl···H-C] hydrogen bonding and [Pt-Cl···C=O] ion-dipole interactions. The synthetic protocol is highly selective. It is not observed in combinations between cucurbit[6]uril and other Pt- and Pd- or Rh-based chloride anions. We have also demonstrated that cucurbit[6]uril is able to separate selectively hexachloroplatinate dianions from mixtures of hexachloroplatinate, tetrachloropalladate, and hexachlororhodate anions. This highly selective and fast co-crystallization process, in principle, could be exploited to recover platinum from the spent vehicular three-way catalytic converters and other platinum-bearing metal waste.

We experimentally investigated several intra-molecular coordinate and environmental changes as potential causes of single-molecule fluorescence spectral heterogeneities (smFSH). We developed a high-throughput single-molecule spectroscopy technique to analyze more than 5,000 single-molecule emission spectra from each of nine commonly used fluorophores with different structural rigidities deposited on substrates with different polarities. We observed an unexpected high smFSH from structurally rigid Rhodamine B compared with a structurally flexible Cyanine dye - Alexa Fluor 647. Based on experimentally measured smFSH, we ruled out the system’s noise uncertainty, single-molecule spectral diffusion, and environmental polarity as the primary causes of the high smFSH. We found that the rotational flexibility of N, N-dialkylated groups contributed to the smFSH. With the high smFSH observed in structurally more rigid model fluorophores, we speculated that other intra-molecular coordinate and environmental changes might also contribute to the high smFSH in Rhodamines.

The end-capping group (EG) is the essential electron-withdrawing component of nonfullerene acceptors (NFAs) in bulk heterojunction (BHJ) organic solar cells (OSCs). To systematically probe the impact of two frequent EG functionalization strategies, π-extension and halogenation, in A-DAD-A type NFAs, we synthesized and characterized four such NFAs: BT-BIC, LIC, L4F, and BO-L4F. To assess the relative importance of these strategies, we contrast these NFAs with the baseline acceptors, Y5 and Y6. Up to 16.6% power conversion efficiency (PCE) in binary inverted OSCs with BT-BO-L4F combining π-extension and halogenation was achieved. When these two factors are combined, the effect on optical absorption is cumulative. Single-crystal π-π stacking distances are similar for the EG strategies of π-extension. Increasing the alkyl substituent length from BT-L4F to BT-BO-L4F significantly alters the packing motif and eliminates the EG core interactions of BT-L4F. Electronic structure computations reveal some of the largest NFA π-π electronic couplings observed to date, 103.8 meV in BT-L4F and 47.5 meV in BT-BO-L4F. Computed electronic reorganization energies, 132 and 133 meV for BT-L4F and BT-BO-L4F, respectively, are also lower than Y6 (150 meV). BHJ blends show preferential π-face-on orientation, and both fluorination and π-extension increase NFA crystallinity. Femto/nanosecond transient absorption spectroscopy (fs/nsTA) and integrated photocurrent device analysis (IPDA) indicate that π-extension modifies the phase separation to enhance film ordering and carrier mobility, while fluorination suppresses unimolecular recombination. This systematic study highlights the synergistic effects of NFA π-extension and fluorination in affording efficient OSCs and provides insights into designing next-generation materials.

Significance Molecules interacting with metallic nanostructures can show tunable exciton-plasmon coupling, ranging from weak to strong. One factor that influences the interactions is the spatial organization of the molecules relative to the localized plasmon-enhanced electromagnetic fields. In this work, we show that the arrangement of aromatic dye molecules can be tuned within plasmonic hotspots by interfacial engineering of nanoparticle surfaces. By controlling the local chemical and physical interactions, we could modulate lasing thresholds. Surface-functionalized plasmonic metasurfaces open prospects for programmable light-matter interactions at the nanoscale.