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Honey truffle sweetener (HTS), a 121 amino acid protein is identified as a high-intensity sweetener found naturally occurring in the Hungarian Sweet Truffle Mattirolomyces terfezioides , an edible mushroom used in regional diets. The protein is intensely sweet, but the truffle is difficult to cultivate; therefore, the protein was systematically characterized, and the gene coding for the protein was expressed in a commonly used host yeast Komagataella phaffii . The heterologously expressed protein maintained the structural characteristics and sweet taste of the truffle. Preliminary safety evaluations for use as a food ingredient were performed on the protein including digestibility and in silico approaches for predicting the allergenicity and toxicity of the protein. HTS is predicted to be nonallergenic, nontoxic, and readily digestible. This protein is readily produced by precision fermentation of the host yeast, making it a potential replacement for both added sugars and small molecule high-intensity sweeteners in food.

Herein, we disclose an expedient visible-light-mediated, organophotoredox-catalyzed multicomponent synthesis of unnatural amino acids using a Katritzky salt, glyoxal derivatives, and substituted anilines. Mechanistically, an alkyl radical is generated from the Katritzky salt via a deaminative process that undergoes addition to the in situ -generated imine to furnish α-amino acids in a moderate diastereoisomeric ratio. For the first time, we have demonstrated this deaminative protocol to access substituted β-amino acids from α-amino acid-derived Katritzky salts. Furthermore, α-amino amides are also generated from the corresponding 2-oxoacetamide derivatives.

In the aftermath of the COVID-19 pandemic, opportunities to modulate biological pathways common to the lifecycles of viruses need to be carefully considered. N -linked glycosylation in humans is mediated exclusively by the oligosaccharyltransferase complex and is frequently hijacked by viruses to facilitate infection. As such, STT3A/B, the catalytic domain of the OST complex, became an intriguing drug target with broad-spectrum antiviral potential. However, due to the critical role N -linked glycosylation plays in a number of fundamental human processes, the toxicological ramifications of STT3A/B inhibition required attention commensurate to that given to antiviral efficacy. Herein, we describe how known STT3A/B inhibitor NGI-1 inspired the discovery of superior tool compounds which were evaluated in in vitro efficacy and translational safety (e.g., CNS, cardiovascular, liver) studies. The described learnings will appeal to those interested in the therapeutic utility of modulating N -linked glycosylation as well as the broader scientific community.

The sensitivity of ferroelectric domain walls to external stimuli makes them functional entities in nanoelectronic devices. Specifically, optically driven domain reconfiguration with in-plane polarization is advantageous and thus is highly sought. Here, we show the existence of in-plane polarized subdomains imitating a single domain state and reversible optical control of its domain wall movement in a single-crystal of ferroelectric BaTiO 3 . Similar optical control in the domain configuration of nonpolar ferroelastic material indicates that long-range ferroelectric polarization is not essential for the optical control of domain wall movement. Instead, flexoelectricity is found to be an essential ingredient for the optical control of the domain configuration, and hence, ferroelastic materials would be another possible candidate for nanoelectronic device applications.

We have devised a highly diastereoselective formal [2 + 1] annulation reaction of arylidene/alkylidine-pyrazolones with in situ-generated supported as well as standard pyridinium ylides to construct spirocyclopropanyl-pyrazolones. The cascade approach exhibits a wide range of functional group tolerance, gram-scale capability, and substrate versatility. A diverse range of spirocyclic cyclopropanes was synthesized extensively with both mediators, and the supported pyridine was reused in subsequent cycles. Density functional theory calculations confirmed the formation of spirocyclopropane as the lower energy pathway.

NASICON structured Na 3 V 2 (PO 4 ) 3 (NVP) has captured enormous attention as a potential cathode for next-generation sodium-ion batteries (SIBs), owing to its sturdy crystal structure and high theoretical capacity. Nonetheless, its poor intrinsic electronic conductivity has led to inferior electrochemical performance in terms of rate capability and long cycling performance. To address this problem, a combined strategy is adopted, such as (1) carbon coating and (2) high valent Sn 4+ ion doping in the lattice site of vanadium in the NVP cathode. Carbon coating can effectively enhance the surface electronic conductivity, wherein high-valent Sn 4+ improves the bulk intrinsic electronic conductivity of the materials. Moreover, Sn is a well-known alloying/dealloying type anode for SIBs; thus, doping of such metal in cathode materials will assume the role of structure stabilizing pillars and establishing high-performing cathode materials. Herein, Na 3 V 2- x Sn x (PO 4 ) 3 /C (denoted as Sn( x )-NVP/C, where x = 0.00, 0.03, 0.05, 0.07, 0.1) were synthesized via sol-gel route, followed by calcination at 800 °C. XRD, Raman, XPS, and electron microscopy data confirmed the high purity of the synthesized cathode. The optimized Sn(0.07)-NVP/C exhibited excellent electrochemical performance in terms of high rate capability and long cycling performance, a high appreciable capacity of 98 mAh g -1 with capacity retention of 85% after 500 cycles. Similarly, at a high current of 20C, it is still able to deliver a stable capacity of 76 mAh g -1 with 85% capacity retention after 3000 cycles. The rate capability study indicates the high current tolerance of Sn(0.07)-NVP/C up to 70 C with a capacity delivery of 55 mAh g -1 . It is worth mentioning that CV and EIS analysis for Sn(0.07)-NVP/C cathode displayed minimum voltage polarization and enhanced diffusion coefficient. Moreover, DFT calculation also proved that the electronic and ionic conductivity of NVP is promoted by Sn doping. Hence, the present results demonstrated that Sn(0.07)-NVP/C is considered a promising cathode for sodium-ion battery application.

Fog harvesting relies on intercepting atmospheric or industrial fog by placing a porous obstacle, for example, a mesh and collecting the deposited water. In the face of global water scarcity, such fog harvesting has emerged as a viable alternative source of potable water. Typical fog harvesting meshes suffer from poor collection efficiency due to aerodynamic bypassing of the oncoming fog stream and poor collection of the deposited water from the mesh. One pestering challenge in this context is the frequent clogging up of mesh pores by the deposited fog water, which not only yields low drainage efficiency but also generates high aerodynamic resistance to the oncoming fog stream, thereby negatively impacting the fog collection efficiency. Minimizing the clogging is possible by rendering the mesh fibers superhydrophobic, but that entails other detrimental effects like premature dripping and flow-induced re-entrainment of water droplets into the fog stream from the mesh fiber. Herein, we improvise on traditional interweaved metal mesh designs by defining critical parameters, viz., mesh pitch, shade coefficient, and fiber wettability, and deducing their optimal values from numerically and experimentally observed morphology of collected fog water droplets under various operating scenarios. We extend our investigations over a varying range of mesh-wettability, including superhydrophilic and hydrophobic fibers, and go on to find optimal shade coefficients which would theoretically render clog-proof fog harvesting meshes. The aerodynamic, deposition, and overall collection efficiencies are characterized. Hydrophobic meshes with square pores, having fiber diameters smaller than the capillary length scale of water, and an optimal shade coefficient are found to be the most effective design of such clog-proof meshes.

Tunable thin-film coating-based reflective color displays have versatile applications including image sensors, camouflage devices, spatial light modulators, and intelligent windows. However, generating high-purity colors using such coatings have posed a challenge. Here, we reveal high-purity color generation using an ultralow-loss phase change material (Sb 2 S 3 )-based tunable aperiodic distributed Bragg reflector (A-DBR). By strategically adjusting the periodicity of the adjacent layers of A-DBRs, we realize a narrow photonic bandgap with high reflectivity to generate high-purity orange and yellow colors. In particular, we demonstrate an A-DBR with a large photonic bandgap tunability by changing the structural phase of Sb 2 S 3 layers from amorphous to crystalline. Moreover, we experimentally tailor multistate tunable colors through external optical stimuli. Unlike conventional nano thin-film coatings, our proposed approach offers an irradiance-free, narrowband, and highly reflective color band, achieving exceptional color purity by effectively suppressing reflections in off-color bands.

A biomimetic cell-based carrier system based on monocyte membranes and liposomes has been designed to create a hybrid "Monocyte-LP" which inherits the surface antigens of the monocytes along with the drug encapsulation property of the liposome. Förster resonance energy transfer (FRET) and polarization gated anisotropy measurements show the stiffness of the vesicles obtained from monocyte membranes (Mons), phosphatidylcholine membranes (LP), and Monocyte-LP to follow an increasing order of Mons > Monocyte-LP > LP. The dynamics of interface bound water molecules plays a key role in the elasticity of the vesicles, which in turn imparts higher delivery efficacy to the hybrid Monocyte-LP for a model anticancer drug doxorubicin than the other two vesicles, indicating a critical balance between flexibility and rigidity for an efficient cellular uptake. The present work provides insight on the influence of elasticity of delivery vehicles for enhanced drug delivery.

In recent times, the evolution of cationic polymerization has taken a multidirectional approach, with the development of cationic reversible addition-fragmentation chain transfer (RAFT) polymerization. In contrast to the conventional cationic polymerization methods, which were typically carried out under inert atmospheres and low temperatures, various novel polymerization techniques have been developed where the reactions are carried out in open air, operate at room temperature, are cost-effective, and are environmentally friendly. Besides, several external stimuli, such as heat, light, chemicals, electrical potential, etc. have been employed to activate and control the polymerization process. It also enables the combination of cationic polymerization with other polymerization methods in a single reaction vessel, eliminating the necessity for isolation and purification during intermediate steps. In addition, significant advancements have been made through various modifications in catalyst systems, resulting in polymers with an exceptionally high level of stereoregularity. This review article comprehensively analyses the recent developments in cationic polymerization, encompassing their applications and offering insights into future perspectives., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

Defect engineering, achieved by precise tuning of the atomic disorder within crystalline solids, forms a cornerstone of structural chemistry. This nuanced approach holds the potential to significantly augment thermoelectric performance by synergistically manipulating the interplay between the charge carrier and lattice dynamics. Here, the current study presents a distinctive investigation wherein the introduction of Hg doping into AgSbTe 2 serves to partially curtail structural disorder. This strategic maneuver mitigates potential fluctuations originating from pronounced charge and size disparities between Ag + and Sb 3+ , positioned in octahedral sites within the rock salt structure. Hg doping significantly improves the phase stability of AgSbTe 2 by restricting the congenital emergence of the Ag 2 Te minor secondary phase and promotes partial atomic ordering in the cation sublattice. Reduction in atomic disorder coalesced with a complementary modification of electronic structure by Hg doping results in increased carrier mobility. The formation of nanoscale superstructure with sizes (2-5 nm) of the order of phonon mean free path in AgSbTe 2 is further promoted by reduced partial disorder, causes enhanced scattering of heat-carrying phonons, and results in a glass-like ultralow lattice thermal conductivity (∼0.32 W m -1 K -1 at 297 K). Cumulatively, the multifaceted influence of Hg doping, in conjunction with the consequential reduction in disorder, allows achieving a high thermoelectric figure-of-merit, zT , of ∼2.4 at ∼570 K. This result defies conventional paradigms that prioritize increased disorder for optimizing zT .

Boron monoxide (BO), prepared by the thermal condensation of tetrahydroxydiboron, was first reported in 1955; however, its structure could not be determined. With the recent attention on boron-based two-dimensional materials, such as borophene and hexagonal boron nitride, there is renewed interest in BO. A large number of stable BO structures have been computationally identified, but none are supported by experiments. The consensus is that the material likely forms a boroxine-based two-dimensional material. Herein, we apply advanced 11 B NMR experiments to determine the relative orientations of B(B)O 2 centers in BO. We find that the material is composed of D 2 h -symmetric O 2 B-BO 2 units that organize to form larger B 4 O 2 rings. Further, powder diffraction experiments additionally reveal that these units organize to form two-dimensional layers with a random stacking pattern. This observation is in agreement with earlier density functional theory (DFT) studies that showed B 4 O 2 -based structures to be the most stable.

Thin film coatings with tunable colors have a broad range of applications, from solid-state reflective displays to steganography. Here, we propose a novel approach to chalcogenide phase change material (PCM)-incorporated steganographic nano-optical coatings (SNOC) as thin film color reflectors for optical steganography. The proposed SNOC design combines a broad-band and a narrow-band absorber made up of PCMs to achieve tunable optical Fano resonance in the visible wavelength, which is a scalable platform for accessing the full-color range. We demonstrate that the line width of the Fano resonance can be dynamically tuned by switching the structural phase of PCM from amorphous to crystalline, which is crucial for obtaining high-purity colors. For steganography applications, the cavity layer of SNOC is divided into an ultralow loss PCM and a high index dielectric material with identical optical thickness. We show that electrically tunable color pixels can be fabricated using the SNOC on a microheater device.

Merrifield resin-anchored pyridines were prepared and applied as reusable mediators for trans -selective cascade synthesis of 2,3-dihydroindoles. The developed approach relied on in situ N -ylide formation followed by Michael substitution reactions. The cascade reaction was also carried out efficiently with simple pyridine. The products were further transformed into synthetically valuable compounds, and supported pyridine was reused for multiple cycles. Density functional theory calculations confirmed the trans -selectivity as the lower-energy pathway.

Condensing atmospheric water vapor on surfaces is a sustainable approach to addressing the potable water crisis. However, despite extensive research, a key question remains: what is the optimal combination of the mode and mechanism of condensation as well as the surface wettability for the best possible water harvesting efficacy? Here, we show how various modes of condensation fare differently in a humid air environment. During condensation from humid air, it is important to note that the thermal resistance across the condensate is nondominant, and the energy transfer is controlled by vapor diffusion across the boundary layer and condensate drainage from the condenser surface. This implies that, unlike condensation from pure steam, filmwise condensation from humid air would exhibit the highest water collection efficiency on superhydrophilic surfaces. To demonstrate this, we measured the condensation rates on different sets of superhydrophilic and superhydrophobic surfaces that were cooled below the dew points using a Peltier cooler. Experiments were performed over a wide range of degrees of subcooling (10-26 °C) and humidity-ratio differences (5-45 g/kg of dry air). Depending upon the thermodynamic parameters, the condensation rate is found to be 57-333% higher on the superhydrophilic surfaces compared to the superhydrophobic ones. The findings of the study dispel ambiguity about the preferred mode of vapor condensation from humid air on wettability-engineered surfaces and lead to the design of efficient atmospheric water harvesting systems.

Effective wound management imposes several challenges in clinical outcomes due to the complexity of the wound microenvironment, bacterial infections, impaired angiogenesis, aggravated inflammation, and enduring pain. In addition, adhesion on wet biological tissue is another extremely challenging task. Addressing all the issues is necessary for an effective wound healing process. Herein, we developed a unique multifunctional, adhesive composite hydrogel composed of gelatin, chitosan, polydopamine-coated bioactive glass (BG), and curcumin-capped silver nanoparticles (Cur-AgNPs) to target the multifaceted complexity of the wound. The PDA-coated BG serves multiple purposes: (1) adhesivity: catechol groups of PDA and Ca ion released from BG chelate the group present in the hydrogel network and surrounding tissues, (2) angiogenesis: promotes vascularization due to the release of Si from BG, and (3) BG also serves as the "reservoir" for the pain-relieving diclofenac sodium drug with a sustained-release behavior. Cur-AgNPs provide excellent bactericidal and anti-inflammatory properties to the composite hydrogel. In situ application of the composite hydrogel could serve the purpose of a "skin biomimetic" and work as a barrier along with bactericidal properties to inhibit the microbial growth. The multifunctional composite hydrogel (MCH) targeted multiple aspects of wound repair including pain alleviation, elimination of microbes (up to 99%), reduced inflammation, high adhesivity, and increased angiogenesis for effective skin regeneration. The MCH showed excellent wound healing potential as significant wound closure was observed at day 7 and also significantly upregulated the expression of crucial genes involved in the skin regeneration process along with increasing vascularization in the wound area.

We report herein a mild highly chemoselective palladium-catalyzed cross-electrophile coupling between readily accessible aromatic diazonium salt and aryl iodide or diaryliodonium salt in water-ethanol (2:1) medium. Mechanistic studies revealed that ethanol is crucial to generate an active Pd(0) catalyst, and the counterion of the diazonium salt renders a cationic Pd(II) species that facilitates subsequent oxidative addition to aryl iodide/diaryliodonium salt. Silver(I) salt was crucial to retain the catalytic activity of palladium, removing the iodide ion as a precipitate.

Structural non-centrosymmetry in semiconducting organic-inorganic hybrid halide perovskites can introduce functionalities like anomalous photovoltaics and nonlinear optical properties. Here we introduce a design principle to prepare Pb- and Bi-based two- and one-dimensional hybrid perovskites with polar non-centrosymmetric space groups. The design principle relies on creating dissimilar hydrogen and halogen bonding non-covalent interactions at the organic-inorganic interface. For example, in organic cations like I-(CH 2 ) 3 -NH 2 (CH 3 ) + (MIPA), -CH 3 is substituted by -CH 2 I at one end, and -NH 3 + is substituted by -NH 2 (CH 3 ) + at the other end. These substitutions of two -H atoms by -I and -CH 3 reduce the rotational symmetry of MIPA at both ends, compared to an unsubstituted cation, for example, H 3 C-(CH 2 ) 3 -NH 3 + . Consequently, the dissimilar hydrogen-iodine and iodine-iodine interactions at the organic-inorganic interface of (MIPA) 2 PbI 4 2D perovskites break the local inversion symmetries of Pb-I octahedra. Owing to this non-centrosymmetry, (MIPA) 2 PbI 4 displays visible to infrared tunable nonlinear optical properties with second and third harmonic generation susceptibility values of 5.73 pm V -1 and 3.45 × 10 -18 m 2 V -2 , respectively. Also, the single crystal shows photocurrent on shining visible light at no external bias, exhibiting anomalous photovoltaic effect arising from the structural asymmetry. The design strategy was extended to synthesize four new non-centrosymmetric hybrid perovskite compounds. Among them, one-dimensional (H 3 N-(CH 2 ) 3 -NH(CH 3 ) 2 )BiI 5 shows a second harmonic generation susceptibility of 7.3 pm V -1 and a high anomalous photovoltaic open-circuit voltage of 22.6 V.

Effective manipulation of liquids on open surfaces without external energy input is indispensable for the advancement of point-of-care diagnostic devices. Open-surface microfluidics has the potential to benefit health care, especially in the developing world. This review highlights the prospects for harnessing capillary forces on surface-microfluidic platforms, chiefly by inducing smooth gradients or sharp steps of wettability on substrates, to elicit passive liquid transport and higher-order fluidic manipulations without off-the-chip energy sources. A broad spectrum of the recent progress in the emerging field of passive surface microfluidics is highlighted, and its promise for developing facile, low-cost, easy-to-operate microfluidic devices is discussed in light of recent applications, not only in the domain of biomedical microfluidics but also in the general areas of energy and water conservation.

In a three-dimensional (3D) representation, each protein molecule displays a specific pattern of chemical and topological features, which are altered during its misfolding and aggregation pathway. Generating a recognizable fingerprint from such features could provide an enticing approach not only to identify these biomolecules but also to gain clues regarding their folding state and the occurrence of pathologically lethal misfolded aggregates. We report here a universal strategy to generate a fluorescent fingerprint from biomolecules by employing the pan-selective molecular recognition feature of a cucurbit[7]uril (CB[7]) macrocyclic receptor. We implemented a direct sensing strategy by covalently tethering CB[7] with a library of fluorescent reporters. When CB[7] recognizes the chemical and geometrical features of a biomolecule, it brings the tethered fluorophore into the vicinity, concomitantly reporting the nature of its binding microenvironment through a change in their optical signature. The photophysical properties of the fluorophores allow a multitude of probing modes, while their structural features provide additional binding diversity, generating a distinct fluorescence fingerprint from the biomolecule. We first used this strategy to rapidly discriminate a diverse range of protein analytes. The macrocyclic sensor was then applied to probe conformational changes in the protein structure and identify the formation of oligomeric and fibrillar species from misfolded proteins. Notably, the sensor system allowed us to differentiate between different self-assembled forms of the disease-specific amyloid-β (Aβ) aggregates and segregated them from other generic amyloid structures with a 100% identification accuracy. Ultimately, this sensor system predicted clinically relevant changes by fingerprinting serum samples from a cohort of pregnant women.

Five new mononuclear lanthanide complexes, [LnL 2 ][Et 3 NH]·THF/H 2 O (Ln = Nd, Tb, Dy) (H 2 L Cl = 2-bis(2-hydroxy-3,5-dichloro benzyl)aminomethyl]pyridine), Ln = Nd ( 1 ), Tb ( 2 ), and Dy ( 3 ), and (H 2 L Br = 2-bis(2-hydroxy-3,5-dibromo benzyl)aminomethyl]pyridine), Ln = Nd ( 4 , H 2 O) and Tb ( 5 ), were synthesized and structurally characterized by single-crystal X-ray diffraction analyses. Being isostructural in all the five cases, the metal center is octa-coordinated with a triangular dodecahedron ( D 2 d symmetry) geometry, and it is independent of the halogen substitution (Cl/Br). This close similarity is due to the composite interplay of hydrogen/halogen bond interactions that control the overall crystal packing, yet notable differences in association patterns among the individual ones arise from the subtle stereo-electronic requirement of individual molecules in the three-dimensional (3D) architecture. Hirshfeld surface and density functional theory (DFT) calculations clearly vouch for the importance of the hydrogen bond and halogen bond interactions observed in the structure. Detailed magnetic measurements using direct-current and alternating-current susceptibility measurements show slow magnetic relaxation in 3 , a characteristic feature of the single-molecule magnets (SMMs), which is not shown by 1 and 2 . Steady-state and time-resolved photoluminescence of Tb(III) complexes shows a strong ligand-to-metal energy transfer that can be modulated by changing the substitution on phenolic ligands. The results from these analyses indicate that it may be advantageous to consider the subtle role of hydrogen bond (HB)/halogen bond (XB) intermolecular interactions judiciously for the design of SMMs and luminescent materials based on halogen-substituted ligands.

Magnetic nanoparticles as drug carriers, despite showing immense promises in preclinical trials, have remained to be only of limited use in real therapeutic practice primarily due to unresolved anomalies concerning their grossly contrasting controllability and variability in performance in artificial test benches as compared to human tissues. To circumvent the deficits of reported in vitro drug testing platforms that deviate significantly from the physiological features of the living systems and result in this puzzling contrast, here, we fabricate a biomimetic microvasculature in a flexible tissue phantom and demonstrate distinctive mechanisms of magnetic-field-assisted controllable penetration of biocompatible iron oxide nanoparticles across the same, exclusively modulated by tissue deformability, which has by far remained unraveled. Our experiments deciphering the transport of magnetic nanoparticles in a blood analogue medium unveil a decisive interplay of the flexibility of the microvascular pathways, magnetic pull, and viscous friction toward orchestrating the optimal vascular penetration and targeting efficacy of the nanoparticles in colorectal tissue-mimicking bioengineered media. Subsequent studies with biological cells confirm the viability of using localized magnetic forces for aiding nanoparticle penetration within cancerous lesions. We establish nontrivially favorable conditions to induce a threshold force for vascular rupture and eventual target of the nanoparticles toward the desired extracellular site. These findings appear to be critical in converging the success of in vitro trials toward patient-specific targeted therapies depending on personalized vascular properties obtained from medical imaging data.

Complexes of cationic liposomes with DNA have emerged as promising nonviral vectors for delivering genetic information into cells for gene therapy. Kinetics of the liposome/DNA complex (lipoplex) formation on a millisecond time scale are studied by monitoring time evolution of fluorescence of 8-anilino-1-naphthalene sulfonic acid (ANS) and ethidium bromide (EtBr) in a continuous flow microfluidic channel coupled to a fluorescence microscope. The formation of lipoplexes between calf thymus DNA and liposomes based on two novel cationic lipids (Lip1810 and Lip1814) are found to follow a two-step process with kinetic constants for the Lip1814/DNA complex ( k 1 = 1120-1383 s -1 , k 2 = 0.227-1.45 s -1 ) being significantly different from those ( k 1 = 68.53-98.5 s -1 , k 2 = 32.3-60.19 s -1 ) corresponding to formation of the Lip1810/DNA complex. The kinetic pathway leading to the formation of Lip1814/DNA complex is diffusion-controlled whereas the formation of Lip1810/DNA complex occurs by a conformational rearrangement-controlled pathway . The observed difference in the kinetics of lipoplex formation likely originates from different structures of the lipid/DNA complexes.

Thin film optical coatings have a wide range of industrial applications from displays and lighting to photovoltaic cells. The realization of electrically tunable thin film optical coatings in the visible wavelength range is particularly important to develop energy efficient and dynamic color filters. Here, we experimentally demonstrate dynamic color generation using electrically tunable thin film optical coatings that consist of two different phase change materials (PCMs). The proposed active thin film nanocavity excites the Fano resonance that results from the coupling of a broadband and a narrowband absorber made up of phase change materials. The Fano resonance is then electrically tuned by structural phase switching of PCM layers to demonstrate active color filters covering the entire visible spectrum. In contrast to existing thin film optical coatings, the developed electrically tunable PCM based Fano resonant thin optical coatings have several advantages in tunable displays and active nanophotonic applications.

Mutant polypeptide GB1HS#124 F26A , which is known to aggregate into amyloid-like fibrils, has been utilized as a model in this study for gaining insights into the mechanism of domain-swapped aggregation through real-time monitoring. Size exclusion with UV monitoring at 280 nm and dynamic light scattering (DLS) profiles through different time points of fibrillation reveal that the dimer transitions into monomeric intermediates during the aggregation, which could further facilitate domain swapping to form amyloid fibrils. The 1D 1 H and 2D 1 H- 13 C HSQC nuclear magnetic resonance (NMR) spectra profiling through different time points of fibrillation reveal that there may be some other species present along with the dimer during aggregation which contribute to different trends for the intensity of protons in the spectral peaks. Diffusion NMR reveals changes in the mobility of the dimeric species during the process of aggregation, indicating that the dimer gives rise to other lower molecular weight species midway during aggregation, which further add up to form the oligomers and amyloid fibrils successively. The present work is a preliminary study which explores the possibility of utilizing biophysical methods to gain atomistic level insights into the different stages of aggregation., Competing Interests: The authors declare no competing financial interest., (© 2021 The Authors. Published by American Chemical Society.)

We present here a metal-free, visible-light- and triphenylphosphine-mediated intermolecular, reductive amination between nitroarenes and boronic acids at ambient temperature without any photocatalyst. Mechanistically, a slow reduction of nitroarenes to a nitroso and, finally, a nitrene intermediate occurs that leads to the amination product with concomitant 1,2-aryl/-alkyl migration from a boronate complex. A wide range of nitroarenes underwent C-N coupling with aryl-/alkylboronic acids providing high yields.

The increased use of transition fuels, such as natural gas, and the resulting increase in methane emissions have resulted in a need for novel methane storage materials. Metal-organic frameworks (MOFs) have shown promise as efficient storage materials. A virtually limitless number of potential MOFs can be hypothesized, which exhibit a wide variety of different structural and chemical characteristics. Because of the numerous possibilities, identification of the best MOF for methane storage can be a potentially challenging problem. In this work, determination of the best such MOF was cast as an inverse function problem. The function, a random forest (RF) model using 12 structural and chemical descriptors, was trained on 10% of a data set consisting of 130 398 hypothetical MOFs (hMOFs) to predict simulated methane uptake. The RF model was tested on the remaining 90% of the data. After validation, a genetic algorithm (GA) was used to evolve in silico the best MOFs for methane adsorption. The RF model was imbedded into the GA as the fitness function to predict the methane uptake of the evolved MOFs (eMOFs). The best 15 eMOFs matched hMOFs found in the top 1% of the database. Nine of the 15 eMOFs were found in the top 0.1%. More impressively, two of the eMOFs matched the top two hypothetical MOFs with the highest methane uptake values out of the entire database of 130 398 MOFs. Further, by leveraging the ensemble nature of the GA, it was possible to characterize the importance of the different material properties for methane adsorption, providing fundamental insight for future material design strategies.

Corn wet distillers' fiber (corn fiber) is a byproduct of the corn-ethanol production process, with high potential as a precursor for activated carbon due to its moderate nitrogen content and availability. However, there has been limited investigation into activated carbons from the corn fiber. In this work, we produce activated carbons from the corn fiber using three procedures, including direct KOH activation, hydrothermal carbonization (HTC) followed by KOH activation, and FeCl 3 -catalyzed HTC followed by KOH activation. Catalytic HTC with FeCl 3 was found to slightly increase the degree of carbonization relative to uncatalyzed HTC while also removing the nitrogen content at increasing concentrations and slightly increasing the porosity. The resulting activated carbon samples are then characterized by thermal gravimetric analysis, Fourier transform infrared spectroscopy, scanning electron microscopy, and nitrogen analysis. The two-step process resulted in activated carbon with substantially higher surface areas than the one-step process (1220 vs 789 m 2 /g), as well as much higher thermal stability and nitrogen content (up to 1.20%). The results show that the corn fiber has potential for activated carbon production, with the two-step HTC followed by the activation process producing more favorable material properties than direct activation., Competing Interests: The authors declare no competing financial interest., (© 2021 The Authors. Published by American Chemical Society.)

The realization of electrically tunable plasmonic resonances in the ultraviolet (UV) to visible spectral band is particularly important for active nanophotonic device applications. However, the plasmonic resonances in the UV to visible wavelength range cannot be tuned due to the lack of tunable plasmonic materials. Here, we experimentally demonstrate tunable plasmonic resonances at visible wavelengths using a chalcogenide semiconductor alloy such as antimony telluride (Sb 2 Te 3 ), by switching the structural phase of Sb 2 Te 3 from amorphous to crystalline. We demonstrate the excitation of a propagating surface plasmon with a high plasmonic figure of merit in both amorphous and crystalline phases of Sb 2 Te 3 thin films. We show polarization-dependent and -independent plasmonic resonances by fabricating one and two-dimensional periodic nanostructures in Sb 2 Te 3 thin films, respectively. Moreover, we demonstrate electrically tunable plasmonic resonances using a microheater integrated with the Sb 2 Te 3 /Si device. The developed electrically tunable Sb 2 Te 3 -based plasmonic devices could find applications in the development of active color filters.

Liquid-jet impact on porous, relatively thin solids has a variety of applications in heat transfer, filtration, liquid-fuel atomization, incontinence products, and solid-substrate erosion, among others. Many prior studies focused on liquid-jet impact on impermeable substrates, and some have investigated the hydraulic jump phenomenon. In the present work, the liquid jet strikes a superhydrophobic, permeable, metal mesh orthogonally, and the radial spreading and throughflow of the liquid are characterized. The prebreakthrough hydraulic jump, the breakthrough velocity, and the postbreakthrough spatial distributions of the liquid are investigated by varying the liquid properties (density, surface tension, and viscosity) and the openness of the metal mesh. The hydraulic jump radius in the prebreakthrough regime increases with jet velocity and is independent of the liquid properties and mesh geometry (pore size, wire diameter and pitch). The breakthrough velocity increases with surface tension of the liquid and decreases with the mesh opening diameter and liquid viscosity. A simple analytical model predicts the jet breakthrough velocity; its predictions are in accordance with the experimental observations. In the postbreakthrough regime, as the jet velocity increases, the liquid flow rate penetrating the mesh shows an initially steep increase, followed by a plateau, which is attributed to a Cassie-Baxter-to-Wenzel transition at the impact area of the mesh.

Communication between neurons relies on the release of diverse neurotransmitters, which represent a key-defining feature of a neuron's chemical and functional identity. Neurotransmitters are packaged into vesicles by specific vesicular transporters. However, tools for labeling and imaging synapses and synaptic vesicles based on their neurochemical identity remain limited. We developed a genetically encoded probe to identify glutamatergic synaptic vesicles at the levels of both light and electron microscopy (EM) by fusing the mini singlet oxygen generator (miniSOG) probe to an intralumenal loop of the vesicular glutamate transporter-2. We then used a 3D imaging method, serial block-face scanning EM, combined with a deep learning approach for automatic segmentation of labeled synaptic vesicles to assess the subcellular distribution of transporter-defined vesicles at nanometer scale. These tools represent a new resource for accessing the subcellular structure and molecular machinery of neurotransmission and for transmitter-defined tracing of neuronal connectivity.

The key feature of the present work is the dexterous utilization of an apparently destructive process, pyrolysis, for the synthesis of the most esteemed nanomaterial, graphene. This work is an attempt to synthesize graphene from nonconventional sources such as tannic acid, alginic acid, and green tea by a controlled pyrolysis technique. The precursors used in this work are not petroleum-derived and hence are green. A set of pyrolysis experiments was carried out at different temperatures, followed by a thorough step-by-step analysis of the product morphology, enabling the optimization of the graphitization conditions. A time-dependent morphological analysis was also carried out along with isothermal thermogravimetric studies to optimize the ideal pyrolysis time for graphitization. The specific capacitance of the graphene obtained from alginic acid was 315 F/g, which makes it fairly suitable for application as green supercapacitors. The same graphene was also used to fabricate a rubber-latex-based flexible supercapacitor film with 137 F/g specific capacitance. The graphene and graphene-based latex film exhibited room-temperature magnetic hysteresis, indicating their ferromagnetic nature, which also supports their spintronic applications., Competing Interests: The authors declare no competing financial interest., (© 2021 American Chemical Society.)

Spreading of liquid droplets on wettability-confined paths has attracted considerable attention in the past decade. On the other hand, the inverse scenario of a gas bubble spreading on a submerged, wettability-confined track has rarely been studied. In the present work, an experimental investigation of the spreading of millimetric gas bubbles on horizontally submerged, textured, wettability-confined tracks is carried out. The width of the track is kept fixed along its entire length, and the spreading behavior of a gas bubble, dispensed at one end of the track, is studied. The effects of varying track width, bubble diameter, and ambient liquid are investigated. Post-contact, the gas bubble spreads along the track at a linear rate with time, while remaining pinned at its back end; the recorded spreading speed is O (0.5 m/s). An inertio-capillary force balance describes the experimentally observed spreading dynamics with excellent agreement.

We report herein a Pd(II)/bis-sulfoxide-catalyzed intramolecular allylic C-H acetoxylation of aryl allyl ether, amine, and amino acids with the retention of a labile allyl moiety. Mechanistically, the reaction proceeds through a distinct double-bond isomerization from the allylic to the vinylic position followed by intramolecular carboxypalladation and the β-hydride elimination pathway. For the first time, C-H oxidation of N -allyl-protected amino acids to furnish five-membered heterocycles through 1,3-syn-addition is established with excellent diastereoselectivity.

A new molecular donor-acceptor-donor (D-A-D) triad, comprised of an electron deficient 1,4,5,8-naphthalene tetracarboxylic diimide (NDI) unit covalently connected to two flanking photosensitizers, i.e., a bis-heteroleptic Ru(II) complex of 1,10-phenanthroline and pyridine triazole hybrid ligand, is described. The single crystal X-ray structure of the perchlorate salt of the triad demonstrates that the electron deficient NDI unit can act as a host for anions via anion-π interaction. Detailed solution-state studies indicate that fluoride selectively interacts with the D-A-D triad to form a dianionic NDI, NDI 2- , via a radical anion, NDI •- . On the contrary, cyanide reduces the NDI moiety to NDI •- , as confirmed by UV-vis, NMR, and EPR spectroscopy. Further, femtosecond transient absorption spectroscopic studies reveal a low luminescence quantum yield of the D-A-D triad attributable to the photoinduced electron transfer (PET) process from the photoactive Ru(II) center to the NDI unit. Interestingly, the triad displays "OFF-ON" luminescence behavior in the presence of fluoride by restoring the Ru(II) to phenanthroline/pyridine-triazole-based MLCT emission, whereas cyanide fails to show a similar property due to a different redox process operational in the latter. The reduction of NDI in the presence of fluoride and cyanide in different polar solvents indicates that involvement of such deprotonated solvents in the electron transfer mechanism may not be operative in our present system. Low-temperature kinetic studies support the formation of a charge transfer associative transient species, which likely allows overcoming the thermodynamically uphill barrier for the direct electron transfer mechanism.

Pt is the best cocatalyst for hydrogen production. It is also well-known that the surface atomic layer is critical for catalysis. To minimize the Pt content as cocatalyst, herein we report on half-a-monolayer of Pt (0.5θ Pt ) decorated on earth-abundant Ni-Cu cocatalyst, which is integrated with a quasi-artificial leaf (QuAL) device (TiO 2 /ZnS/CdS) and demonstrated for efficient solar hydrogen production. For the QuAL, TiO 2 is sensitized with ZnS and CdS quantum dots by the SILAR method. The 0.5θ Pt -decorated Ni-Cu shows an onset potential of 0.05 V vs reversible hydrogen electrode for the hydrogen evolution reaction, which is almost similar to that of commercial Pt/C. Photoactivity of the present QuAL device with either bulk Pt or 0.5θ Pt -coated Ni-Cu cocatalyst is, surprisingly, equal. Our findings underscore that a fraction of a monolayer of Pt can enhance the activity of the cocatalyst, and it is worth exploring further for the high activity associated with atomic Pt and other noble metals.

Supramolecular block copolymerzation with optically or electronically complementary monomers provides an attractive bottom-up approach for the non-covalent synthesis of nascent axial organic heterostructures, which promises to deliver useful applications in energy conversion, optoelectronics, and catalysis. However, the synthesis of supramolecular block copolymers (BCPs) constitutes a significant challenge due to the exchange dynamics of non-covalently bound monomers and hence requires fine microstructure control. Furthermore, temporal stability of the segmented microstructure is a prerequisite to explore the applications of functional supramolecular BCPs. Herein, we report the cooperative supramolecular block copolymerization of fluorescent monomers in solution under thermodynamic control for the synthesis of axial organic heterostructures with light-harvesting properties. The fluorescent nature of the core-substituted naphthalene diimide (cNDI) monomers enables a detailed spectroscopic probing during the supramolecular block copolymerization process to unravel a nucleation-growth mechanism, similar to that of chain copolymerization for covalent block copolymers. Structured illumination microscopy (SIM) imaging of BCP chains characterizes the segmented microstructure and also allows size distribution analysis to reveal the narrow polydispersity (polydispersity index (PDI) ≈ 1.1) for the individual block segments. Spectrally resolved fluorescence microscopy on single block copolymerized organic heterostructures shows energy migration and light-harvesting across the interfaces of linearly connected segments. Molecular dynamics and metadynamics simulations provide useful mechanistic insights into the free energy of interaction between the monomers as well as into monomer exchange mechanisms and dynamics, which have a crucial impact on determining the copolymer microstructure. Our comprehensive spectroscopic, microscopic, and computational analyses provide an unambiguous structural, dynamic, and functional characterization of the supramolecular BCPs. The strategy presented here is expected to pave the way for the synthesis of multi-component organic heterostructures for various functions.

Utah Electrode Arrays (UEAs) have previously been characterized and implanted for neural recordings and stimulation at relatively low current levels. This proof-of-concept study investigated the applicability of UEAs in sub-surface cardiac pacing, for the first time, particularly to selectively sense and pace the His-Bundle (HB). HB pacing produces synchronous ventricular depolarization and improved cardiac function. Modified UEAs with sputtered iridium oxide film (SIROF) tips (100 - 150 μm) were characterized for SIROF delamination using an electrochemical impedance spectroscopy (EIS), scanning electron microscopy (SEM), and voltage transient (VT) techniques at various current levels of up to 8 mA for a biphasic pulse with 1 ms duration per phase at 4 Hz. Our results indicate that at a short pacing duration of 20 s with current levels of up to 4 mA, the SIROF exhibited a strong charge-transfer performance. For the longer pacing duration (6 min), SIROF demonstrated its holding capacity at all current levels except for ≥2 mA when delamination commenced for the time exceeded 4 min (EIS) and 2 min (VT). UEAs were inserted in isolated, perfused goat hearts to record the HB electrograms in real-time. Both stimulated and unstimulated electrodes were characterized for SIROF delamination before, during and after in vivo work. Our findings indicate that UEA was stable during the heart's contraction and relaxation phase. Further, at a short pacing duration with current levels of up to 4 mA, UEA demonstrated high selectively in sensing the HB. This proof-of-concept work demonstrates the potential applicability of UEAs in cardiac applications., Competing Interests: Conflict of Interest: Authors declare no conflict of interest.

Multicomponent supramolecular copolymerization promises to construct complex nanostructures with emergent properties. However, even with two monomeric components, various possible outcomes such as self-sorted supramolecular homopolymers, a random (statistical) supramolecular copolymer, an alternate supramolecular copolymer, or a complex supramolecular block copolymer can occur, determined by their intermolecular interactions and monomer exchange dynamics and hence structural prediction is extremely challenging. Herein, we target this challenge and demonstrate unprecedented two-component sequence controlled supramolecular copolymerization by manipulating thermodynamic and kinetic routes in the pathway complexity of self-assembly of the constitutive monomers. Extensive molecular dynamics simulations provided useful mechanistic insights into the monomer exchange rates and free energy of interactions between the monomers that dictate the self-assembly pathway and sequence. The fluorescent nature of core-substituted naphthalene diimide monomers has been further utilized to characterize the three sequences via Structured Illumination Microscopy (SIM).

Cells at disease onset are often associated with subtle changes in the expression level of a single or few molecular components, making traditionally used biomarker-driven clinical diagnosis a challenging task. We demonstrate here the design of a DNA nanosensor array with multichannel output that identifies the normal or pathological state of a cell based on the alteration of its global proteomic signature. Fluorophore-encoded single-stranded DNA (ssDNA) strands were coupled via supramolecular interaction with a surface-functionalized gold nanoparticle quencher to generate this integrated sensor array. In this design, ssDNA sequences exhibit dual roles, where they provide differential affinities with the receptor gold nanoparticle as well as act as transducer elements. The unique interaction mode of the analyte molecules disrupts the noncovalent supramolecular complexation, generating simultaneous multichannel fluorescence output to enable signature-based analyte identification via a linear discriminant analysis-based machine learning algorithm. Different cell types, particularly normal and cancerous cells, were effectively distinguished using their fluorescent fingerprints. Additionally, this DNA sensor array displayed excellent sensitivity to identify cellular alterations associated with chemical modulation of catabolic processes. Importantly, pharmacological effectors, which could modulate autophagic flux, have been effectively distinguished by generating responses from their global protein signatures. Taken together, these studies demonstrate that our multichannel DNA nanosensor is well suited for rapid identification of subtle changes in a complex mixture and thus can be readily expanded for point-of-care clinical diagnosis, high-throughput drug screening, or predicting the therapeutic outcome from a limited sample volume.

The impact of liquid droplets on permeable substrates is important for a number of applications, such as fog collection, liquid atomization, and interaction of liquids with filters and textiles. When a water droplet impacts a wettable mesh, it penetrates the mesh easily with a part of the liquid remaining pinned. On the other hand, when striking a superhydrophobic mesh, part of the water droplet may penetrate and detach from the parent droplet, depending upon the impact velocity and the relative length scales of the droplet and the mesh. In most cases, the remaining droplet would rebound from the top of the superhydrophobic mesh. In this work, we study the impact of a water droplet on a wettability-patterned mesh, with the droplet centrally impacting the wettability-contrast line between the superhydrophobic and superhydrophilic semi-infinite domains. Half of the droplet seeing the superhydrophobic domain responds to it in a fashion that differs from the half hitting the superhydrophilic mesh side. This creates a wide range of post-impact scenarios, depending on the impact conditions and the relative characteristics of the droplet and the mesh. The difference in mesh wettability leads to a net unbalanced surface-tension force that makes the droplet rebound with a horizontal momentum component directed from the non-wettable to the wettable side. Some part of the droplet may even detach during such directional rebounding (i.e., vectoring). Along with the experimental results, a simplified analytical model is presented, which differentiates the cases of detachment or no detachment during vectoring.

A recent report from the United Nations has warned about the excessive CO 2 emissions and the necessity of making efforts to keep the increase in global temperature below 2 °C. Current CO 2 capture technologies are inadequate for reaching that goal, and effective mitigation strategies must be pursued. In this work, we summarize trends in materials development for CO 2 adsorption with focus on recent studies. We put adsorbent materials into four main groups: (I) carbon-based materials, (II) silica/alumina/zeolites, (III) porous crystalline solids, and (IV) metal oxides. Trends in computational investigations along with experimental findings are covered to find promising candidates in light of practical challenges imposed by process economics.

There is growing interest in estimating quantum observables while circumventing expensive computational overhead for facile in silico materials screening. Machine learning (ML) methods are implemented to perform such calculations in shorter times. Here, we introduce a multistep method based on machine learning algorithms to estimate total energy on the basis of spatial coordinates and charges for various chemical structures, including organic molecules, inorganic molecules, and ions. This method quickly calculates total energy with 0.76 au in root-mean-square error (RMSE) and 1.5% in mean absolute percent error (MAPE) when tested on a database of optimized and unoptimized structures. Using similar molecular representations, experimental thermochemical properties were estimated, with MAPE as low as 6% and RMSE of 8 cal/mol·K for heat capacity in a 10-fold cross-validation.

The generalized Brewster angle (GBA) is the incidence angle at polarization by reflection for p- or s-polarized light. Realizing an s-polarization Brewster effect requires a material with magnetic response, which is challenging at optical frequencies since the magnetic response of materials at these frequencies is extremely weak. Here, we experimentally realize the GBA effect in the visible using a thin-film absorber system consisting of a dielectric film on an absorbing substrate. Polarization by reflection is realized for both p - and s - polarized light at different angles of incidence and multiple wavelengths. We provide a theoretical framework for the generalized Brewster effect in thin-film light absorbers. We demonstrate hydrogen gas sensing using a single-layer graphene film transferred on a thin-film absorber at the GBA with ∼1 fg/mm 2 aerial mass sensitivity. The ultrahigh sensitivity stems from the strong phase sensitivity near the point of darkness, particularly at the GBA, and the strong light-matter interaction in planar nanocavities. These findings depart from the traditional domain of thin films as mere interference optical coatings and highlight its many potential applications including gas sensing and biosensing., Competing Interests: The authors declare no competing financial interest.

A practical copper-catalyzed, 2-picolinamide-directed ortho C-H amination of anilines with benzoyl-protected hydroxylamines has been disclosed that proceeds smoothly without any external stoichiometric oxidant or additives. Remarkably, besides anilines, bicyclic naphthyl or heterocyclic amines furnished amination products with five- and six-membered cyclic and acyclic amines at the ortho position selectively. This electrophilic C-H amination also proceeds smoothly in water under slightly modified reaction conditions.

We report herein a visible-light-promoted, highly practical carboxylation of readily accessible aryl triflates at ambient temperature and a balloon pressure of CO 2 by the combined use of palladium and photoredox Ir(III) catalysts. Strikingly, the stoichiometric metallic reductant is replaced by a nonmetallic amine reductant providing an environmentally benign carboxylation process. In addition, one-pot synthesis of a carboxylic acid directly from phenol and modification of estrone and concise synthesis of pharmaceutical drugs adapalene and bexarotene have been accomplished via late-stage carboxylation reaction. Furthermore, a parallel decarboxylation-carboxylation reaction has been demonstrated in an H-type closed vessel that is an interesting concept for the strategic sector. Spectroscopic and spectroelectrochemical studies indicated electron transfer from the Ir(III)/DIPEA combination to generate aryl carboxylate and Pd(0) for catalytic turnover.

Protein-protein interactions (PPIs) have emerged as significant targets for therapeutic development, owing to their critical nature in diverse biological processes. An ideal PPI-based target is the protein myeloid cell leukemia 1 (MCL1), a critical prosurvival factor in cancers such as multiple myeloma where MCL1 levels directly correlate to disease progression. Current strategies for halting the antiapoptotic properties of MCL1 revolve around inhibiting its sequestration of proapoptotic factors. Existing inhibitors disrupt endogenous regulatory proteins; however, this strategy actually leads to an increase of MCL1 protein levels. Here, we show the development of hetero-bifunctional small molecules capable of selectively targeting MCL1 using a proteolysis targeting chimera (PROTAC) methodology leading to successful degradation. We have confirmed the involvement of the E3 ligase CUL4A-DDB1 cereblon ubiquitination pathway, making these PROTACs a first step toward a new class of antiapoptotic B-cell lymphoma 2 family protein degraders.

meso-Substituted calix[4]pyrroles 2-6 containing a direct meso-ethynyl linker displayed high binding affinities and unique conformational features on halide anion binding. A general conformational bias for the equatorial alignments of the meso-(aryl)ethynyl groups was observed in the host-halide complexes which was attributed to the repulsive anion-alkyne interactions and released steric strain. Such conformational features of host-halide complexes persisted even in the case of calix[4]pyrrole 6 bearing cationic meso components, which displayed the highest binding affinity for chloride anions among known meso-aryl calix[4]pyrroles. Synthetic details, conformational features, and comparative halide anion binding properties of this series of calix[4]pyrroles are described.