Ru-catalyzed asymmetric hydrogenation of α,ß-unsaturated ketones via a hydrogenation/isomerization cascade.

Ru-catalyzed asymmetric hydrogenation of α-substituted α,ß-unsaturated ketones has been developed for the enantioselective synthesis of chiral α-substituted secondary alcohols with high diastereo- and enantioselectivities (up to >99 : 1 dr, 98% ee). Mechanistic experiments suggest that the reaction proceeds via a Ru-catalyzed asymmetric hydrogenation of the CO bond in concert with a base-promoted allylic alcohol isomerization, and the final stereoselectivities were controlled by a DKR process during the asymmetric hydrogenation of the ketone intermediate.

Skin preparation-free, stretchable microneedle adhesive patches for reliable electrophysiological sensing and exoskeleton robot control.

High-fidelity and comfortable recording of electrophysiological (EP) signals with on-the-fly setup is essential for health care and human-machine interfaces (HMIs). Microneedle electrodes allow direct access to the epidermis and eliminate time-consuming skin preparation. However, existing microneedle electrodes lack elasticity and reliability required for robust skin interfacing, thereby making long-term, high-quality EP sensing challenging during body movement. Here, we introduce a stretchable microneedle adhesive patch (SNAP) providing excellent skin penetrability and a robust electromechanical skin interface for prolonged and reliable EP monitoring under varying skin conditions. Results demonstrate that the SNAP can substantially reduce skin contact impedance under skin contamination and enhance wearing comfort during motion, outperforming gel and flexible microneedle electrodes. Our wireless SNAP demonstration for exoskeleton robot control shows its potential for highly reliable HMIs, even under time-dynamic skin conditions. We envision that the SNAP will open new opportunities for wearable EP sensing and its real-world applications in HMIs.

Hydrogenation of functionalised pyridines with a rhodium oxide catalyst under mild conditions.

Piperidines are one of the most widely used building blocks in the synthesis of pharmaceutical and agrochemical compounds. The hydrogenation of pyridines is a convenient method to synthesise such compounds as it only requires reactant, catalyst, and a hydrogen source. However, this reaction still remains difficult for the reduction of functionalised and multi-substituted pyridines. Here we report the use of a stable, commercially available rhodium compound, Rh2O3, for the reduction of various unprotected pyridines. The reaction only requires mild conditions, and the substrate scope is broad, making it practically useful.

Werner Salt as Nickel and Ammonia Source for Photochemical Synthesis of Primary Aryl Amines.

Cheap, stable and easy-to-handle Werner ammine salts have been known for more than a century; but they have been rarely used in organic synthesis. Herein, we report that the Werner hexammine complex [Ni(NH3 )6 ]Cl2 can be used as both a nitrogen and a catalytic nickel source that allow for the efficient amination of aryl chlorides in the presence of a catalytic amount of bipyridine ligand under the irradiation of 390-395 nm light without the need of any additional catalysts. More than 80 aryl chlorides, including more than 20 drug molecules, were aminated, demonstrating the practicality and generality of this method in synthetic chemistry. A slow NH3 release mechanism is in operation, obviating the problem of catalyst poisoning. Still interestingly, we show that the Werner salt can be easily recovered and reused, solving the problem of difficult recovery of transition metal nickel catalysts. The protocol thus provides an efficient new strategy for the synthesis of primary aryl amines.

Flexible Optoelectronic Multimodal Proximity/Pressure/Temperature Sensors with Low Signal Interference.

Multimodal tactile sensors are a crucial part of intelligent human-machine interaction and collaboration. Simultaneous detection of proximity, pressure, and temperature on a single sensor can greatly promote the safety, interactivity, and compactness of interaction systems. However, severe signal interference and complex decoupling algorithms hinder the actual applications. Here, this work reports a flexible optoelectronic multimodal sensor capable of detecting and decoupling proximity/pressure/temperature by integrating a light waveguide and an interdigital electrode (IDE) into a compact fibrous sensor. Negligible signal interference is realized by combining heterogeneous sensing mechanisms of optics and electronics, which encodes proximity into capacitance, pressure into light intensity and temperature into resistance. The sensor exhibits a large sensing distance of 225 mm with fast responses for proximity detection, a pressure sensitivity of 0.42 N-1 , and a temperature sensitivity of 7% °C-1 . As a proof of concept, a doll equipped with the sensor can accurately discriminate and detect various stimuli, thus achieving safe and immersive interactions with the user. This work opens up promising paths for self-decoupled multimodal sensors and related human/machine/environment interaction applications.

Soft, flexible pressure sensors for pressure monitoring under large hydrostatic pressure and harsh ocean environments.

Traditional rigid ocean pressure sensors typically require protection from bulky pressure chambers and complex seals to survive the large hydrostatic pressure and harsh ocean environment. Here, we introduce soft, flexible pressure sensors that can eliminate such a need and measure a wide range of hydrostatic pressures (0.1 MPa to 15 MPa) in environments that mimic the ocean, achieving small size, high flexibility, and potentially low power consumption. The sensors are fabricated from lithographically patterned gold thin films (100 nm thick) encapsulated with a soft Parylene C film and tested in a customized pressure vessel under well-controlled pressure and temperature conditions. Using a rectangular pressure sensor as an example, the resistance of the sensor is found to decrease linearly with the increase of the hydrostatic pressure from 0.1 MPa to 15 MPa. Finite element analysis (FEA) reveals the strain distributions in the pressure sensor under hydrostatic pressures of up to 15 MPa. The effect of geometry on sensor performance is also studied, and radially symmetric pressure sensors (like circular and spike-shaped) are shown to have more uniform strain distributions under large hydrostatic pressures and, therefore, have a potentially enhanced pressure measurement range. Pressure sensors of all geometries show high consistency and negligible hysteresis over 15 cyclic tests. In addition, the sensors exhibit excellent flexibility and operate reliably under a hydrostatic pressure of 10 MPa for up to 70 days. The developed soft pressure sensors are promising for integration with many platforms including animal tags, diver equipment, and soft underwater robotics.

ß-Arylation of Racemic Secondary Benzylic Alcohols to Access Enantioenriched ß-Arylated Alcohols.

The transformation of alcohols into value-added products is of great importance, as simple alcohols are widespread and can be easily derived from both fossil fuels and biomass. The selective functionalization of a sp3 C-H bond on the alkyl side chain of an alcohol over its hydroxyl group would offer an expedient route to expand the chemical space of alcohols but it remains a challenging task. Harnessing the borrowing hydrogen strategy, the ß-arylation of secondary alcohols with aryl bromides has been achieved in this study, which allows for the selective functionalization of a ß-Csp3 -H bond in an alcohol substrate. Under the catalysis of a Pd complex, secondary alcohols reacted with aryl bromides to afford 1,2-diaryl alcohols with broad substrate scope in the presence of a ketone additive. Furthermore, the enantioconvergent version of the reaction has also been realized, transforming racemic secondary alcohols into enantioenriched chiral 1,2-diaryl alcohols under the cooperative Pd and Ru catalysis. Mechanism studies indicate that the reactions are enabled by borrowing hydrogen catalysis.

Ni-Catalyzed Photochemical C-N Coupling of Amides with (Hetero)aryl Chlorides.

This paper reports a photochemical C-N coupling of abundant, but less reactive aryl chlorides, with structurally diverse primary and secondary amides by Ni-mediated without an external photocatalyst. Under the irradiation of light (390-395 nm) with a soluble organic amine as the base, the reaction allows for the successful transformation of (hetero)aryl chlorides to a wide range of N-aryl amides. More than 60 examples are shown, demonstrating the feasibility and applicability of this protocol in organic synthesis. Mechanic studies indicate that this amidation proceeds via a Ni(I)-Ni(III) catalytic cycle.

Light-Promoted Ni-Catalyzed Cross-Coupling of Aryl Chlorides with Hydrazides: Application to the Synthesis of Rizatriptan.

A general and highly efficient photochemical C-N coupling reaction of challenging (hetero)aryl chlorides with hydrazides is reported. Catalyzed by a Ni(II)-bipyridine complex, this reaction provides an efficient tool for the synthesis of arylhydrazines in the presence of a soluble organic amine base without an external photosensitizer. The reaction features a wide substrate range (54 examples) and excellent functional group tolerance. The method has also been successfully applied to the three-step concise synthesis of rizatriptan, an effective drug for migraine and cluster headaches.

Chemoselective Decarboxylative Oxygenation of Carboxylic Acids To Access Ketones, Aldehydes, and Peroxides.

Reported here is a photocatalytic strategy for the chemoselective decarboxylative oxygenation of carboxylic acids using Ce(III) catalysts and O2 as the oxidant. By simply changing the base employed, we demonstrate that the selectivity of the reaction can be channeled to favor hydroperoxides or carbonyls, with each class of products obtained in good to excellent yields and high selectivity. Notably, valuable ketones, aldehydes, and peroxides are produced directly from readily available carboxylic acid without additional steps.

Wireless, AI-enabled wearable thermal comfort sensor for energy-efficient, human-in-the-loop control of indoor temperature.

The conventional heating, ventilation, and air conditioning (HVAC) systems are based on a set-point control approach that only considers the temperature of the environment without reflecting the thermophysiological status of the occupant. This approach not only fails to fully satisfy individual thermal preferences, but it also makes an HVAC operation energy-inefficient. One possible solution is to control the indoor thermal condition based on an accurate prediction of the occupant's thermal comfort to prevent any unnecessary energy consumption. Here, we present an artificial intelligence (AI) wearable sensor-based human-in-the-loop HVAC control system that is operated on a real-time basis reflecting the thermophysiological condition of the occupant to automatically improve their thermal comfort while reducing the energy consumption of the building. The wristband-type, AI-based, three-point wearable temperature sensor offers excellent thermal comfort prediction accuracy (93.9%), enabling a human-centric HVAC control operation. A proof-of-concept demonstration of closed human-in-the-loop HVAC control using the AI-enabled wearable sensor system confirms both the accuracy of the thermal comfort prediction and the energy-efficiency of this approach, demonstrating its potential as a new solution that improves the occupant's thermal comfort and provides building energy savings.

Ni(I)-Catalyzed Hydroxylation of Aryl Halides with Water under Thermal Catalysis.

A highly efficient hydroxylation of (hetero)aryl halides using water as a hydroxyl source via Ni catalysis promoted by PhSiH3 under thermal catalysis is reported. This methodology provides a general procedure to obtain diverse multifunctional pharmaceutically phenols and polyphenols, some of which are proven challenging to be synthesized using literature methods. Mechanism studies demonstrated that the addition of PhSiH3 led to the generation of active Ni(I) species, which catalyze the hydroxylation via a Ni(I)-Ni(III) pathway.

Successive Cleavage and Reconstruction of Lignin ß-O-4 Models and Polymer to Access Quinoxalines.

The construction of N-heterocyclic compounds from lignin remains a great challenge due to the complex lignin structure and the involvement of multiple steps, including the cleavage of lignin C-O linkages and the formation of heterocyclic aromatic rings. Herein, the first example of KOH mediated sustainable synthesis of quinoxaline derivatives from lignin ß-O-4 model compounds in a one-pot fashion under transition-metal-free conditions has been achieved. Mechanistic studies suggested that this transformation includes highly coupled cascade steps of cleavage of C-O bonds, dehydrative condensation, sp3 C-H bond oxidative activation, and intramolecular dehydrative coupling reaction. With this protocol, a wide range of functionalized quinoxalines, including an important drug compound AG1295, were synthesized from lignin ß-O-4 model compounds and ß-O-4 polymer, showcasing the application potential of lignin in pharmaceutical synthesis.

Observer-based finite-time adaptive fuzzy back-stepping control for MIMO coupled nonlinear systems.

An attempt is made in this paper to devise a finite-time adaptive fuzzy back-stepping control scheme for a class of multi-input and multi-output (MIMO) coupled nonlinear systems with immeasurable states. In view of the uncertainty of the system, adaptive fuzzy logic systems (AFLSs) are used to approach the uncertainty of the system, and the unmeasured states of the system are estimated by the finite-time extend state observers (FT-ESOs), where the state of the observer is a sphere around the state of the system. The accuracy and efficiency of the control effect are ensured by combining the back-stepping and finite-time theory. It is proved that all the states of the closed-loop adaptive control system are semi-global practical finite-time stability (SGPFS) by the finite-time Lyapunov stability theorem, and the tracking errors of the system states converge to a tiny neighborhood of the origin in a finite time. The validity of this scheme is demonstrated by a simulation.

Fe-Catalyzed Amidation of Allylic Alcohols by Borrowing Hydrogen Catalysis.

Allylic amines are useful building blocks in organic synthesis, so the development of green and efficient methods for the preparation of allylic amines are of great importance. An Fe-catalyzed amidation of allylic alcohols with chiral tert-butylsulfinamide has been developed. With water as the only by-product, a range of synthetically useful chiral sulfinamide olefin derivatives (30 examples) were obtained under mild reaction conditions. The reaction can be performed on a gram-scale, and the products could serve as chiral ligands for asymmetric catalysis. Mechanistic studies suggest that the reaction proceeds by an Fe-catalyzed borrowing hydrogen process, which is different from most of the reported allylic amination reactions.

General Method for the Amination of Aryl Halides with Primary and Secondary Alkyl Amines via Nickel Photocatalysis.

The Buchwald-Hartwig C-N coupling reaction has been ranked as one of the 20 most frequently used reactions in medicinal chemistry. Owing to its much lower cost and higher reactivity toward less reactive aryl chlorides than palladium, the C-N coupling reaction catalyzed by Ni-based catalysts has received a great deal of attention. However, there appear to be no universal, practical Ni catalytic systems so far that could enable the coupling of electron-rich and electron-poor aryl halides with both primary and secondary alkyl amines. In this study, it is reported that a Ni(II)-bipyridine complex catalyzes efficient C-N coupling of aryl chlorides and bromides with various primary and secondary alkyl amines under direct excitation with light. Intramolecular C-N coupling is also demonstrated. The feasibility and applicability of the protocol in organic synthesis is attested by more than 200 examples.

Self-Cooling Gallium-Based Transformative Electronics with a Radiative Cooler for Reliable Stiffness Tuning in Outdoor Use.

Reconfigurability of a device that allows tuning of its shape and stiffness is utilized for personal electronics to provide an optimal mechanical interface for an intended purpose. Recent approaches in developing such transformative electronic systems (TES) involved the use of gallium liquid metal, which can change its liquid-solid phase by temperature to facilitate stiffness control of the device. However, the current design cannot withstand excessive heat during outdoor applications, leading to undesired softening of the device when the rigid mode of operation is favored. Here, a gallium-based TES integrated with a flexible and stretchable radiative cooler is presented, which offers zero-power thermal management for reliable rigid mode operation in the hot outdoors. The radiative cooler can both effectively reflect the heat transfer from the sun and emit thermal energy. It, therefore, allows a TES-in-the-air to maintain its temperature below the melting point of gallium (29.8 â„ƒ) under hot weather with strong sun exposure, thus preventing unwanted softening of the device. Comprehensive studies on optical, thermal, and mechanical characteristics of radiative-cooler-integrated TES, along with a proof-of-concept demonstration in the hot outdoors verify the reliability of this design approach, suggesting the possibility of expanding the use of TES in various environments.

Transition-metal-free synthesis of pyrimidines from lignin ß-O-4 segments via a one-pot multi-component reaction.

Heteroatom-participated lignin depolymerization for heterocyclic aromatic compounds production is of great importance to expanding the product portfolio and meeting value-added biorefinery demand, but it is also particularly challenging. In this work, the synthesis of pyrimidines from lignin ß-O-4 model compounds, the most abundant segment in lignin, mediated by NaOH through a one-pot multi-component cascade reaction is reported. Mechanism study suggests that the transformation starts by NaOH-induced deprotonation of Cα-H bond in ß-O-4 model compounds, and involves highly coupled sequential cleavage of C-O bonds, alcohol dehydrogenation, aldol condensation, and dehydrogenative aromatization. This strategy features transition-metal free catalysis, a sustainable universal approach, no need of external oxidant/reductant, and an efficient one-pot process, thus providing an unprecedented opportunity for N-containing aromatic heterocyclic compounds synthesis from biorenewable feedstock. With this protocol, an important marine alkaloid meridianin derivative can be synthesized, emphasizing the application feasibility in pharmaceutical synthesis.

Elastomeric tubes with self-regulated distension.

Compliant elastomer tubing with a fabric "jacket" has been essential in various applications as soft robotic actuators, such as in biomedical exomuscles and massage therapy implements. Here, our study shows that a similar design concept can be an effective strategy in realizing passive regulation in the tube's distension, as well as in preventing aneurysm-like asymmetric rupture of the tube. A custom hydraulic pressure testing rig was built to perform experiments. The jacketed tubes initially deform rapidly as pressure increases, but a self-regulation behavior suppresses the tube's continued distension by strain-stiffening of the "jacket". In addition, highly asymmetric distension, common to elastomeric tubes due to imperfection in fabrication, is prevented dramatically by the "jacket". A three-dimensional finite element model predicts the distension of all tested tubes quantitatively across the entire experimental pressure ranges and beyond. Incorporating custom-designed kirigami relief patterns in the "jackets" expands the potential of the elastomeric tubes.