Protomer of Imipramine Captured in Cucurbit[7]uril.

Small molecules possessing multiple proton-accessible sites are important not only to many biological systems but also to host-guest chemistry; their protonation states are causal to boosting or hindering specific host-guest interactions. However, determining the protonation site is not trivial. Herein, we conduct electrospray ionization ion mobility spectrometry-mass spectrometry to imipramine, a known molecule with two protonation sites, based on the introduction of cucurbit[7]uril as a host molecule. For protonated imipramine, the proposed strategy allows clear distinction of the two protomers as host-guest complex ions and can be leveraged to capture the energetically less preferable protomer of the protonated imipramine.

Flow Synthesis of Gigantic Porphyrinic Cages: Facile Synthesis of P12 L24 and Discovery of Kinetic Product P9 L18.

A continuous flow methodology for the facile and high-yielding synthesis of the porphyrin-based self-assembled organic cage, P12 L24 is reported, along with the serendipitous discovery of a kinetic product, P9 L18 cage, which has been characterized by MALDI-TOF MS, NMR, and AFM analysis. A theoretical study suggests a tricapped trigonal prismatic geometry for P9 L18 . Unlike P12 L24 , P9 L18 is unstable and readily decomposes into monomers and small oligomers. While the batch synthesis produces only the thermodynamic product P12 L24 , the continuous flow process generates not only the thermodynamic product but also kinetic products, such as P9 L18 , illustrating the advantages of the continuous flow process for the synthesis of self-assembled cages and the exploration of new non-equilibrium assemblies.

Dramatically Enhanced Reactivity of Fullerenes and Tetrazine towards the Inverse-Electron-Demand Diels-Alder Reaction inside a Porous Porphyrinic Cage.

Inverse-electron-demand Diels-Alder reaction (IEDDA) between fullerenes and 1,2,4,5-tetrazine generally requires harsh conditions and long reaction times due to their strong electron-accepting nature. Herein, we report a dramatic enhancement in the reactivity of the fullerenes (C60 /C70 )-tetrazine reaction inside a porous Zn-porphyrinic cage (Zn-PB) under sustainable conditions by installing a tetrazine-based axle (LA) via metal-ligand coordination bond, which modulates the cavity size to facilitate the encapsulation of fullerenes. Upon encapsulation, the close proximity of fullerenes and the tetrazine group of LA dramatically increase their reactivity towards the IEDDA reaction to form fullerene-tetrazine adducts. Furthermore, the C60 -tetrazine adduct is rearranged upon hydration to a bent-shaped C60 -pyrazoline adduct that can be released from the Zn-PB cavity in the presence of excess LA, thus catalyzing the formation of C60 -pyrazoline adduct inside Zn-PB without product inhibition.

Reduction in urban atmospheric CO2 enhancement in Seoul, South Korea, resulting from social distancing policies during the COVID-19 pandemic.

With the spread of the COVID-19 virus globally, cities worldwide have implemented unprecedented social distancing policies to mitigate infection rates. Many studies have demonstrated that improved air quality and reduced carbon emissions have resulted from the COVID-19 pandemic. Yet, questions remain regarding changes in atmospheric CO2 concentrations because of the complex cycles involving the interaction of CO2 with the natural environment. In this study, we compared the changes in urban CO2 enhancement (△CO2) reflecting the contribution of local CO2 emissions to the atmospheric CO2 in urban areas, according to the intensity of social distancing policies implemented during the COVID-19 pandemic in Seoul, South Korea. We used data from three CO2 ground observation sites in the central area of Seoul and outside the urban area of Seoul. By comparing the urban CO2 concentration in Seoul with that of the background area using two different methods, considering both vertical and horizontal differences in CO2 concentration, we quantified the △CO2 of the pre-COVID-19 period and two COVID-19 periods, during which intensive social distancing policies with different intensities were implemented (Level 1, Level 2.5). During the pre-COVID-19 period, the average △CO2 calculated using the two methods was 24.82 ppm, and it decreased significantly to 16.42 and 14.36 ppm during the Level 1 and Level 2.5 periods, respectively. In addition, the urban contribution of Seoul to atmospheric CO2 concentration decreased from 5.27% during the pre-COVID-19 period to 3.54% and 3.19% during the Level 1 and Level 2.5 periods, respectively. The results indicate that the social distancing policies implemented in Seoul resulted in reduced local CO2 emissions, leading to a reduction in atmospheric CO2 concentration. Interestingly, it also shows that the extent of atmospheric CO2 concentration reduction can be greatly affected by the intensity of policies. Our study suggests that changes in human activity could reduce the urban direct contribution to the background CO2 concentration helping to further mitigate climate change.

One-pot Synthesis of a Truncated Cone-shaped Porphyrin Macrocycle and Its Self-assembly into Permanent Porous Material.

Here, we report the synthesis of a truncated cone-shaped triangular porphyrinic macrocycle, P3 L3 , via a single step imine condensation of a cis-diaminophenylporphyrin and a bent dialdehyde-based linker as building units. X-ray diffraction analysis reveals that the truncated cone-shaped P3 L3 molecules are stacked on top of each other by π⋯π and CH⋯π interactions, to form 1.7 nm wide hollow columns in the solid state. The formation of the triangular macrocycle is corroborated by quantum chemical calculations. The permanent porosity of the P3 L3 crystals is demonstrated by several gas sorption experiments and powder X-ray diffraction analysis.

Bioinspired Gradient Conductivity and Stiffness for Ultrasensitive Electronic Skins.

Hierarchical and gradient structures in biological systems with special mechanical properties have inspired innovations in materials design for construction and mechanical applications. Analogous to the control of stress transfer in gradient mechanical structures, the control of electron transfer in gradient electrical structures should enable the development of high-performance electronics. This paper demonstrates a high performance electronic skin (e-skin) via the simultaneous control of tactile stress transfer to an active sensing area and the corresponding electrical current through the gradient structures. The flexible e-skin sensor has extraordinarily high piezoresistive sensitivity at low power and linearity over a broad pressure range based on the conductivity-gradient multilayer on the stiffness-gradient interlocked microdome geometry. While stiffness-gradient interlocked microdome structures allow the efficient transfer and localization of applied stress to the sensing area, the multilayered structure with gradient conductivity enables the efficient regulation of piezoresistance in response to applied pressure by gradual activation of current pathways from outer to inner layers, resulting in a pressure sensitivity of 3.8 × 105 kPa-1 with linear response over a wide range of up to 100 kPa. In addition, the sensor indicated a rapid response time of 0.016 ms, a low minimum detectable pressure level of 0.025 Pa, a low operating voltage (100 µV), and high durability during 8000 repetitive cycles of pressure application (80 kPa). The high performance of the e-skin sensor enables acoustic wave detection, differentiation of gas characterized by different densities, subtle tactile manipulation of objects, and real-time monitoring of pulse pressure waveform.

High-Resolution Filtration Patterning of Silver Nanowire Electrodes for Flexible and Transparent Optoelectronic Devices.

Silver nanowire (AgNW) electrodes attract significant attention in flexible and transparent optoelectronic devices; however, high-resolution patterning of AgNW electrodes remains a considerable challenge. In this study, we have introduced a simple technique for high-resolution solution patterning of AgNW networks, based on simple filtration of AgNW solution on a patterned polyimide shadow mask. This solution process allows the smallest pattern size of AgNW electrodes, down to a width of 3.5 µm. In addition, we have demonstrated the potential of these patterned AgNW electrodes for applications in flexible optoelectronic devices, such as photodetectors. Specifically, for flexible and semitransparent UV photodetectors, AgNW electrodes are embedded in sputtered ZnO films to enhance the photocurrent by light scattering and trapping, which resulted in a significantly enhanced photocurrent (up to 800%) compared to devices based on AgNW electrodes mounted on top of ZnO films. In addition, our photodetector could be operated well under extremely bent conditions (bending radius of approximately 770 µm) and provide excellent durability even after 500 bending cycles.

Transfer Printing of Electronic Functions on Arbitrary Complex Surfaces.

Transfer printing of electronic functions on arbitrary surfaces is essential for next-generation applications of skin-attachable electronics, wearable sensors, and implantable/medical devices. For transfer printing of electronic functions on multidimensional surfaces, such as curved regions of the skin and different objects, various strategies have been devised based on the materials and structural design of electronic components and transfer stamps, such as ultrathin membranes or in-plane structures of electronic components, soft interfacial glues or adhesives between devices and surfaces, and smart transfer adhesives with bioinspired micro/nanostructures. These techniques enable high conformity of adhesion, mechanical robustness, and high compliance of electronic devices on arbitrary surfaces under mechanical deformation. In this Perspective, we provide an overview of recent transfer printing techniques and discuss their advantages and challenges. In addition, we report a recently developed transfer printing technique based on bioinspired smart adhesives with reversible adhesion, which enables compliant electronics on various arbitrary complex surfaces without performance degradation, providing solutions for various technical challenges remaining in transfer printing. Finally, we present potential applications of transfer printing and future perspectives for this emerging field.

Gate-Tunable and Programmable n-InGaAs/Black Phosphorus Heterojunction Diodes.

Semiconductor heterostructures have enabled numerous applications in diodes, photodetectors, junction field-effect transistors, and memory devices. Two-dimensional (2D) materials and III-V compound semiconductors are two representative materials providing excellent heterojunction platforms for the fabrication of heterostructure devices. The marriage between these semiconductors with completely different crystal structures may enable a new heterojunction with unprecedented physical properties. In this study, we demonstrate a multifunctional heterostructure device based on 2D black phosphorus and n-InGaAs nanomembrane semiconductors that exhibit gate-tunable, photoresponsive, and programmable diode characteristics. The device exhibits clear rectification with a large gate-tunable forward current, which displays rectification and switching with a maximum rectification ratio of 4600 and an on/off ratio exceeding 105, respectively. The device also offers nonvolatile memory properties, including large hysteresis and stable retention of storage charges. By combining the memory and gate-tunable rectifying properties, the rectification ratio of the device can be controlled and memorized from 0.06 to 400. Moreover, the device can generate three different electrical signals by combining a photoresponsivity of 0.704 A/W with the gate-tunable property, offering potential applications, for example, multiple logic operator. This work presents a heterostructure design based on 2D and III-V compound semiconductors, showing unique physical properties for the development of multifunctional heterostructure devices.

Preliminary Comparison of the Efficacy and Safety of Needle-Embedding Therapy with Acupuncture for Atopic Dermatitis Patients.

OBJECTIVES: Among Traditional Korean Medicine approaches, needle-embedding therapy is used in various fields and consistently studied; however, there have been no clinical studies of the treatment of adult atopic dermatitis (AD) with needle-embedding therapy. Thus, there is a need to investigate the effects of needle-embedding therapy for treatment of AD. This study was performed to identify possible effects of needle-embedding therapy at Quchi acupoint (LI11) on AD and to compare these effects with those of acupuncture therapy. METHODS: A total of 14 participants were enrolled in this study. Participants received acupuncture or needle-embedding treatments for 4 weeks and then were followed for an additional 2 weeks because of safety assessment. The participants were divided into 2 groups: the acupuncture group, receiving treatment at Quchi acupoint (LI11) 3 times per week, and the needle-embedding group, receiving treatment at Quchi acupoint (LI11) once per week. The groups were compared on the basis of the SCORing Atopic Dermatitis (SCORAD) index, Transepidermal Water Loss (TEWL), skin hydration, and Dermatology Life Quality Index (DLQI) at baseline and 1 week after treatment was completed (5th week). RESULTS: The SCORAD index, TEWL, Skin hydration, and DLQI at 1 week after treatment were significantly improved in both groups (p<0.05). However, there were no significant differences between the acupuncture and needle-embedding groups in any of the main evaluation indices (p>0.05). The study participants received a total of 84 acupuncture treatments or 28 needle-embedding treatments. No adverse events occurred during the study period. CONCLUSIONS: Based on changes in the SCORAD index, TEWL, skin hydration, and DLQI value, we found that both needle-embedding and acupuncture treatments at the Quchi acupoint (LI11) were effective in decreasing the symptoms of AD and exhibited similar therapeutic effects, which suggests that needle-embedding treatment may be more clinically convenient than acupuncture, with longer effects and fewer treatments.

Nanometric Water Channels in Water-in-Salt Lithium Ion Battery Electrolyte.

Lithium-ion batteries (LIBs) have been deployed in a wide range of energy-storage applications and helped to revolutionize technological development. Recently, a lithium ion battery that uses superconcentrated salt water as its electrolyte has been developed. However, the role of water in facilitating fast ion transport in such highly concentrated electrolyte solutions is not fully understood yet. Here, femtosecond IR spectroscopy and molecular dynamics simulations are used to show that bulk-like water coexists with interfacial water on ion aggregates. We found that dissolved ions form intricate three-dimensional ion-ion networks that are spontaneously intertwined with nanometric water hydrogen-bonding networks. Then, hydrated lithium ions move through bulk-like water channels acting like conducting wires for lithium ion transport. Our experimental and simulation results indicate that water structure-breaking chaotropic anion salts with a high propensity to form ion networks in aqueous solutions would be excellent candidates for water-based LIB electrolytes. We anticipate that the present work will provide guiding principles for developing aqueous LIB electrolytes.

Fano cavity test for electron Monte Carlo transport algorithms in magnetic fields: comparison between EGSnrc, PENELOPE, MCNP6 and Geant4.

A Fano cavity test was performed for four general-purpose Monte Carlo codes, EGSnrc, PENELOPE, MCNP6 and Geant4 to evaluate the accuracy of their electron transport algorithms in magnetic fields. In the simulations, a plane-parallel ionization chamber was modelled as a circular gas disk sandwiched between two circular solid wall disks. It was assumed that an isotropic and uniform line source per unit mass along the central axis of the gas and solid emits mono-energetic electrons with energies 0.01, 0.1, 1.0 and 3.0 MeV at different magnetic field strengths 0, 0.35, 1.0, 1.5 and 3.0 T in the electron transport mode (no Bremsstrahlung). The relative difference between the calculated dose to the gas region and the initial total energy of emitted electrons per unit mass was defined as the accuracy of Monte Carlo codes. In all results, EGSnrc with the enhanced electric and magnetic field (EEMF) macros was not considerably sensitive to the step size parameters and showed accuracy less than 0.18% ± 0.06% with a coverage factor k = 2. The other codes could not achieve competent accuracy with their default settings of step size parameters, compared to EGSnrc with the EEMF macros. With the step size parameters carefully selected, the accuracy of PENELOPE and MCNP6 was within 1.0% and 0.4%, respectively. However, Geant4 showed accuracy within 1.7% except in 3.0 T. EGSnrc with the EEMF macros achieved the best accuracy for the Fano test at the electron energies and the magnetic field strengths investigated in this study and thus, would be recommended to simulate dose responses of ionization chambers in the presence of magnetic fields.

Transparent and conductive nanomembranes with orthogonal silver nanowire arrays for skin-attachable loudspeakers and microphones.

We demonstrate ultrathin, transparent, and conductive hybrid nanomembranes (NMs) with nanoscale thickness, consisting of an orthogonal silver nanowire array embedded in a polymer matrix. Hybrid NMs significantly enhance the electrical and mechanical properties of ultrathin polymer NMs, which can be intimately attached to human skin. As a proof of concept, we present a skin-attachable NM loudspeaker, which exhibits a significant enhancement in thermoacoustic capabilities without any significant heat loss from the substrate. We also present a wearable transparent NM microphone combined with a micropyramid-patterned polydimethylsiloxane film, which provides excellent acoustic sensing capabilities based on a triboelectric voltage signal. Furthermore, the NM microphone can be used to provide a user interface for a personal voice-based security system in that it can accurately recognize a user's voice. This study addressed the NM-based conformal electronics required for acoustic device platforms, which could be further expanded for application to conformal wearable sensors and health care devices.

Asymmetric polar localization dynamics of the serine chemoreceptor protein Tsr in Escherichia coli.

The spatial location of proteins in living cells can be critical for their function. For example, the E. coli chemotaxis machinery is localized to the cell poles. Here we describe the polar localization of the serine chemoreceptor Tsr using a strain synthesizing a fluorescent Tsr-Venus fusion at a low level from a single-copy chromosomal construct. Using photobleaching and imaging during recovery by new synthesis, we observed distinct asymmetry between a bright (old) pole and a dim (new) pole. The old pole was shown to be a more stable cluster and to recover after photobleaching faster, which is consistent with the hypothesis that newly synthesized Tsr proteins are inserted directly at or near the old pole. The new pole was shown to be a less stable cluster and to exchange proteins freely with highly mobile Tsr-Venus proteins diffusing in the membrane. We propose that the new pole arises from molecules escaping from the old pole and diffusing to the new pole where a more stable cluster forms over time. Our localization imaging data support a model in which a nascent new pole forms prior to stable cluster formation.

Flexible Ferroelectric Sensors with Ultrahigh Pressure Sensitivity and Linear Response over Exceptionally Broad Pressure Range.

Flexible pressure sensors with a high sensitivity over a broad linear range can simplify wearable sensing systems without additional signal processing for the linear output, enabling device miniaturization and low power consumption. Here, we demonstrate a flexible ferroelectric sensor with ultrahigh pressure sensitivity and linear response over an exceptionally broad pressure range based on the material and structural design of ferroelectric composites with a multilayer interlocked microdome geometry. Due to the stress concentration between interlocked microdome arrays and increased contact area in the multilayer design, the flexible ferroelectric sensors could perceive static/dynamic pressure with high sensitivity (47.7 kPa-1, 1.3 Pa minimum detection). In addition, efficient stress distribution between stacked multilayers enables linear sensing over exceptionally broad pressure range (0.0013-353 kPa) with fast response time (20 ms) and high reliability over 5000 repetitive cycles even at an extremely high pressure of 272 kPa. Our sensor can be used to monitor diverse stimuli from a low to a high pressure range including weak gas flow, acoustic sound, wrist pulse pressure, respiration, and foot pressure with a single device.

Graph Theory and Ion and Molecular Aggregation in Aqueous Solutions.

In molecular and cellular biology, dissolved ions and molecules have decisive effects on chemical and biological reactions, conformational stabilities, and functions of small to large biomolecules. Despite major efforts, the current state of understanding of the effects of specific ions, osmolytes, and bioprotecting sugars on the structure and dynamics of water H-bonding networks and proteins is not yet satisfactory. Recently, to gain deeper insight into this subject, we studied various aggregation processes of ions and molecules in high-concentration salt, osmolyte, and sugar solutions with time-resolved vibrational spectroscopy and molecular dynamics simulation methods. It turns out that ions (or solute molecules) have a strong propensity to self-assemble into large and polydisperse aggregates that affect both local and long-range water H-bonding structures. In particular, we have shown that graph-theoretical approaches can be used to elucidate morphological characteristics of large aggregates in various aqueous salt, osmolyte, and sugar solutions. When ion and molecular aggregates in such aqueous solutions are treated as graphs, a variety of graph-theoretical properties, such as graph spectrum, degree distribution, clustering coefficient, minimum path length, and graph entropy, can be directly calculated by considering an ensemble of configurations taken from molecular dynamics trajectories. Here we show percolating behavior exhibited by ion and molecular aggregates upon increase in solute concentration in high solute concentrations and discuss compelling evidence of the isomorphic relation between percolation transitions of ion and molecular aggregates and water H-bonding networks. We anticipate that the combination of graph theory and molecular dynamics simulation methods will be of exceptional use in achieving a deeper understanding of the fundamental physical chemistry of dissolution and in describing the interplay between the self-aggregation of solute molecules and the structure and dynamics of water.

Ultrafast fluxional exchange dynamics in electrolyte solvation sheath of lithium ion battery.

Lithium cation is the charge carrier in lithium-ion battery. Electrolyte solution in lithium-ion battery is usually based on mixed solvents consisting of polar carbonates with different aliphatic chains. Despite various experimental evidences indicating that lithium ion forms a rigid and stable solvation sheath through electrostatic interactions with polar carbonates, both the lithium solvation structure and more importantly fluctuation dynamics and functional role of carbonate solvent molecules have not been fully elucidated yet with femtosecond vibrational spectroscopic methods. Here we investigate the ultrafast carbonate solvent exchange dynamics around lithium ions in electrolyte solutions with coherent two-dimensional infrared spectroscopy and find that the time constants of the formation and dissociation of lithium-ion···carbonate complex in solvation sheaths are on a picosecond timescale. We anticipate that such ultrafast microscopic fluxional processes in lithium-solvent complexes could provide an important clue to understanding macroscopic mobility of lithium cation in lithium-ion battery on a molecular level.

High-Performance MoS2/CuO Nanosheet-on-One-Dimensional Heterojunction Photodetectors.

van der Waals heterostructures based on stacked two-dimensional (2D) materials provide novel device structures enabling high-performance electronic and optoelectronic devices. While 2D-2D or 2D-bulk heterostructures have been largely explored for fundamental understanding and novel device applications, 2D-one-dimensional (1D) heterostructures have been rarely studied because of the difficulty in achieving high-quality heterojunctions between 2D and 1D structures. In this study, we introduce nanosheet-on-1D van der Waals heterostructure photodetectors based on a wet-transfer printing of a MoS2 nanosheet on top of a CuO nanowire (NW). MoS2/CuO nanosheet-on-1D photodetectors show an excellent photocurrent rectification ratio with an ideality factor of 1.37, which indicates the formation of an atomically sharp interface and a high-quality heterojunction in the MoS2/CuO heterostructure by wet-transfer-enhanced van der Waals bonding. Furthermore, nanosheet-on-1D heterojunction photodetectors exhibit excellent photodetection capabilities with an ultrahigh photoresponsivity (∼157.6 A/W), a high rectification ratio (∼6000 at ±2 V), a low dark current (∼38 fA at -2 V), and a fast photoresponse time (∼34.6 and 51.9 ms of rise and decay time), which cannot be achievable with 1D-on-nanosheet heterojunction photodetectors. The wet-transfer printing of nanosheet-on-1D heterostructures introduced in this study provides a robust platform for the fundamental study of various combinations of 2D-on-1D heterostructures and their applications in novel heterojunction devices.

Computational Vibrational Spectroscopy of HDO in Osmolyte-Water Solutions.

The IR absorption and time-resolved IR spectroscopy of the OD stretch mode of HDO in water was successfully used to study osmolyte effects on water H-bonding network. Protecting osmolytes such as sorbitol and trimethylglycine (TMG) make the vibrational OD stretch band red-shifted, whereas urea affects the OD band marginally. Furthermore, we recently showed that, even though sorbitol and TMG cause a slow-down of HDO rotation in their aqueous solutions, urea does not induce any change in the rotational relaxation of HDO in aqueous urea solutions even at high concentrations. To clarify the underlying osmolyte effects on water H-bonding structure and dynamics, we performed molecular dynamics (MD) simulations of a variety of aqueous osmolyte solutions. Using the vibrational solvatochromism model for the OD stretch mode and taking into account the vibrational non-Condon and polarization effects on the OD transition dipole moment, we then calculated the IR absorption spectra and rotational anisotropy decay of the OD stretch mode of HDO for the sake of direct comparisons with our experimental results. The simulation results on the OD stretch IR absorption spectra and the rotational relaxation rate of HDO in osmolyte solutions are found to be in quantitative agreement with experimental data, which confirms the validity of the MD simulation and vibrational solvatochromism approaches. As a result, it becomes clear that the protecting osmolytes like sorbitol and TMG significantly modulate water H-bonding network structure, while urea perturbs water structure little. We anticipate that the computational approach discussed here will serve as an interpretive method with atomic-level chemical accuracy of current linear and nonlinear time-resolved IR spectroscopy of structure and dynamics of water near the surfaces of membranes and proteins under crowded environments.

Octopus-Inspired Smart Adhesive Pads for Transfer Printing of Semiconducting Nanomembranes.

By mimicking muscle actuation to control cavity-pressure-induced adhesion of octopus suckers, smart adhesive pads are developed in which the thermoresponsive actuation of a hydrogel layer on elastomeric microcavity pads enables excellent switchable adhesion in response to a thermal stimulus (maximum adhesive strength: 94 kPa, adhesion switching ratio: ≈293 for temperature change between 22 and 61 °C).