Class Of Substrates Research Articles

Highly Transparent and Self-Healable Solar Thermal Anti-/Deicing Surfaces: When Ultrathin MXene Multilayers Marry a Solid Slippery Self-Cleaning Coating.

Solar anti-/deicing can solve icing problems by converting sunlight into heat. One of the biggest problems, which has long been plaguing the design of solar anti-/deicing surfaces, is that photothermal materials are always lightproof and appear black, because of the mutual exclusiveness between generating heat and retaining transparency. Herein, a highly transparent and scalable solar anti-/deicing surface is reported, which enables the coated glass to exhibit high transparency (>77% transmittance at 550nm) and meanwhile causes a >30 °Csurface temperature increase relative to the ambient environment under 1.0 sun illumination. Such a transparent anti-/deicing surface can be fabricated onto a large class of substrates (e.g., glass, ceramics, metals, plastics), by applying a solid omniphobic slippery coating onto layer-by-layer-assembled ultrathin MXene multilayers. Hence, the surface possesses a self-cleaning ability to shed waterborne and oil-based liquids thanks to residue-free slipping motion. Passive anti-icing and active deicing capabilities are, respectively, obtained on the solar thermal surface, which effectively prevents water from freezing and simultaneously melts pre-formed ice and thick frost. The self-cleaning effect enables residue-free removal of unfrozen water and interfacially melted ice/frost to boost the anti-/deicing efficiency. Importantly, the surface is capable of self-healing under illumination to repair physical damage and chemical degradation.

Mapping subaerial sand-gravel-cobble fluvial sediment facies using airborne lidar and machine learning

Substrate facies monitoring is critical for the understanding of fluvial geomorphologic and ecohydraulic patterns and processes. However, direct substrate measurement is time-consuming and subjected to data sparsity because of small sample, size, and limited data collections within an area of interest, which make it difficult to capture facies patterns. Most new experimental studies focus on mapping substrate based on median grain size of a specific grain size class using automatic or semiautomatic photosieving techniques. This study aimed to develop and apply a method to accurately predict size-mixture facies patterns on exposed riverbeds with minimal ground truth plots (100) using airborne lidar and machine learning. The selected testbed river was a 37.5-km stretch of the regulated lower Yuba River in California, USA, mapped at sub-meter resolution in 2017. First, we designed a grid-by-point grain size sampling method and binned grain sizes into representative mixtures, such as fine or large gravel, to assign subaerial facies labels. Second, we classified facies based on a multivariate cluster analysis. Third, we generated 15 lidar-derived topographic and spectral predictors. Six distinct size-mixture facies were identified from field data and a seventh, pure sand facies, from UAV data. A random forest predictive model with an 86% 10-fold cross-validation accuracy was applied to produce a facies map at the 1.54 m pixel scale. The detrended elevation was identified as the most important variable for predicting facies spatial patterning, followed by baseflow, wetted area proximity, and green lidar intensity. We conclude that machine learning combined with intensity lidar data is highly effective for distinguishing mixed classes of substrates. Ultimately, the new substrate mixture-binning approach also provides novel insights into the arrangement of river sediment facies patterns.

Synergistic Catalyst-Mediator Pairings for Electroreductive Cross-Electrophile Coupling Reactions.

Electroreductive cross-electrophile coupling (eXEC) represents an attractive approach for the direct C-C coupling of two electrophiles but generally suffers from limited scope compared to reactions with chemical reductants. This work demonstrates that mediator-assisted electrocatalysis is a general strategy for the enhancement of eXEC reactions. While eXEC reactions catalyzed by a variety of widely available ligand-nickel complexes are low yielding when applied to reductive couplings of challenging substrates, reactions with the same complexes generate products in near-quantitative yield when a redox-matched mediator is included. We identify a library of catalyst-mediator systems that provide complementary reactivity and enable coupling of a range of substrate classes in high yields. These catalyst systems are applicable to both chemical and electrochemical reduction, but some require electroreduction due to the low potentials required for activation. Finally, mechanistic studies offer insights that facilitate catalyst-mediator pairing.

Using Data Science To Guide Aryl Bromide Substrate Scope Analysis in a Ni/Photoredox-Catalyzed Cross-Coupling with Acetals as Alcohol-Derived Radical Sources.

Ni/photoredox catalysis has emerged as a powerful platform for C(sp2)-C(sp3) bond formation. While many of these methods typically employ aryl bromides as the C(sp2) coupling partner, a variety of aliphatic radical sources have been investigated. In principle, these reactions enable access to the same product scaffolds, but it can be hard to discern which method to employ because nonstandardized sets of aryl bromides are used in scope evaluation. Herein, we report a Ni/photoredox-catalyzed (deutero)methylation and alkylation of aryl halides where benzaldehyde di(alkyl) acetals serve as alcohol-derived radical sources. Reaction development, mechanistic studies, and late-stage derivatization of a biologically relevant aryl chloride, fenofibrate, are presented. Then, we describe the integration of data science techniques, including DFT featurization, dimensionality reduction, and hierarchical clustering, to delineate a diverse and succinct collection of aryl bromides that is representative of the chemical space of the substrate class. By superimposing scope examples from published Ni/photoredox methods on this same chemical space, we identify areas of sparse coverage and high versus low average yields, enabling comparisons between prior art and this new method. Additionally, we demonstrate that the systematically selected scope of aryl bromides can be used to quantify population-wide reactivity trends and reveal sources of possible functional group incompatibility with supervised machine learning.

Photocatalyst-free hydroacylations of electron-poor alkenes and enones under visible-light irradiation.

Herein we present a photocatalyst- and additive-free radical hydroacylation of electron-poor double bonds under mild reaction conditions. Using 4-acyl-Hantzsch ester radical reservoirs, various Michael acceptors, enones and para-quinone methide substrates could be used. The protocol enabled further derivatizations and it could also be extended to a few unactivated alkenes. Moreover, the nature of the radical process was also investigated.

Nuclear RNA Exosome and Pervasive Transcription: Dual Sculptors of Genome Function.

The genome is pervasively transcribed across various species, yielding numerous non-coding RNAs. As a counterbalance for pervasive transcription, various organisms have a nuclear RNA exosome complex, whose structure is well conserved between yeast and mammalian cells. The RNA exosome not only regulates the processing of stable RNA species, such as rRNAs, tRNAs, small nucleolar RNAs, and small nuclear RNAs, but also plays a central role in RNA surveillance by degrading many unstable RNAs and misprocessed pre-mRNAs. In addition, associated cofactors of RNA exosome direct the exosome to distinct classes of RNA substrates, suggesting divergent and/or multi-layer control of RNA quality in the cell. While the RNA exosome is essential for cell viability and influences various cellular processes, mutations and alterations in the RNA exosome components are linked to the collection of rare diseases and various diseases including cancer, respectively. The present review summarizes the relationships between pervasive transcription and RNA exosome, including evolutionary crosstalk, mechanisms of RNA exosome-mediated RNA surveillance, and physiopathological effects of perturbation of RNA exosome.

Crosstalk between the ancestral type VII secretion system ESX-4 and other T7SS in Mycobacterium marinum

SummaryThe type VII secretion system (T7SS) of Mycobacterium tuberculosis secretes three substrate classes: Esx, Esp, and PE/PPE proteins, that play important roles in bacterial physiology and host interaction. Five subtypes of T7SS, namely ESX-1 to ESX-5, are present in M. tb. ESX-4 is the progenitor of T7SS but its function is not understood. We investigated the ESX-4 system in Mycobacterium marinum. We show that ESX-4 of M. marinum does not secrete its cognate substrates, EsxT and EsxU, under the conditions tested. Paradoxically, the deletion of eccC4, an essential component of ESX-4, resulted in elevated secretion of protein substrates of ESX-1 and ESX-5. Consequently, the ΔeccC4 mutant was more efficient in inducing actin cytoskeleton rearrangement, which led to enhanced phagocytosis by macrophages. Our results reveal an intimate crosstalk between the progenitor of T7SS and its more recent duplication and expansion, and provide new insight into the evolution of T7SS in mycobacteria.

A binary classifier based on a reconfigurable dense network of metallic nanojunctions

Major efforts to reproduce the brain performances in terms of classification and pattern recognition have been focussed on the development of artificial neuromorphic systems based on top-down lithographic technologies typical of highly integrated components of digital computers. Unconventional computing has been proposed as an alternative exploiting the complexity and collective phenomena originating from various classes of physical substrates. Materials composed of a large number of non-linear nanoscale junctions are of particular interest: these systems, obtained by the self-assembling of nano-objects like nanoparticles and nanowires, results in non-linear conduction properties characterized by spatiotemporal correlation in their electrical activity. This appears particularly useful for classification of complex features: nonlinear projection into a high-dimensional space can make data linearly separable, providing classification solutions that are computationally very expensive with digital computers. Recently we reported that nanostructured Au films fabricated from the assembling of gold clusters by supersonic cluster beam deposition show a complex resistive switching behaviour. Their non-linear electric behaviour is remarkably stable and reproducible allowing the facile training of the devices on precise resistive states. Here we report about the fabrication and characterization of a device that allows the binary classification of Boolean functions by exploiting the properties of cluster-assembled Au films interconnecting a generic pattern of electrodes. This device, that constitutes a generalization of the perceptron, can receive inputs from different electrode configurations and generate a complete set of Boolean functions of n variables for classification tasks. We also show that the non-linear and non-local electrical conduction of cluster-assembled gold films, working at room temperature, allows the classification of non-linearly separable functions without previous training of the device.

Parahydrogen Hyperpolarization Allows Direct NMR Detection of α‐Amino Acids in Complex (Bio)mixtures

AbstractThe scope of non‐hydrogenative parahydrogen hyperpolarization (nhPHIP) techniques has been expanding over the last years, with the continuous addition of important classes of substrates. For example, pyruvate can now be hyperpolarized using the Signal Amplification By Reversible Exchange (SABRE) technique, offering a fast, efficient and low‐cost PHIP alternative to Dynamic Nuclear Polarization for metabolic imaging studies. Still, important biomolecules such as amino acids have so far resisted PHIP, unless properly functionalized. Here, we report on an approach to nhPHIP for unmodified α‐amino acids that allows their detection and quantification in complex mixtures at sub‐micromolar concentrations. This method was tested on human urine, in which natural α‐amino acids could be measured after dilution with methanol without any additional sample treatment.

Sandmeyer-Type Reductive Disulfuration of Anilines.

A transition metal/ligand-free disulfuration of anilines with disulfur transfer reagents (dithiosulfonate or tetrasulfide) is reported herein. The reaction, which can be considered as a reductive disulfuration variation of the classic Sandmeyer reaction, is performed under mild conditions and exhibits broad scope across the aniline substrate and disulfur transfer reagent classes. The gram-scale synthesis of disulfides is successfully achieved through this method, rendering the approach highly valuable.

Hook-basal-body assembly state dictates substrate specificity of the flagellar type-III secretion system.

The assembly of the bacterial flagellum is orchestrated by the secretion of distinct early and late secretion substrates via the flagellar-specific type-III secretion system (fT3SS). However, how the fT3SS is able to distinguish between the different (early and late) substrate classes during flagellar assembly remains poorly understood. In this study, we investigated the substrate selectivity and specificity of the fT3SS of Salmonella enterica at different assembly stages. For this, we developed an experimental setup that allowed us to synchronize hook-basal-body assembly and to monitor early and late substrate secretion of fT3SSs operating in either early or late secretion mode, respectively. Our results demonstrate that the fT3SS features a remarkable specificity for only the substrates required at the respective assembly stage. No crosstalk of substrates was observed for fT3SSs operating in the opposing secretion mode. We further found that a substantial fraction of fT3SS surprisingly remained in early secretion mode. Our results thus suggest that the secretion substrate specificity switch of the fT3SS is unidirectional and irreversible. The developed secretion substrate reporter system further provides a platform for future investigations of the underlying molecular mechanisms of the elusive substrate recognition of the T3SS.

Assembling Complex Structures through Cascade and Cycloaddition Processes via Non-Acceptor Gold or Rhodium Carbenes

AbstractThe ability of highly energetic metal–carbene intermediates to engage in complex cascade or formal cycloaddition processes is one of the most powerful tools for building intricate molecular architectures in a straightforward manner. Among this type of organometallic intermediates, non-acceptor metal carbenes are particularly challenging to access and, therefore, have experienced slower development. In this regard, our group has exploited the use of electrophilic gold(I) complexes to selectively activate certain classes of substrates for the generation of this type of intermediate. Thus, very different types of molecules, such as enynes or 7-substituted cycloheptatrienes, lead to the formation of carbenes under gold(I) catalysis. Related rhodium(II) carbenes can also be generated from cycloheptatrienes. In this account, we aim to summarize our efforts towards the in situ generation of such highly versatile organometallic species as well as studies on their reactivity through formal cycloadditions or complex cascade reactions.1 Introduction2 Generation of Au(I)-Vinylcarbenes via a Cycloisomerization/1,5-Alkoxy Migration Cascade2.1 Intramolecular Trapping of Au(I) Vinylcarbenes2.1.1 Applications in Total Synthesis2.2 Intermolecular Trapping of Au(I) Vinylcarbenes2.2.1 Total Synthesis of Schisanwilsonene A2.2.2 Trapping with Furans, 1,3-Dicarbonyl Compounds and Cyclic Alkenes2.2.3 Mechanism of the Cycloisomerization/1,5-Migration Sequence and the Role of the OR Migrating Group2.2.4 (4+3) Cycloadditions from Enynes3 Formal Cycloadditions of Simple Donor Metal Carbenes3.1 The Metal-Catalyzed Retro-Buchner Reaction3.2 Formal Cycloadditions with Non-Acceptor Carbenes via Metal-Catalyzed Aromative Decarbenations3.2.1 (4+1) Cycloadditions of Au(I) Carbenes3.2.2 (3+2) Cycloadditions of Au(I) Carbenes3.2.3 (4+3) Cycloadditions of Rh(II) Carbenes4 Concluding Remarks

Stable softening bioelectronics: A paradigm for chronically viable ester-free neural interfaces such as spinal cord stimulation implants

Polymer toughness is preserved at chronic timepoints in a new class of modulus-changing bioelectronics, which hold promise for commercial chronic implant components such as spinal cord stimulation leads. The underlying ester-free chemical network of the polymer substrate enables device rigidity during implantation, soft, compliant, conforming structures during acute phases in vivo, and gradual stabilization of materials properties chronically, maintaining materials toughness as device stiffness changes. In the past, bioelectronics device designs generally avoided modulus-changing and materials due to the difficulty in demonstrating consistent, predictable performance over time in the body. Here, the acute, and chronic mechanical and chemical properties of a new class of ester-free bioelectronic substrates are described and characterized via accelerated aging at elevated temperatures, with an assessment of their underlying cytotoxicity. Furthermore, spinal cord stimulation leads consisting of photolithographically-defined gold traces and titanium nitride (TiN) electrodes are fabricated on ester-free polymer substrates. Electrochemical properties of the fabricated devices are determined in vitro before implantation in the cervical spinal cord of rat models and subsequent quantification of device stimulation capabilities. Preliminary in vivo evidence demonstrates that this new generation of ester-free, softening bioelectronics holds promise to realize stable, scalable, chronically viable components for bioelectronic medicines of the future.

Mechanistic study of enantioselective Pd-catalyzed C(sp3)-H activation of thioethers involving two distinct stereomodels.

Enantioselective C(sp3)-H activation has gained considerable attention from the synthetic chemistry community. Despite the intense interest in these reactions, the mechanisms responsible for enantioselection are still vague. In the course of the development of aryl thioether-directed C(sp3)-H arylation, we noticed extreme variation in sensitivity of two substrate classes to substituent effects of ligands and directing groups: whereas 3-pentyl sulfides (prochiral α-center) responded positively to substitution on ligands and directing groups, isobutyl sulfides (prochiral β-center) were entirely insensitive. Quantitative structure selectivity relationship (QSSR) analyses of directing group and ligand substitution and the development of a new class of mono-N-acetyl protected amino anilamide (MPAAn) ligands led to high enantiomeric ratios (up to 99:1) for thioether-directed C(sp3)-H arylation. Key to the realization of this method was the exploitation of transient chirality at sulfur, which relays stereochemical information from the ligand backbone to enantiotopic carbons of the substrate in a rate- and enantio-determining cyclometallation deprotonation. The absolute stereochemistry of the products for these two substrates were revealed to be opposite. DFT evaluation of all possible diastereomeric transition states confirmed initial premises that guided rational ligand and directing group design. The implications of this study will assist in the further development of enantioselective C(sp3)-H activation, namely by highlighting the non-innocence of directing groups, distal steric influences, and the delicate interplay between steric Pauli repulsion and London dispersion in enantioinduction.

Access to α‐ and β‐Hydroxyamides and Ureas Through Metal‐Catalyzed C≡N Bond Hydration and Transfer Hydration Reactions

AbstractThe hydration of nitriles is an important transformation because the resulting primary amides present a huge number of applications in synthetic organic chemistry, as well as industrial and pharmaceutical interest. Metallic compounds (complexes, oxides, and nanoparticles) are known to catalyze the hydration of nitriles by activating the nitrile substrate, the water molecule, or both partners, upon coordination. In this Minireview article, the application of metal‐based catalysts in the hydration of α‐ and β‐hydroxynitriles and cyanamides is comprehensively discussed. Compared to more classical organonitriles, little attention has been paid to the hydration of these particular class of substrates despite the synthetic relevance of the respective carboxamides, i. e. α‐/β‐hydroxyamides and ureas. Transfer hydration strategies, in which a water surrogate is employed to convert the C≡N group into the C(=O)NH2 one, are also covered.

Insight into Hydrogen Abstractions by Nitrate Radical: Structural, Solvent Effects, and Evidence for a Polar Transition State.

The role of a polarized transition state and solvent effects on nitrate radical reactions was examined with a previously under-reported class of substrates, ethers, for their atmospheric implications. Absolute rate constants for hydrogen abstraction from a series of alcohols, ethers, and alkanes by nitrate radical have been measured in acetonitrile, water, and mixtures of these two solvents. Across all of these classes of compounds, using a modified form of the Evans-Polanyi relationship, it is demonstrated that the observed structure/reactivity trends can be reconciled by considering the number of abstractable hydrogens, strength of the C-H bond, and ionization potential (IP) of the substrate. Hydrogen abstractions by nitrate radical occur with low selectivity and are characterized by an early transition state (α ≈ 0.3). The dependence of the rate constant on IP suggests a polar transition state with some degree (<10%) of charge transfer. These conclusions stand for reactions conducted in solution (CH3CN and H2O) as well as gas-phase values. Because of this polar transition state, the rate constants increase going from the gas phase to a polar solvent, and the magnitude of the increase is consistent with Kirkwood theory.

Electrochemical Nozaki-Hiyama-Kishi Coupling: Scope, Applications, and Mechanism.

One of the most oft-employed methods for C-C bond formation involving the coupling of vinyl-halides with aldehydes catalyzed by Ni and Cr (Nozaki-Hiyama-Kishi, NHK) has been rendered more practical using an electroreductive manifold. Although early studies pointed to the feasibility of such a process, those precedents were never applied by others due to cumbersome setups and limited scope. Here we show that a carefully optimized electroreductive procedure can enable a more sustainable approach to NHK, even in an asymmetric fashion on highly complex medicinally relevant systems. The e-NHK can even enable non-canonical substrate classes, such as redox-active esters, to participate with low loadings of Cr when conventional chemical techniques fail. A combination of detailed kinetics, cyclic voltammetry, and in situ UV-vis spectroelectrochemistry of these processes illuminates the subtle features of this mechanistically intricate process.

Radical Chain Reduction via Carbon Dioxide Radical Anion (CO2•-).

We developed an effective method for reductive radical formation that utilizes the radical anion of carbon dioxide (CO2•-) as a powerful single electron reductant. Through a polarity matched hydrogen atom transfer (HAT) between an electrophilic radical and a formate salt, CO2•- formation occurs as a key element in a new radical chain reaction. Here, radical chain initiation can be performed through photochemical or thermal means, and we illustrate the ability of this approach to accomplish reductive activation of a range of substrate classes. Specifically, we employed this strategy in the intermolecular hydroarylation of unactivated alkenes with (hetero)aryl chlorides/bromides, radical deamination of arylammonium salts, aliphatic ketyl radical formation, and sulfonamide cleavage. We show that the reactivity of CO2•- with electron-poor olefins results in either single electron reduction or alkene hydrocarboxylation, where substrate reduction potentials can be utilized to predict reaction outcome.

Anapole-assisted giant electric field enhancement for surface-enhanced coherent anti-Stokes Raman spectroscopy

The coherent anti-Stokes Raman spectroscopy (CARS) techniques are recognized for their ability to detect and identify vibrational coherent processes down to the single-molecular levels. Plasmonic oligomers supporting full-range Fano-like line profiles in their scattering spectrum are one of the most promising class of substrates in the context of surface-enhanced (SE) CARS application. In this work, an engineered assembly of metallic disk-shaped nanoparticles providing two Fano-like resonance modes is presented as a highly-efficient design of SECARS substrate. We show that the scattering dips corresponding to the double-Fano spectral line shapes are originated from the mutual interaction of electric and toroidal dipole moments, leading to the so-called non-trivial first- and second-order anapole states. The anapole modes, especially the higher-order ones, can result in huge near-field enhancement due to their light-trapping capability into the so-called “hot spots”. In addition, independent spectral tunability of the second Fano line shape is exhibited by modulating the gap distance of the corner particles. This feature is closely related to the electric current loop associated with the corner particles in the second-order anapole state and provides a simple design procedure of an optimum SECARS substrate, where the electric field hot spots corresponding to three involved wavelengths, i.e., anti-Stokes, pump, and Stokes, are localized at the same spatial position. These findings yield valuable insight into the plasmonic substrate design for SECARS applications as well as for other nonlinear optical processes, such as four-wave mixing and multi-photon surface spectroscopy.

Functional Cooperativity between the Trigger Factor Chaperone and the ClpXP Proteolytic Complex

A functional association is uncovered between the ribosome-associated trigger factor (TF) chaperone and the ClpXP degradation complex. Bioinformatic analyses demonstrates conservation of the close proximity of tig, gene coding for TF, and genes coding for ClpXP suggesting a functional interaction. Effect of TF on ClpXP-dependent degradation varies based on the nature of substrate. While degradation of some substrates are slowed down or are unaffected by TF, surprisingly, TF increases the degradation rate of a third class of substrates. These include λ phage replication protein λO, master regulator of stationary phase RpoS, and SsrA-tagged proteins. Globally, TF acts to enhance the degradation of about 2% of newly synthesized proteins. TF is found to interact through multiple sites with ClpX in a highly dynamic fashion to promote protein degradation. This chaperone-protease cooperation constitutes a unique and likely ancestral aspect of cellular protein homeostasis in which TF acts as an adaptor for ClpXP.