Memristors with diffusive dynamics as synaptic emulators for neuromorphic computing

The accumulation and extrusion of Ca2+ in the pre- and postsynaptic compartments play a critical role in initiating plastic changes in biological synapses. To emulate this fundamental process in electronic devices, we developed diffusive Ag-in-oxide memristors with a temporal response during and after stimulation similar to that of the synaptic Ca2+ dynamics. In situ high-resolution transmission electron microscopy and nanoparticle dynamics simulations both demonstrate that Ag atoms disperse under electrical bias and regroup spontaneously under zero bias because of interfacial energy minimization, closely resembling synaptic influx and extrusion of Ca2+, respectively. The diffusive memristor and its dynamics enable a direct emulation of both short- and long-term plasticity of biological synapses and represent a major advancement in hardware implementation of neuromorphic functionalities

Anatomy of Ag/Hafnia‐Based Selectors with 1010 Nonlinearity

Sneak path current is a significant remaining obstacle to the utilization of large crossbar arrays for non-volatile memories and other applications of memristors. A two-terminal selector device with an extremely large current-voltage nonlinearity and low leakage current could solve this problem. We present here a Ag/oxide-based threshold switching (TS) device with attractive features such as high current-voltage nonlinearity (~1010 ), steep turn-on slope (less than 1 mV/dec), low OFF-state leakage current (~10-14 A), fast turn ON/OFF speeds (108 cycles). The feasibility of using this selector with a typical memristor has been demonstrated by physically integrating them into a multilayered 1S1R cell. Structural analysis of the nanoscale crosspoint device suggests that elongation of a Ag nanoparticle under voltage bias followed by spontaneous reformation of a more spherical shape after power off is responsible for the observed threshold switching of the device. Such mechanism has been quantitatively verified by the Ag nanoparticle dynamics simulation based on thermal diffusion assisted by bipolar electrode effect and interfacial energy minimization

Revealing Brown Carbon Chromophores Produced in Reactions of Methylglyoxal with Ammonium Sulfate

Atmospheric brown carbon (BrC) is an important contributor to light absorption and climate forcing by aerosols. Reactions between small water-soluble carbonyls and ammonia or amines have been identified as one of the potential pathways of BrC formation. However, detailed chemical characterization of BrC chromophores has been challenging and their formation mechanisms are still poorly understood. Understanding BrC formation is impeded by the lack of suitable methods which can unravel the variability and complexity of BrC mixtures. This study applies high performance liquid chromatography (HPLC) coupled to photodiode array (PDA) detector and high resolution mass spectrometry (HRMS) to investigate optical properties and chemical composition of individual BrC components produced through reactions of methylglyoxal (MG) and ammonium sulfate (AS), both of which are abundant in the atmospheric environment. A direct relationship between optical properties and chemical composition of 30 major BrC chromophores is established. Nearly all of these chromophores are nitrogen-containing compounds that account for >70% of the overall light absorption by the MG+AS system in the 300–500 nm range. These results suggest that reduced-nitrogen organic compounds formed in reactions between atmospheric carbonyls and ammonia/amines are important BrC chromophores. It is also demonstrated that improved separation of BrC chromophores by HPLC will significantly advance understanding of BrC chemistry

Organosulfates in Humic-like Substance Fraction Isolated from Aerosols at Seven Locations in East Asia: A Study by Ultra-High-Resolution Mass Spectrometry

Humic-like substances (HULIS) in ambient aerosols collected at seven locations in East Asia were analyzed using electrospray ionization (ESI) coupled with an ultra-high-resolution mass spectrometer (UHRMS). Locations included a 3 km high mountaintop site in Taiwan, rural, suburban, and urban locations in the Pearl River Delta (PRD), South China, and in Taiwan. Organosulfates (OS) in the HULIS fraction were tentatively identified through accurate mass measurements and MS/MS spectra interpretation. In the two mountaintop samples collected in regional background atmosphere, little OS were detected, while a few hundred OS formulas were identified in the six samples taken in Taiwan and PRD. Many of the OS ions were among the most intense peaks in the negative ESI–UHRMS spectra, and their elemental formulas were identical to OS derived from biogenic volatile organic compounds (BVOCs) (e.g., monoterpenes) that have been identified in chamber studies. With OS having less than 6 carbon atoms too hydrophilic to be effectively retained in the HULIS fraction, OS containing 10 carbon atoms were the most abundant, indicating monoterpenes as important precursors of OS in the HULIS fraction. Clear spatial variation in abundance of OS was found among different atmospheric environments, with enhanced coupling of BVOCs with anthropogenic acidic aerosols observed in the PRD samples over the Taiwan samples. The double bond equivalent (DBE) values indicate the majority of OS (>90%) in the HULIS fraction are aliphatic. The elemental compositions of OS compounds containing N atoms (defined as CHONS) indicate that they are probably nitrooxy OS. Some insights into OS formation mechanisms are also gained through examining the presence/absence of perceived reactant–product formula pairs in the mass spectra. The results suggest the dominant epoxide intermediate pathway for formation of OS compounds without N atoms (defined as CHOS) and confirm the more readily hydrolyzed characteristics of the −ONO₂ group than the −OSO₃ group. There is a lack of evidence for the epoxide pathway to account for the formation of OS in the CHONS subgroup

Al-TiO₂ Composite-Modified Single-Layer Graphene as an Efficient Transparent Cathode for Organic Solar Cells

While there are challenges in tuning the properties of graphene (surface wettability, work function alignment, and carrier transport) for realizing an efficient graphene cathode in organic solar cells (OSCs), we propose and demonstrate using an Al-TiO₂ composite to modify single-layer graphene as an efficient cathode for OSCs. To unveil the contributions of the composite in addressing the aforementioned challenges, the evaporated aluminum nanoclusters in the composite benefit the graphene cathode by simultaneously achieving two roles of improving its surface wettability for subsequent TiO₂ deposition and reducing its work function to offer better energy alignment. To address challenges related to charge transport, solution-processed TiO₂ with excellent electron transport can offer charge extraction enhancement to the graphene cathode, which is essential to efficient devices. However, it is a well-known issue for methods such as spin-coating to produce uniform films on the initially hydrophobic graphene, even with improved wettability. The undesirable morphology of TiO₂ by such methods considerably inhibits its effectiveness in enhancing charge extraction. We propose a self-assembly method to deposit the solution-processed TiO₂ on the Al-covered graphene for forming the Al-TiO₂ composite. Compared with spin-coating, the self-assembly method is found to achieve more uniform coating on the graphene surface, with highly controllable thickness. Consequently, the graphene cathode modified with the Al-TiO₂ composite in inverted OSCs gives rise to enhanced power conversion efficiency of 2.58%, which is 2-fold of the previously best reported efficiency (1.27%) for graphene cathode OSCs, reaching ∼75% performance of control devices using indium tin oxide

Elemental Composition of HULIS in the Pearl River Delta Region, China: Results Inferred from Positive and Negative Electrospray High Resolution Mass Spectrometric Data

The HUmic-LIke Substances (HULIS) fraction isolated from aerosol samples collected at a rural location of the Pearl River Delta Region (PRD), China, during the harvest season was analyzed by both positive and negative mode electrospray ionization (ESI) coupled with an ultrahigh resolution mass spectrometer (UHRMS). With the remarkable resolving power and mass accuracy of ESI-UHRMS, thousands of elemental formulas were identified. Formulas detected in the positive (ESI+) and the negative (ESI-) mode complement each other due to differences in the ionization mechanism, and the use of both provides a more complete characterization of HULIS. Compounds composed of C, H, and O atoms were preferentially detected in ESI- by deprotonation, implying their acidic properties. Tandem MS and Kendrick Mass Defect analysis implies that carboxyl groups are abundant in the CHO compounds. This feature is similar to those of natural fulvic acids, but relatively smaller molecular weights are observed in the HULIS samples. A greater number of reduced nitrogen organic compounds were observed in the ESI+ compared to ESI-. Compounds with biomass burning origin including alkaloids, amino acids, and their derivatives are their probable constituents. Sulfur-containing species were dominantly detected in ESI-. The presence of sulfate fragments in the MS/MS spectra of these species and their high O/S ratios implies that they are mainly organosulfates. Organosulfates and nitrooxy-organosulfates were often the most intensive peaks in the ESI- spectra. They are believed to be products of reactive uptake of photooxidation products of reactive volatile organic compounds by acidic sulfate particles. The elemental compositions deduced from the UHRMS analysis confirm the conclusion from our previous study that biomass burning and SOA formation are both important sources of HULIS in the PRD region

Elemental Composition of HULIS in the Pearl River Delta Region, China: Results Inferred from Positive and Negative Electrospray High Resolution Mass Spectrometric Data

The HUmic-LIke Substances (HULIS) fraction isolated from aerosol samples collected at a rural location of the Pearl River Delta Region (PRD), China, during the harvest season was analyzed by both positive and negative mode electrospray ionization (ESI) coupled with an ultrahigh resolution mass spectrometer (UHRMS). With the remarkable resolving power and mass accuracy of ESI-UHRMS, thousands of elemental formulas were identified. Formulas detected in the positive (ESI+) and the negative (ESI-) mode complement each other due to differences in the ionization mechanism, and the use of both provides a more complete characterization of HULIS. Compounds composed of C, H, and O atoms were preferentially detected in ESI- by deprotonation, implying their acidic properties. Tandem MS and Kendrick Mass Defect analysis implies that carboxyl groups are abundant in the CHO compounds. This feature is similar to those of natural fulvic acids, but relatively smaller molecular weights are observed in the HULIS samples. A greater number of reduced nitrogen organic compounds were observed in the ESI+ compared to ESI-. Compounds with biomass burning origin including alkaloids, amino acids, and their derivatives are their probable constituents. Sulfur-containing species were dominantly detected in ESI-. The presence of sulfate fragments in the MS/MS spectra of these species and their high O/S ratios implies that they are mainly organosulfates. Organosulfates and nitrooxy-organosulfates were often the most intensive peaks in the ESI- spectra. They are believed to be products of reactive uptake of photooxidation products of reactive volatile organic compounds by acidic sulfate particles. The elemental compositions deduced from the UHRMS analysis confirm the conclusion from our previous study that biomass burning and SOA formation are both important sources of HULIS in the PRD region

Reactive Oxygen Species Production Mediated by Humic-like Substances in Atmospheric Aerosols: Enhancement Effects by Pyridine, Imidazole, and Their Derivatives

Ambient particulate matter (PM) can cause adverse health effects via their ability to produce reactive oxygen species (ROS). Humic-like substances (HULIS), a complex mixture of amphiphilic organic compounds, have been demonstrated to contain the majority of redox activity in the water-extractable organic fraction of PM. Reduced organic nitrogen compounds, such as alkaloids resulting from biomass burning emissions, are among HULIS constituents. In this study, we examined the redox activities of pyridine, imidazole and their alkyl derivatives using a cell-free dithiothreitol (DTT) assay under simulated physiological conditions (37 °C, pH = 7.40). These compounds were found to have little redox activity on their own as measured by the DTT assay, but they enhanced ROS generation catalyzed by 1,4-naphthoquinone (as a model quinone compound) and HULIS isolated from multiple aerosol samples. The enhancement effect by the individual nitrogen-containing bases was determined to be proportional to their amount in the assay solutions. It is postulated that the underlying mechanism involves the unprotonated N atom acting as a H-bonding acceptor to facilitate hydrogen-atom transfer in the ROS generation cycle. The enhancement capability was found to increase with their basicity (i.e., p<i>K</i>_a of their conjugated acids, BH⁺), consistent with the proposed mechanism for enhancement. Among the imidazole homologues, a linear relationship was observed between the enhancement factors (in log scale) of the unprotonated form of the imidazole compounds (B) and the p<i>K</i>_a of their conjugated acids (BH⁺). This relationship predicts that the range of alkylimidazole homologues (C₆–C₁₃) observed in atmospheric HULIS would be 1.5–4.4 times more effective than imidazole in facilitating HULIS-mediated ROS generation. Our work reveals that the ability of atmospheric PM organics to catalyze generation of ROS in cells could be affected by coexisting redox inactive organic constituents and suggests further work deploying multiple assays be conducted to quantify redox capabilities and enhancement effects of the HULIS components

Major behavioral and serologic variables by Hukou among drug users from the detoxification center and community.

<p>IDU: injection drug use.</p>*<p>Variable represents characteristic of injection drug users.</p

Social demographic characteristics among drug users from the detoxification center and community.

<p>IDU injection drug use. <i>CI</i> confidence interval.</p>*<p>Denotes significance at alpha value of 0.05.</p