Oscillatory Neural Network-Based Ising Machine Using 2D Memristors.

Neural networks are increasingly used to solve optimization problems in various fields, including operations research, design automation, and gene sequencing. However, these networks face challenges due to the nondeterministic polynomial time (NP)-hard issue, which results in exponentially increasing computational complexity as the problem size grows. Conventional digital hardware struggles with the von Neumann bottleneck, the slowdown of Moore's law, and the complexity arising from heterogeneous system design. Two-dimensional (2D) memristors offer a potential solution to these hardware challenges, with their in-memory computing, decent scalability, and rich dynamic behaviors. In this study, we explore the use of nonvolatile 2D memristors to emulate synapses in a discrete-time Hopfield neural network, enabling the network to solve continuous optimization problems, like finding the minimum value of a quadratic polynomial, and tackle combinatorial optimization problems like Max-Cut. Additionally, we coupled volatile memristor-based oscillators with nonvolatile memristor synapses to create an oscillatory neural network-based Ising machine, a continuous-time analog dynamic system capable of solving combinatorial optimization problems including Max-Cut and map coloring through phase synchronization. Our findings demonstrate that 2D memristors have the potential to significantly enhance the efficiency, compactness, and homogeneity of integrated Ising machines, which is useful for future advances in neural networks for optimization problems.

In-situ Monitoring of Photocontrollable Wrinkle Erasure in Azobenzene-based Supramolecular Systems.

In this contribution, dynamic photoinduced wrinkle erasure enabled by photomechanical changes in supramolecular polymer-azo complexes was characterized via confocal microscopy. Different photoactive molecules, disperse yellow 7 (DY7) and 4,4'-dihydroxyazobenzene (DHAB), were compared to 4-hydroxy-4'-dimethylaminoazobenzene (OH-azo-DMA). The characteristic erasure times of wrinkles were quickly assessed by using an image processing algorithm. The results confirm that the photoinduced movement on the topmost layer can be successfully transferred to the substrate. Furthermore, the chosen supramolecular strategy allows decoupling the effect of molecular weight of the polymer and photochemistry of the chromophore, allowing quantitative comparison of wrinkling erasure efficiency of different materials and providing a facile way to optimize the system for specific applications.

Theoretical Insight on the High Reactivity of Reductive Elimination of NiIII Based on Energy- and Electron-Transfer Mechanisms.

Iridium/nickel (Ir/Ni) metallaphotoredox dual catalysis overcomes the challenging reductive elimination (RE) of Ni(II) species and has made a breakthrough progress to construct a wide range of C-X (X = C, N, S, and P) bonds. However, the corresponding reaction mechanisms are still ambiguous and controversial because the systematic research on the nature of this synergistic catalysis is not sufficient. Herein, IrIII/NiII and IrIII/Ni0 metallaphotoredox catalysis have been theoretically explored taking the aryl esterification reaction of benzoic acid and aryl bromide as an example by a combination of density functional theory (DFT), molecular dynamics, and time-dependent DFT computations. It is found that an electron-transfer mechanism is applicable to IrIII/NiII metallaphotoredox catalysis, but an energy-transfer mechanism is applicable to IrIII/Ni0 combination. The IrIII/NiII metallaphotoredox catalysis succeeds to construct a NiI-NiIII catalytic cycle to avoid the challenging RE of Ni(II) species, while the RE occurs from triplet excited-state Ni(II) species in the IrIII/Ni0 metallaphotoredox catalysis. In addition, the lower lowest unoccupied molecular orbital energy level of Ni(III) species than that of Ni(II) species accelerates RE from Ni(III) one. The triplet excited-state Ni(II) species can resemble a Ni(III) center, considering the metal-to-ligand charge transfer character to promote the RE.

Divergent regioselective Heck-type reaction of unactivated alkenes and N-fluoro-sulfonamides.

The control of regioselectivity in Heck-type reaction of unactivated alkenes represents a longstanding challenge due to several detachable hydrogens in ß-H elimination step, which generally afford either one specific regioisomer or a mixture. Herein, a copper-catalyzed intermolecular Heck-type reaction of unactivated alkenes and N-fluoro-sulfonamides with divergent regioselectivities is reported. The complete switch of regioselectivity mainly depends on the choice of different additives. Employment of alcohol solvent gives access to vinyl products, while the addition of carboxylate leads to the formation of allylic products. In addition, exclusion of these two promoting factors results in ß-lactams via a C-N reductive elimination. This protocol shows a broad substrate scope for both alkenes and structurally diverse N-fluoro-sulfonamides, producing the corresponding products with excellent regio- and stereoselectivities. Further control experiments and DFT calculations provide in-depth insights into the reaction mechanism, highlighting the distinct effect of the additives on a bidentate auxiliary-stabilized Cu(III) intermediate.

Oscillator-Network-Based Ising Machine.

With the slowdown of Moore's law, many emerging electronic devices and computing architectures have been proposed to sustain the performance advancement of computing. Among them, the Ising machine is a non-von-Neumann solver that has received wide attention in recent years. It is capable of solving intractable combinatorial optimization (CO) problems, which are difficult to be solve using conventional digital computers. In fact, many CO problems can be mapped to finding the corresponding ground states of Ising model. At present, Ising machine prototypes based on different physical principles, such as emerging memristive oscillators, have been demonstrated, among which the Ising Hamiltonian solver based on the coupled oscillator network simultaneously holds the advantages of room-temperature operation, compact footprint, low power consumption, and fast speed to solution. This paper comprehensively surveys the recent developments in this important field, including the types of oscillators, the implementation principle of the Ising model, and the solver's performance. Finally, methods to further improve the performance have also been suggested.

Theoretical insight into decatungstate photocatalyzed alkylation of N-tosylimine via hydrogen atom transfer and proton-coupled electron transfer.

Decatungstate as a photocatalyst can activate various C(sp3)-H bonds to successfully construct the C(sp3)-C(sp2) bond with N-tosylimines. Herein density functional theory (DFT) calculations reveal a unique radical mechanism triggered by the reductive quenching cycle of decatungstate. First of all, photoexcited *[W10O32]4- activates the C(sp3)-H bond of ether through the hydrogen atom transfer (HAT) mechanism to generate [HW10O32]4- and a C-centered radical species. Next, the C-centered radical will selectively attack the imine carbon of N-tosylimine to provide the N-centered radical species containing the C(sp3)-C(sp2) bond. Finally, the C(sp3)-C(sp2) coupling product can be afforded by the stepwise proton-coupled electron transfer (PCET) process between [HW10O32]4- and the N-centered radical. Importantly, the bridging oxygen in the lateral position of [W10O32]4- is the most active. Intrinsic bond orbital (IBO) analysis confirms that *[W10O32]4- activates C(sp3)-H through HAT instead of PCET. Furthermore, the origin of the regio-selectivity has been explored in depth. We hope that the reductive quenching cycle mechanism ([W10O32]4--*[W10O32]4--[HW10O32]4--[W10O32]4-) can provide a clear understanding of the alkylation of N-tosylimine.

Recent progress and challenges facing ballast water treatment - A review.

The transoceanic movement of non-indigenous microorganisms and organic and inorganic contaminants through the transfer of ballast water of ocean-going vessels can be considered highly likely. The introduction of contaminants and non-indigenous microorganisms can cause changes in indigenous microorganisms, marine species, and biota, which can create problems for the ecology, economy, environment, and human health. This paper compiles and presents ballast water treatment system concepts, principles of inactivation mechanisms used, and the advantages and challenges of the treatment technologies. In addition, the paper aims to draw attention to the relationship between various organisms and the individual mechanism to be inactivated, including the effect of external factors (e.g., pH, salinity, turbidity) on inactivation efficiency. This review can assist in the choice of a suitable ballast water treatment system, taking into account the water conditions (e.g., pH, temperature, salinity) and indigenous species of the maritime areas where the ships intend to operate. This review also provides information describing the responses of the various organisms to different treatment techniques.

Theoretical mechanistic study of 4CzIPN/Ni0-metallaphotoredox catalyzed enantioselective desymmetrization of cyclic meso-anhydrides.

Visible-light-induced inexpensive photocatalyst and transition metal dual catalytic cross-coupling has attracted much attention for efficiently constructing various chemical bonds. The 4CzIPN/Ni0-metallaphotoredox catalyzed enantioselective desymmetrization of cyclic meso-anhydrides with benzyl trifluoroborates has been systematically investigated using density functional theory (DFT) calculations. A radical mechanism merging reductive quenching (PC-*PC-PC--PC) and nickel catalytic cycles (Ni0-NiII-NiIII-NiI-Ni0) is favourable. It consists of seven major processes: single-electron reduction of *PC by benzyl trifluoroborates to generate benzyl radical, ligand exchange, oxidative addition, radical addition, reductive elimination, reduction of NiI by PC- complex via single-electron transfer (SET) process to obtain ground-state PC, and the ion exchange to afford the desired product enantio-enriched keto-acids and regenerate Ni0 catalyst. The oxidative addition is not only the enantio-determining step but also the rate-determining step of the catalytic cycle. In addition, we tried to disclose the origin of high enantioselectivity from both the steric and electronic effects and explain the origin of diastereoselectivity based on the proposed mechanism. Meanwhile, the difference of catalytic activity between Ni0 and NiII as the initial catalysts is caused by the different activation energy barriers based on their respective favourable reaction pathways. This study will hopefully benefit the future understanding of such photoredox-mediated dual catalyzed asymmetric synthesis.

Origin and Regioselectivity of Direct Hydrogen Atom Transfer Mechanism of C(sp3)-H Arylation by [W10O32]4-/Ni Metallaphotoredox Catalysis.

Polyoxometalates (POMs) have a broad array of applied platforms with well-characterized catalysis including photocatalysis to achieve aliphatic C(sp3)-H bond functionalization. However, the reaction mechanism of POMs in organic transformation remains unknown due to the complexity of POM structures. Here, a challenging [W10O32]4-/Ni metallaphotoredox-catalyzed C(sp3)-H arylation of alkane has been investigated by density functional theory (DFT) calculations. The calculation revealed that the superficial active center located in bridged oxygen of *[W10O32]4- is responsible for the abstraction of a foreign hydrogen atom and the activation of a C(sp3)-H bond. Furthermore, we discussed this activated process using the direct activation model of the C(sp3)-H σ-bond to deepen our mechanistic understanding of POM mediated C-H bond activation via the hydrogen atom transfer (HAT) pathway. Specifically, comparing three common mechanisms for nickel catalysis inducing by Ni0, NiI, and NiII to construct a C-C bond, the nickel catalytic cycle induced by the NiI active catalyst is profitable in kinetics and thermodynamics. Finally, a radical mechanism merging the ([W10O32]4--*[W10O32]4--[HW10O32]4--[W10O32]4-) decatungstate reductive quenching cycle, ([HW10O32]4--[H2W10O32]4--[HW10O32]4-) electron relay, and (NiI-NiII-NiI-NiIII-NiI) nickel catalytic cycle is proposed to be favorable. We hope that this work would provide a better understanding of the unique catalytic activity of decatungstate anions for the direct functionalization of the C(sp3)-H bond.

Multiscale Hierarchical Surface Patterns by Coupling Optical Patterning and Thermal Shrinkage.

Herein, a simple hierarchical surface patterning method is presented by effectively combining buckling instability and azopolymer-based surface relief grating inscription. In this technique, submicron patterns are achieved using azopolymers, whereas the microscale patterns are fabricated by subsequent thermal shrinkage. The wetting characterization of various topographically patterned surfaces confirms that the method permits tuning of contact angles and choosing between isotropic and anisotropic wetting. Altogether, this method allows efficient fabrication of hierarchical surfaces over several length scales in relatively large areas, overcoming some limitations of fabricating multiscale roughness in lithography and also methods of creating merely random patterns, such as black silicon processing or wet etching of metals. The demonstrated fine-tuning of the surface patterns may be useful in optimizing surface-related material properties, such as wetting and adhesion, producing substrates that are of potential interest in mechanobiology and tissue engineering.

Superiority of Iridium Photocatalyst and Role of Quinuclidine in Selective α-C(sp3)-H Alkylation: Theoretical Insights.

Recent experimental work reported that visible-light photoredox catalysis coupled with primary sulfonamides and electron-deficient alkenes could efficiently construct C-C bonds at the α-position of primary amine derivatives under mild conditions. Here, a systematic study was conducted to explore the non-negligible excited-state single-electron-transfer (SET) processes and the catalytic cycle. Hydrogen atom transfer (HAT) catalysis containing different site-selective functionalization, involved as a critical process during the reaction, was computationally characterized. The superiorities of iridium-based photoredox catalysts in terms of photoabsorption properties, phosphorescence rates, and electron-transfer rates for SET processes were focused on. In addition, the function of quinuclidine in the entire photocatalytic reaction was also probed. These intrinsic properties and detailed insights into the mechanism are supposed to be helpful to the understanding of the C-C bond functionalization reaction and the future application of the iridium-based photoredox catalyst.

Coexisting hidden and self-excited attractors in a locally active memristor-based circuit.

This paper presents a chaotic circuit based on a nonvolatile locally active memristor model, with non-volatility and local activity verified by the power-off plot and the DC V-I plot, respectively. It is shown that the memristor-based circuit has no equilibrium with appropriate parameter values and can exhibit three hidden coexisting heterogeneous attractors including point attractors, periodic attractors, and chaotic attractors. As is well known, for a hidden attractor, its attraction basin does not intersect with any small neighborhood of any unstable equilibrium. However, it is found that some attractors of this circuit can be excited from an unstable equilibrium in the locally active region of the memristor, meaning that its basin of attraction intersects with neighborhoods of an unstable equilibrium of the locally active memristor. Furthermore, with another set of parameter values, the circuit possesses three equilibria and can generate self-excited chaotic attractors. Theoretical and simulated analyses both demonstrate that the local activity and an unstable equilibrium of the memristor are two reasons for generating hidden attractors by the circuit. This chaotic circuit is implemented in a digital signal processing circuit experiment to verify the theoretical analysis and numerical simulations.

Ultrafast Absorption of Polysulfides through Electrostatic Confinement by Protonated Molecules for Highly Efficient Li-S Batteries.

The lithium-sulfur battery is a promising high-energy-density storage system, which suffers from severe capacity fading due to the "shuttle effect" and low Coulombic efficiency caused by the dissolution of lithium polysulfides. At the molecular level, suppressing the shuttle effect has been greatly required for high-performance Li-S batteries. Herein, we propose a new strategy by utilizing a protonated organic absorbent (N1,N4-bis(pyridine-3-ylmethyl)butane-1,4-diammonium nitrate ([H2PBD]2+·(NO3)22-) for ultrafast absorption of polysulfides through electrostatic attractions and for fixing the polysulfides in the cathode by hydrogen-bond interactions. A lithium-sulfur battery cathode based on a commercial carbon black (CB) and an absorbent (10%) with high sulfur content (70%) exhibits a low capacity decay of 0.099% per cycle over 400 cycles at a rate of 0.5C along with 91% Coulombic efficiency. This strategy and the finding of an electrostatic absorbent offer a new alternative insight into designing cheaper lithium-sulfur batteries for their practical application in the future.

Entangled and colloidally stable microcrystalline cellulose matrices in controlled drug release.

Drug release from a new type of matrix material consisting of partially fibrillated microcrystalline cellulose was investigated. A mechanical treatment of novel AaltoCell™ cellulose microcrystals caused partial opening of the nanofibrillary structure of the cellulose particles and entanglement of individual particles led into formation of an elastic network of microcrystalline cellulose. The rheological properties of the stable hydrogel-like materials were characterised by shear rheometry. Model compounds metronidazole and lysozyme were successfully employed in drug release experiments carried out by delignified (bleached) and lignin-containing matrices. The viscosity as well as the lignin-content played a role in the release dynamics of the drugs. Microcrystalline AaltoCell™ was proven as high-performing material for diffusion controlled release of the chosen model compounds and can be seen as a safe and economical alternative for novel matrix materials such as nanocellulose or cellulose derivatives.

Pectin and Mucin Enhance the Bioadhesion of Drug Loaded Nanofibrillated Cellulose Films.

PURPOSE: Bioadhesion is an important property of biological membranes, that can be utilized in pharmaceutical and biomedical applications. In this study, we have fabricated mucoadhesive drug releasing films with bio-based, non-toxic and biodegradable polymers that do not require chemical modifications. METHODS: Nanofibrillar cellulose and anionic type nanofibrillar cellulose were used as film forming materials with known mucoadhesive components mucin, pectin and chitosan as functional bioadhesion enhancers. Different polymer combinations were investigated to study the adhesiveness, solid state characteristics, film morphology, swelling, mechanical properties, drug release with the model compound metronidazole and in vitro cytotoxicity using TR146 cells to model buccal epithelium. RESULTS: SEM revealed lamellar structures within the films, which had a thickness ranging 40-240 µm depending on the film polymer composition. All bioadhesive components were non-toxic and showed high adhesiveness. Rapid drug release was observed, as 60-80% of the total amount of metronidazole was released in 30 min depending on the film formulation. CONCLUSIONS: The liquid molding used was a straightforward and simple method to produce drug releasing highly mucoadhesive films, which could be utilized in treating local oral diseases, such as periodontitis. All materials used were natural biodegradable polymers from renewable sources, which are generally regarded as safe.

[Effect of controlled release fertilizer on nitrous oxide emission from paddy field under plastic film mulching cultivation].

A field experiment was conducted to assess the effect of controlled release fertilizer on N2O emission in paddy field under plastic film mulching cultivation (PM) with water-saving irrigation. Results showed that in the rice growing season, cumulative N2O emissions from the plots applied with urea (PM+U) and with controlled release fertilizer (PM+CRF) were (38.2 +/- 4.4) and (21.5 +/- 5.2) mg N x m(-2), respectively. The N2O emission factors were 0.25% and 0.14% in the treatments PM+U and PM+CRF, respectively. The controlled release fertilizer decreased the total N2O emission by 43.6% compared with urea, of which 49.6% was reduced before the drying period. It also reduced the peak of N2O emission by 52.6%. However, it did not affect soil microbial biomass N and soil NH(4+)-N content at any rice growing stage, and grain yield either. No significant correlation was observed between N2O flux and soil Eh or soil temperature at the depth of 5 cm.