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.

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.

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.

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.

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.

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.

Dynamics of the serine chemoreceptor in the Escherichia coli inner membrane: a high-speed single-molecule tracking study.

We investigated the mobility of the polar localized serine chemoreceptor, Tsr, labeled by the fluorescent protein Venus in the inner membrane of live Escherichia coli cells at observation rates up to 1000 Hz. A fraction (7%) of all Tsr molecules shows free diffusion over the entire cell surface with an average diffusion coefficient of 0.40 ± 0.01 µm(2) s(-1). The remaining molecules were found to be ultimately confined in compartments of size 290 ± 15 nm and showed restricted diffusion at an inner barrier found at 170 ± 10 nm. At the shortest length-scales (<170 nm), all Tsr molecules diffuse equally. Disruption of the cytoskeleton and rounding of the cells resulted in an increase in the mobile fraction of Tsr molecules and a fragmenting of the previously polar cluster of Tsr consistent with a curvature-based mechanism of Tsr cluster maintenance.

Vibrational solvatochromism: towards systematic approach to modeling solvation phenomena.

Vibrational solvatochromic frequency shift of IR probe is an effect of interaction between local electric field and IR probe in condensed phases. Despite prolonged efforts to develop empirical maps for vibrational frequency shifts and transition dipoles of IR probes, a systematic approach to ab initio calculation of vibrational solvatochromic charges and multipoles has not been developed. Here, we report on density functional theory (DFT) calculations of N-methylacetamide (NMA) frequency shifts using implicit and coarse-grained models. The solvatochromic infrared spectral shifts are estimated based on the distributed multipole analysis of electronic densities calculated for gas-phase equilibrium structure of NMA. Thus obtained distributed solvatochromic multipole parameters are used to calculate the amide I vibrational frequency shifts of NMA in water clusters that mimic the instantaneous configurations of the liquid water. Our results indicate that the spectral shifts are primarily electrostatic in nature and can be quantitatively reproduced using the proposed model with semi-quantitative accuracy when compared to the corresponding DFT results.

Vibrational spectroscopic determination of local solvent electric field, solute-solvent electrostatic interaction energy, and their fluctuation amplitudes.

IR probes have been extensively used to monitor local electrostatic and solvation dynamics. Particularly, their vibrational frequencies are highly sensitive to local solvent electric field around an IR probe. Here, we show that the experimentally measured vibrational frequency shifts can be inversely used to determine local electric potential distribution and solute-solvent electrostatic interaction energy. In addition, the upper limits of their fluctuation amplitudes are estimated by using the vibrational bandwidths. Applying this method to fully deuterated N-methylacetamide (NMA) in D(2)O and examining the solvatochromic effects on the amide I' and II' mode frequencies, we found that the solvent electric potential difference between O(═C) and D(-N) atoms of the peptide bond is about 5.4 V, and thus, the approximate solvent electric field produced by surrounding water molecules on the NMA is 172 MV/cm on average if the molecular geometry is taken into account. The solute-solvent electrostatic interaction energy is estimated to be -137 kJ/mol, by considering electric dipole-electric field interaction. Furthermore, their root-mean-square fluctuation amplitudes are as large as 1.6 V, 52 MV/cm, and 41 kJ/mol, respectively. We found that the water electric potential on a peptide bond is spatially nonhomogeneous and that the fluctuation in the electrostatic peptide-water interaction energy is about 10 times larger than the thermal energy at room temperature. This indicates that the peptide-solvent interactions are indeed important for the activation of chemical reactions in aqueous solution.

Vibrational solvatochromism and electrochromism. II. Multipole analysis.

Small infrared probe molecules have been widely used to study local electrostatic environment in solutions and proteins. Using a variety of time- and frequency-resolved vibrational spectroscopic methods, one can accurately measure the solvation-induced vibrational frequency shifts and the timescales and amplitudes of frequency fluctuations of such IR probes. Since the corresponding frequency shifts are directly related to the local electric field and its spatial derivatives of the surrounding solvent molecules or amino acids in proteins, one can extract information on local electric field around an IR probe directly from the vibrational spectroscopic results. Here, we show that, carrying out a multipole analysis of the solvatochromic frequency shift, the solvatochromic dipole contribution to the frequency shift is not always the dominant factor. In the cases of the nitrile-, thiocyanato-, and azido-derivatized molecules, the solvatochromic quadrupole contributions to the corresponding stretch mode frequency shifts are particularly large and often comparable to the solvatochromic dipole contributions. Noting that the higher multipole moment-solvent electric field interactions are short range effects in comparison to the dipole interaction, the H-bonding interaction-induced vibrational frequency shift can be caused by such short-range multipole-field interaction effects. We anticipate that the present multipole analysis method specifically developed to describe the solvatochromic vibrational frequency shifts will be useful to understand the intermolecular interaction-induced vibrational property changes and to find out a relationship between vibrational solvatochromism and electrochromism of IR probes in condensed phases.

Hofmeister anionic effects on hydration electric fields around water and peptide.

Specific ion effects on water dynamics and local solvation structure around a peptide are important in understanding the Hofmeister series of ions and their effects on protein stability in aqueous solution. Water dynamics is essentially governed by local hydrogen-bonding interactions with surrounding water molecules producing hydration electric field on each water molecule. Here, we show that the hydration electric field on the OD bond of HOD molecule in water can be directly estimated by measuring its OD stretch infrared (IR) radiation frequency shift upon increasing ion concentration. For a variety of electrolyte solutions containing Hofmeister anions, we measured the OD stretch IR bands and estimated the hydration electric field on the OD bond to be about a hundred MV∕cm with standard deviation of tens of MV∕cm. As anion concentration increases from 1 to 6 M, the hydration electric field on the OD bond decreases by about 10%, indicating that the local H-bond network is partially broken by dissolved ions. However, the measured hydration electric fields on the OD bond and its fluctuation amplitudes for varying anions are rather independent on whether the anion is a kosmotrope or a chaotrope. To further examine the Hofmeister effects on H-bond solvation structure around a peptide bond, we examined the amide I' and II' mode frequencies of N-methylacetamide in various electrolyte D(2)O solutions. It is found that the two amide vibrational frequencies are not affected by ions, indicating that the H-bond solvation structure in the vicinity of a peptide remains the same irrespective of the concentration and character of ions. The present experimental results suggest that the Hofmeister anionic effects are not caused by direct electrostatic interactions of ions with peptide bond or water molecules in its first solvation shell. Furthermore, even though the H-bond network of water is affected by ions, thus induced change of local hydration electric field on the OD bond of HOD is not in good correlation with the well-known Hofmeister series. We anticipate that the present experimental results provide an important clue about the Hofmeister effect on protein structure and present a discussion on possible alternative mechanisms.

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.

Vibrational solvatochromism and electrochromism of cyanide, thiocyanate, and azide anions in water.

Small IR probe molecules have been found to be useful to measure local electric fields in condensed phases and proteins and also to study nucleic acid and protein structure and dynamics by monitoring their vibrational couplings and frequency shifts. However, it is still difficult to accurately describe the vibrational solvatochromic frequency shifts of such IR probes, because the local electric fields produced by surrounding solvent molecules or by protein peptide and side groups are spatially non-uniform and highly inhomogeneous around a probe. We recently developed a distributed interaction site model to describe the vibrational solvatochromism and electrochromism of nitrile-, thiocyanato-, and azido-derivatized compounds and amino acids in solutions. Here, the nitrile or azido stretch is the maker mode. It was found that those interaction sites distributed over the IR probe molecule collectively act as an antenna sensing local electric field distributions around the IR probes. Once the vibrational solvatochromism of a given IR probe is understood, it becomes possible to quantitatively describe their vibrational Stark effects. Carrying out quantum chemistry calculations of cyanide, thiocyanate, and azide anions in water clusters, we extended the distributed site model for ionic IR probes and calculated the vibrational Stark tuning rates for direct comparisons with experimental results. It turns out that the charge transfers from an anionic solute to surrounding water molecules are significant, but their effects on vibrational solvatochromism and electrochromism of pseudohalide ionic IR probes are not. We anticipate that the present computational results will be of use to establish the relationship between vibrational frequency of an ionic IR probe and local electric field in condensed phases and protein matrices.

Chiroptical nature of two-exciton states of light-harvesting complex: Doubly resonant three-wave-mixing spectroscopy.

Photosynthetic light-harvesting complex is a coupled multichromophore system. Due to electronic couplings between neighboring chlorophylls in the complex, the one- and two-exciton states are delocalized and they can be written as linear combinations of singly and doubly excited configurations, respectively. Despite that the chiroptical properties of one-exciton states in such a multichromophore system have been investigated by using linear optical activity measurement techniques; those of two-exciton states have not been studied before due to a lack of appropriate measurement methods. Here, we present a theoretical description on chiroptical chi((2)) spectroscopy and show that it can be used to investigate such properties of a photosynthetic light-harvesting system, which is the Fenna-Matthews-Olson complex, consisting of seven bacteriochlorophylls in its protein subunit. To simulate the doubly resonant sum- and difference-frequency-generation spectra of the complex, one- and two-exciton transition dipoles were calculated. Carrying out quantum chemistry calculations of electronically excited states of a model bacteriochlorophyll system and taking into account the dipole-induced dipole electronic transition processes between the ground state and two-exciton states, we could calculate the two-dimensional sum-frequency-generation spectra revealing dominant second-order chiroptical transition pathways and involved one- and two-exciton states. It is believed that the present computational scheme and the theoretically proposed doubly resonant two-dimensional three-wave-mixing spectroscopy would be of use to shed light on the chiroptical natures of two-exciton states of arbitrary coupled multichromophore systems.

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.

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.

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.

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.