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The magnetic properties of molecularstructures can be tailoredby chemical synthesis or bottom-up assembly at the atomic scale. Weused scanning tunneling microscopy to study charge and spin transferin individual complexes of transition metals with the charge acceptor,tetracyanoethylene (TCNE). The complexes were formed on a thin insulator,Cu2N on Cu(100), by manipulation of individual atoms andmolecules. The Cu2N layer decouples the complexes fromCu electron density, enabling direct imaging of the TCNE molecularorbitals as well as spin-flip inelastic electron tunneling spectroscopy.Results were obtained at low temperature down to 1 K and in magneticfields up to 7 T in order to resolve splitting of spin states in thecomplexes. We also performed spin-polarized density functional theorycalculations to compare with the experimental data. Our results indicatethat charge transfer to TCNE leads to a change in spin magnitude,Kondo resonance, and magnetic anisotropy for the metal atoms. [ABSTRACT FROM AUTHOR]

Deflectors are essential for modulating beam direction in optical systems but often face form factor issues or chromatic aberration with conventional optical elements, such as prisms, mirrors, and diffractive/holographic optical elements. Despite recent efforts to address such issues using metasurfaces, their practicality remains limited due to operation wavelengths in the near-infrared or the fabrication difficulties inherent in the multilayer scheme. Here, we propose a novel single-layer metasurface achieving multiwavelength chromatic aberration-free deflection across the visible spectrum by employing the robust freeform design strategy to simplify the fabrication process. By properly selecting diffraction orders for red, green, and blue wavelengths to achieve identical wavelength-diffraction-order products, the metasurface deflects light at a consistent angle of 41.3° with a high efficiency. The coupled Bloch mode analysis explains the physical properties, and experimental fabrication and characterization confirm its effectiveness. This approach holds potential for various applications such as AR/VR, digital cameras, and high-quality optical systems.

Excited-ground-state transition and strand slippage of RNA play key roles in transcription and translation of central dogma. Due to limitation of current experimental techniques, the dynamic structure ensembles of RNA remain inadequately understood. Molecular dynamics simulations offer a promising complementary approach, whose accuracy depends on the force field. Here, we develop the new version of RNA base-specific force field (BSFF2) to address underestimation of base pairing stability and artificial backbone conformations. Extensive evaluations on typical RNA systems have comprehensively confirmed the accuracy of BSFF2. Furthermore, BSFF2 demonstrates exceptional efficiency in de novo folding of tetraloops and reproducing base pair reshuffling transition between RNA excited and ground states. Then, we explored the RNA strand slippage mechanism with BSFF2. We conducted a comprehensive three-dimensional structural investigation into the strand slippage of the most complex r(G4C2) 9 repeat element and presented the molecular details in the dynamic transition along with the underlying mechanism. Our results of capturing the strand slippage, excited-ground transition, de novo folding, and simulations for various typical RNA motifs indicate that BSFF2 should be one of valuable tools for dynamic conformation research and structure prediction of RNA, and a future contribution to RNA-targeted drug design as well as RNA therapy development.

Robust ferroelectricity in HfO 2 -based ultrathin films has the potential to revolutionize nonvolatile memory applications in nanoscale electronic devices because of their compatibility with the existing Si technology. However, to fully exploit the potential of ferroelectric HfO 2 -based thin films, it is crucial to develop strategies for the controlled stabilization of various HfO 2 -based polymorphs in nanoscale heterostructures. This study demonstrates how substrate-orientation-induced anisotropic strain can engineer the crystal symmetry, structural domain morphology, and growth orientation of ultrathin Hf 0.5 Zr 0.5 O 2 (HZO) films. Epitaxial ultrathin HZO films were grown on the heterostructures of (001)- and (110)-oriented La 2/3 Sr 1/3 MnO 3 /SrTiO 3 (LSMO/STO) substrate. Various structural analyses revealed that the (110)-oriented substrate promotes a higher degree of structural order (crystallinity) with improved stability of the (111)-oriented orthorhombic phase ( Pca 2 1 ) of HZO. Conversely, the (001)-oriented substrate not only induces a distorted orthorhombic structure but also facilitates the partial stabilization of nonpolar phases. Electrical measurements revealed robust ferroelectric properties in epitaxial thin films without any wake-up effect, where the well-ordered crystal symmetry stabilized by STO(110) facilitated better ferroelectric characteristics. This study suggests that tuning the epitaxial growth of ferroelectric HZO through substrate orientation can improve the stability of the metastable ferroelectric orthorhombic phase and thereby offer a better understanding of device applications.

Molecular dynamics simulations play a pivotal role in elucidating the dynamic behaviors of RNA structures, offering a valuable complement to traditional methods such as nuclear magnetic resonance or X-ray. Despite this, the current precision of RNA force fields lags behind that of protein force fields. In this work, we systematically compared the performance of four RNA force fields ( ff99 bsc0 χOL3 , AMBER DES , ff99OL3_CMAP1 , AMBER MaxEnt ) across diverse RNA structures. Our findings highlight significant challenges in maintaining stability, particularly with regard to cross-strand and cross-loop hydrogen bonds. Furthermore, we observed the limitations in accurately describing the conformations of nonhelical structural motif, terminal nucleotides, and also base pairing and base stacking interactions by the tested RNA force fields. The identified deficiencies in existing RNA force fields provide valuable insights for subsequent force field development. Concurrently, these findings offer recommendations for selecting appropriate force fields in RNA simulations.

Electrically conductive hydrogels represent an innovative platform for the development of bioelectronic devices. While photolithography technologies have enabled the fabrication of complex architectures with high resolution, photoprinting conductive hydrogels is still a challenging task because the conductive polymer absorbs light which can outcompete photopolymerization of the insulating scaffold. In this study, we introduce an approach to synthesizing conductive hydrogels in one step. Our approach combines the simultaneous photo-cross-linking of a polymeric scaffold and the polymerization of 3,4-ethylene dioxythiophene (EDOT), without additional photocatalysts. This process involves the copolymerization of photo-cross-linkable coumarin-containing monomers with sodium styrenesulfonate to produce a water-soluble poly(styrenesulfonate- co -coumarin acrylate) (P(SS- co -CoumAc)) copolymer. Our findings reveal that optimizing the [SS]:[CoumAc] ratio at 100:5 results in hydrogels with the strain at break up to 16%. This mechanical resilience is coupled with an electronic conductivity of 9.2 S m -1 suitable for wearable electronics. Furthermore, the conductive hydrogels can be photopatterned to achieve micrometer-sized structures with high resolution. The photo-cross-linked hydrogels are used as electrodes to record stable and reliable surface electromyography (sEMG) signals. These novel photo-cross-linkable polymers combined with one-pot PEDOT (poly-EDOT) polymerization open possibilities for rapidly prototyping complex bioelectronic devices and creating custom-designed interfaces between electronics and biological systems., Competing Interests: The authors declare no competing financial interest., (© 2023 The Authors. Published by American Chemical Society.)

Investigating the quantum properties of individual spins adsorbed on surfaces by electron spin resonance combined with scanning tunneling microscopy (ESR-STM) has shown great potential for the development of quantum information technology on the atomic scale. A magnetic tip exhibiting high spin polarization is critical for performing an ESR-STM experiment. While the tip has been conventionally treated as providing a static magnetic field in ESR-STM, it was found that the tip can exhibit bistability, influencing ESR spectra. Ideally, the ESR splitting caused by the magnetic interaction between two spins on a surface should be independent of the tip. However, we found that the measured ESR splitting of a metal atom-molecule heterodimer can be tip-dependent. Detailed theoretical analysis reveals that this tip-dependent ESR splitting is caused by a different interaction energy between the tip and each spin of the heterodimer. Our work provides a comprehensive reference for characterizing tip features in ESR-STM experiments and highlights the importance of employing a proper physical model when describing the ESR tip, in particular, for heterospin systems.

Allosteric modulators are important regulation elements that bind the allosteric site beyond the active site, leading to the changes in dynamic and/or thermodynamic properties of the protein. Allosteric modulators have been a considerable interest as potential drugs with high selectivity and safety. However, current experimental methods have limitations to identify allosteric sites. Therefore, molecular dynamics simulation based on empirical force field becomes an important complement of experimental methods. Moreover, the precision and efficiency of current force fields need improvement. Deep learning and reweighting methods were used to train allosteric protein-specific precise force field (named APSF ). Multiple allosteric proteins were used to evaluate the performance of APSF . The results indicate that APSF can capture different types of allosteric pockets and sample multiple energy-minimum reference conformations of allosteric proteins. At the same time, the efficiency of conformation sampling for APSF is higher than that for ff14SB . These findings confirm that the newly developed force field APSF can be effectively used to identify the allosteric pocket that can be further used to screen potential allosteric drugs based on these pockets.

A novel series of donor (D)-π-acceptor (A) merocyanine molecules harnessed with intramolecular chalcogen bonding (ChaB) is designed, synthesized, and characterized. ChaB comprises periodic chalcogen atoms, S, Se, and Te, and a neighboring oxygen atom of a carbonyl moiety. Compared to the D-π-A merocyanine dye with nontraditional intramolecular hydrogen bonding, the novel molecules with an intramolecular ChaB exhibit remarkably smaller absorption spectral widths and higher absorption coefficients attributed to their cyanine-like characteristics approaching the resonance parameter ( c 2 ) ∼0.5; furthermore, they exhibit better thermal stabilities and electrical charge-carrier transport properties in films. These novel D-π-A merocyanines harnessed with intramolecular ChaB networks are successfully utilized in high-performance color-selective organic photon-to-current conversion optoelectronic devices with excellent thermal stabilities. This study reports that the unique intramolecular ChaB plays an essential role in locking the molecular conformation of merocyanine molecules and enhancing the optical, thermal, and optoelectronic properties of high-performance and high-efficiency organic photon-to-current conversion devices.

While valley polarization with strong Zeeman splitting is the most prominent characteristic of two-dimensional (2D) transition metal dichalcogenide (TMD) semiconductors under magnetic fields, enhancement of the Zeeman splitting has been demonstrated by incorporating magnetic dopants into the host materials. Unlike Fe, Mn, and Co, V is a distinctive dopant for ferromagnetic semiconducting properties at room temperature with large Zeeman shifting of band edges. Nevertheless, little known is the excitons interacting with spin-polarized carriers in V-doped TMDs. Here, we report anomalous circularly polarized photoluminescence (CPL) in a V-doped WSe 2 monolayer at room temperature. Excitons couple to V-induced spin-polarized holes to generate spin-selective positive trions, leading to differences in the populations of neutral excitons and trions between left and right CPL. Using transient absorption spectroscopy, we elucidate the origin of excitons and trions that are inherently distinct for defect-mediated and impurity-mediated trions. Ferromagnetic characteristics are further confirmed by the significant Zeeman splitting of nanodiamonds deposited on the V-doped WSe 2 monolayer.

Control of single electron spins constitutes one of the most promising platforms for spintronics, quantum sensing, and quantum information processing. Utilizing single molecular magnets as their hosts establishes an interesting framework since their molecular structure is highly flexible and chemistry-based large-scale synthesis directly provides a way toward scalability. Here, we demonstrate coherent spin manipulation of single molecules on a surface, which we control individually using a scanning tunneling microscope in combination with electron spin resonance. We previously found that iron phthalocyanine (FePc) molecules form a spin-1/2 system when placed on an insulating thin film of magnesium oxide (MgO). Performing Rabi oscillation and Hahn echo measurements, we show that the FePc spin can be coherently manipulated with a phase coherence time T 2 Echo of several hundreds of nanoseconds. Tunneling current-dependent measurements demonstrate that interaction with the tunneling electrons is the dominating source of decoherence. In addition, we perform Hahn echo measurements on small self-assembled arrays of FePc molecules. We show that, despite additional intermolecular magnetic coupling, spin resonance and T 2 Echo are much less perturbed by T 1 spin flip events of neighboring spins than by the tunneling current. This will potentially allow for individual addressable molecular spins in self-assemblies and with application for quantum information processing.

Stacked structures employing wavelength-selective organic photodiodes (OPDs) have been studied as promising alternatives to the conventional Si-based image sensors because of their color constancy. Herein, novel donor (D)-π-acceptor (A) molecules are designed, synthesized, and characterized as green-light-selective absorbers for application in organic-on-Si hybrid complementary metal-oxide-semiconductor (CMOS) color image sensors. The p-type molecules, combined with two fused-type heterocyclic donors and an electron-accepting unit, exhibit cyanine-like properties that are characterized by intense and sharp absorption. This molecular design leads to improved absorption properties, thermal stability, and higher photoelectric conversion compared to those of a molecular design based on a nonfused ring. A maximum external quantum efficiency of 66% (λ max = 550 nm) and high specific detectivity ( D *) of 8 × 10 13 cm Hz 1/2 /W are achieved in an OPD consisting of a bulk heterojunction blend with two transparent electrodes on both sides. Finally, the green-light-detection capability of the narrow-band green-selective OPD is demonstrated by the optical simulation of an organic-on-Si hybrid, stacked-type, full-color photodetector comprising the green-light-selective OPD and a bottom Si photodiode with only blue and red color filters. Based on this molecular design, further optimization of the OPDs can allow the development of various optoelectronic sensors including 3D-stacked image sensors with enhanced sensitivities to replace the conventional Si-based CMOS image sensors.

Single spins are considered as a versatile candidate for miniaturizing information devices down to the nanoscale. To engineer the spin's properties, metal-organic frameworks provide a promising route which in turn requires thorough understanding of the metal-molecule interaction. Here, we investigate the magnetic robustness of a single iron (Fe) atom in artificially built Fe-tetracyanoethylene (TCNE) complexes by using low-temperature scanning tunneling microscopy (STM). We find that the magnetic anisotropy and spin relaxation dynamics of the Fe atom within the complexes remain unperturbed in comparison to well-isolated Fe atoms. Density functional theory (DFT) calculations support our experimental findings, suggesting that the 3d orbitals of the Fe atom remain largely undisturbed while the 4s and 4p orbitals are rearranged in the process of forming a complex. To precisely determine the location of the spin center within the complex, we utilize STM-based spin relaxometry, mapping out the spatial dependence of spin relaxation with subnanometer resolution. Our work suggests that the magnetic properties of atoms can remain unchanged while being embedded in a weakly bound molecular framework.

Spin resonance of single spin centers bears great potential for chemical structure analysis, quantum sensing, and quantum coherent manipulation. Essential for these experiments is the presence of a two-level spin system whose energy splitting can be chosen by applying a magnetic field. In recent years, a combination of electron spin resonance (ESR) and scanning tunneling microscopy (STM) has been demonstrated as a technique to detect magnetic properties of single atoms on surfaces and to achieve sub-microelectronvolts energy resolution. Nevertheless, up to now the role of the required magnetic fields has not been elucidated. Here, we perform single-atom ESR on individual Fe atoms adsorbed on magnesium oxide (MgO) using a two-dimensional vector magnetic field as well as the local field of the magnetic STM tip in a commercially available STM. We show how the ESR amplitude can be greatly improved by optimizing the magnetic fields, revealing in particular an enhanced signal at large in-plane magnetic fields. Moreover, we demonstrate that the stray field from the magnetic STM tip is a versatile tool. We use it here to drive the electron spin more efficiently and to perform ESR measurements at constant frequency by employing tip-field sweeps. Lastly, we show that it is possible to perform ESR using only the tip field, under zero external magnetic field, which promises to make this technique available in many existing STM systems.

We report a compressible monolithic catalyst based on a microporous organic polymer (MOP) sponge. The monolithic MOP sponge was synthesized via Sonogashira-Hagihara coupling reaction between 1,4-diiodotetrafluorobenzene and 1,3,5-triethynylbenzene in a cosolvent of toluene and TEA (2:1, v/v) without stirring. The MOP sponge had an intriguing microstructure, where tubular polymer fibers having a diameter of hundreds of nanometers were entangled. It showed hierarchical porosity with a Brunauer-Emmett-Teller (BET) surface area of 512 m 2 g -1 . The MOP sponge was functionalized with sulfur groups by the thiol-yne reaction. The functionalized MOP sponge exhibited a higher BET surface area than the MOP sponge by 13% due to the increase in the total pore and micropore volumes. A MOP sponge-Ag heterogeneous catalyst (S-MOPS-Ag) was prepared by in situ growth of silver nanoparticles inside the sulfur-functionalized MOP sponge by the reduction of Ag + ions. The catalytic activity of S-MOPS-Ag was investigated for the reduction reaction of 4-nitrophenol in an aqueous condition. When S-MOPS-Ag was compressed and released during the reaction, the rate of the reaction was considerably increased. S-MOPS-Ag was easily removed from the reaction mixture owing to its monolithic character and was reused after washing and drying.

Semiconducting two-dimensional (2D) transition metal dichalcogenides (TMDCs) are promising gas-sensing materials due to their large surface-to-volume ratio. However, their poor gas-sensing performance resulting from the low response, incomplete recovery, and insufficient selectivity hinders the realization of high-performance 2D TMDC gas sensors. Here, we demonstrate the improvement of gas-sensing performance of large-area tungsten disulfide (WS 2 ) nanosheets through surface functionalization using Ag nanowires (NWs). Large-area WS 2 nanosheets were synthesized through atomic layer deposition of WO 3 followed by sulfurization. The pristine WS 2 gas sensors exhibited a significant response to acetone and NO 2 but an incomplete recovery in the case of NO 2 sensing. After AgNW functionalization, the WS 2 gas sensor showed dramatically improved response (667%) and recovery upon NO 2 exposure. Our results establish that the proposed method is a promising strategy to improve 2D TMDC gas sensors.

We developed a technique for transferring graphene and hexagonal boron nitride (hBN) in dry conditions for fabrication of van der Waals heterostructures. The graphene layer was encapsulated between two hBN layers so that it was kept intact during fabrication of the device. For comparison, we also fabricated the devices containing graphene on SiO2/Si wafer and graphene on hBN. Electrical properties of the devices were investigated at room temperature. The mobility of the graphene on SiO2 devices and graphene on hBN devices were 15,000 and 37,000 cm(2) V(-1) s(-1), respectively, while the mobility of the sandwich structure device reached the highest value of ∼100,000 cm(2) V(-1) s(-1), at room temperature. The electrical measurements of the samples were carried out in air and vacuum environments. We found that the electrical properties of the encapsulated graphene devices remained at a similar level both in a vacuum and in air, whereas the properties of the graphene without encapsulation were influenced by the external environment.

We report an ultraclean, cost-effective, and easily scalable method of transferring and patterning large-area graphene using pressure sensitive adhesive films (PSAFs) at room temperature. This simple transfer is enabled by the difference in wettability and adhesion energy of graphene with respect to PSAF and a target substrate. The PSAF-transferred graphene is found to be free from residues and shows excellent charge carrier mobility as high as ∼17,700 cm(2)/V·s with less doping compared to the graphene transferred by thermal release tape (TRT) or poly(methyl methacrylate) (PMMA) as well as good uniformity over large areas. In addition, the sheet resistance of graphene transferred by recycled PSAF does not change considerably up to 4 times, which would be advantageous for more cost-effective and environmentally friendly production of large-area graphene films for practical applications.

Without introducing defects in the monolayer of carbon lattice, the deposition of high-κ dielectric material is a significant challenge because of the difficulty of high-quality oxide nucleation on graphene. Previous investigations of the deposition of high-κ dielectrics on graphene have often reported significant degradation of the electrical properties of graphene. In this study, we report a new way to integrate high-κ dielectrics with graphene by transferring a high-κ dielectric nanosheet onto graphene. Al2O3 film was deposited on a sacrificial layer using an atomic layer deposition process and the Al2O3 nanosheet was fabricated by removing the sacrificial layer. Top-gated graphene field-effect transistors were fabricated and characterized using the Al2O3 nanosheet as a gate dielectric. The top-gated graphene was demonstrated to have a field-effect mobility up to 2200 cm(2)/(V s). This method provides a new method for high-performance graphene devices with broad potential impacts reaching from high-frequency high-speed circuits to flexible electronics.

The synthesis of atomically thin transition-metal disulfides (MS2) with layer controllability and large-area uniformity is an essential requirement for their application in electronic and optical devices. In this work, we describe a process for the synthesis of WS2 nanosheets through the sulfurization of an atomic layer deposition (ALD) WO3 film with systematic layer controllability and wafer-level uniformity. The X-ray photoemission spectroscopy, Raman, and photoluminescence measurements exhibit that the ALD-based WS2 nanosheets have good stoichiometry, clear Raman shift, and bandgap dependence as a function of the number of layers. The electron mobility of the monolayer WS2 measured using a field-effect transistor (FET) with a high-k dielectric gate insulator is shown to be better than that of CVD-grown WS2, and the subthreshold swing is comparable to that of an exfoliated MoS2 FET device. Moreover, by utilizing the high conformality of the ALD process, we have developed a process for the fabrication of WS2 nanotubes.

Hysteretic metal-insulator transitions (MIT) mediated by ionic dynamics or ferroic phase transitions underpin emergent applications for nonvolatile memories and logic devices. The vast majority of applications and studies have explored the MIT coupled to the electric field or temperarture. Here, we argue that MIT coupled to ionic dynamics should be controlled by mechanical stimuli, the behavior we refer to as the piezochemical effect. We verify this effect experimentally and demonstrate that it allows both studying materials physics and enabling novel data storage technologies with mechanical writing and current-based readout.

We report the fabrication of graphene-encapsulated nanoballs with copper nanoparticle (Cu NP) cores whose size range from 40 nm to 1 μm using a solid carbon source of poly(methyl methacrylate) (PMMA). The Cu NPs were prone to agglomerate during the annealing process at high temperatures of 800 to 900 °C when gas carbon source such as methane was used for the growth of graphene. On the contrary, the morphologies of the Cu NPs were unchanged during the growth of graphene at the same temperature range when PMMA coating was used. The solid source of PMMA was first converted to amorphous carbon layers through a pyrolysis process at the temperature regime of 400 °C, which prevented the Cu NPs from agglomeration, and they were converted to few-layered graphene (FLG) at the elevated temperatures. Raman and transmission electron microscope analyses confirmed the synthesis of FLG with thickness of approximately 3 nm directly on the surface of the Cu NPs. X-ray diffraction and X-ray photoelectron spectroscopy analyses, along with electrical resistance measurement according to temperature changes showed that the FLG-encapsulated Cu NPs were highly resistant to oxidation even after exposure to severe oxidation conditions.

Single tetracyanoethyelene (TCNE) molecules on Cu(111) are reversibly switched among five states by applying voltage pulses with the tip of a scanning tunneling microscope. A pronounced Kondo resonance in tunneling spectroscopy indicates that one of the states is magnetic. Side bands of the Kondo resonance appear at energies which correspond to inter- and intramolecular vibrational modes. Density functional theory suggests that molecular deformation changes the occupancy in TCNE's molecular orbitals, thus producing the magnetic state.

Nuclear ribonucleoprotein (RNP) complexes that contain the U1 and U2 RNA of chromatin of Novikoff hepatoma cells were extracted with 0.01 M Tris-HCl (pH 8.0) after the nuclei were initially washed with 0.075 M NaCl and 0.025 M EDTA (pH 8.0). These RNP complexes were purified by chromatography on Sepharose 6B columns and centrifugation on sucrose density gradients. The identity of the U1 and U2 RNA in these particles was established by their electrophoretic mobility in polyacrylamide gels and their T1 RNase fingerprints which were identical with those of authentic U1 and U2 RNA (R. Reddy et al. (1974), J. Biol. Chem.249, 6486-6494; H. Shibata et al. (1974), Mol. Cell. Biochem. 4, 3-19). The nuclear riboncleoproteins had a buoyant density of 1.47 g/ml in CsCl gradients. Two-dimensional polyacrylamide gel electrophoresis of their proteins showed these RNP complexes contain 10 polypeptide spots, of which two are phosphorylated in vivo.

Studies were made on the effects of alpha-amanitin, cycloheximide, and thioacetamide on synthesis and content of low molecular weight nuclear RNA. Cycloheximide, an inhibitor of protein synthesis and the synthesis of 45S pre-rRNA and 5S RNA, also inhibited synthesis of nuclear U1 and U3 RNAs. alpha-Amanitin, an inhibited the synthesis of U1 and U2 low molecular weight nuclear RNA. Thioacetamide, which induces nucleolar hypertrophy and increased nucleolar RNA polymerase activity, markedly increased synthesis of 5.8S RNA and U3 RNA. These results show that syntheses of individual low molecular weight nuclear (LMWN) RNAs are controlled by different regulatory mechanisms. In particular, there appears to be a specific relationship between U3 RNA and functional states of the nucleolus.