Self-assembly of water-filled molecular saddles to generate diverse morphologies and high proton conductivity.

The design of single-component organic compounds acting as efficient solid-state proton conduction (SSPC) materials has been gaining significant traction in recent times. Molecular design and controlled self-assembly are critical components in achieving highly efficient SSPC. In this work, we report the design, synthesis, and self-assembly of an organic macrocyclic aza-crown-type compound, P2Mac, which complements synthetic ease with efficient SSPC. P2Mac is derived from the pyridine-2,6-dicarboxamide (PDC) framework and contains polar amide and amine residues in its inner region, while aromatic residues occupy the periphery of the macrocycle. The crystal structure analysis revealed that P2Mac adopts a saddle-shaped geometry. Each P2Mac molecule interacts with one water molecule that is present in its central polar cavity, stabilized by a network of five hydrogen bonds. We could self-assemble P2Mac in a variety of unique, aesthetically pleasing morphologies such as micron-sized octahedra, hexapods, as well as hollow nanoparticles, and microrods. The water-filled polar channels formed through the stacking of P2Mac allow attaining a high proton conductivity value of 21.1 mS cm-1 at 27 °C under a relative humidity (RH) of 95% in the single crystals of P2Mac, while the as-prepared P2Mac pellet sample exhibited about three-orders of magnitude lower conduction under these conditions. The low activation energy of 0.39 eV, calculated from the Arrhenius plot, indicates the presence of the Grotthus proton hopping mechanism in the transport process. This report highlights the pivotal role of molecular design and self-assembly in creating high-performance SSPC organic materials.

On the intramolecular vibrational energy redistribution dynamics of aromatic complexes: A comparative study on C6H6-C6H5Cl, C6H6-C6H3Cl3, C6H6-C6Cl6 and C6H6-C6H5F, C6H6-C6H3F3, C6H6-C6F6.

Chemical dynamics Simulation studies on benzene dimer (Bz2) and benzene-hexachlorobenzene (Bz-HCB) as performed in the past suggest that the coupling between the monomeric (intramolecular) vibrational modes and modes generated due to the association of two monomers (intermolecular) has to be neither strong nor weak for a fast dissociation of the complex. To find the optimum coupling, four complexes are taken into consideration in this work, namely, benzene-monofluorobenzene, benzene-monochlorobenzene, benzene-trifluorobenzene (Bz-TFB), and benzene-trichlorobenzene. Bz-TFB has the highest rate of dissociation among all seven complexes, including Bz2, Bz-HCB, and Bz-HFB (HFB stands for hexafluorobenzene). The set of vibrational frequencies of Bz-TFB is mainly the reason for this fast dissociation. The mass of chlorine in Bz-HCB is optimized to match its vibrational frequencies similar to those of Bz-TFB, and the dissociation of Bz-HCB becomes faster. The power spectrum of Bz-TFB, Bz-HCB, and Bz-HCB with the modified mass of chlorine is also computed to understand the extent of the said coupling in these complexes.

Post-Transition State Direct Dynamics Simulations on the Ozonolysis of Catechol in an N2 Bath and Comparison with Gas-Phase Results.

Chemical dynamics simulations on the post-transition state dynamics of ozonolysis of catechol are performed in this article using a newly developed QM + MM simulation model. The reaction is performed in a bath of N2 molecules equilibrated at 300 K. Two bath densities, namely, 20 and 324 kg/m3, are considered for the simulation. The excitation temperatures of a catechol-O3 moiety are taken as 800, 1000, and 1500 K for each density. At these new excitation temperatures, the gas-phase results are also computed to compare the results and quantify the effect of surrounding molecules on this reaction. Like the previous findings, five reaction channels are observed in the present investigation, producing CO2, CO, O2, small carboxylic acid (SCA), and H2O. The probabilities of these products are discussed with the role of bath densities. Results from the gas-phase simulation and density of 20 kg/m3 are very similar, whereas results differ significantly at a higher bath density of 324 kg/m3. The rate constants for the unimolecular channel at each temperature and density are also calculated and reported. The QM + MM setup used here can also be used for other chemical reactions, where the solvent effect is important.

Electrochemical Gold-Catalyzed 1,2-Difunctionalization of C-C Multiple Bonds.

Herein, we disclose the first report of 1,2-difunctionalization of C-C multiple bonds using electrochemical gold redox catalysis. By adopting the electrochemical strategy, the inherent π-activation and cross-coupling reactivity of gold catalysis are harnessed to develop the oxy-alkynylation of allenoates under external-oxidant-free conditions. Detailed mechanistic investigations such as 31 P NMR, control experiments, mass studies, and cyclic voltammetric (CV) analysis have been performed to support the proposed reaction mechanism.

Unimolecular dissociation of C6H6-C6H5Cl, C6H6-C6H3Cl3, and C6H6-C6Cl6 complexes using machine learning approach.

The application of Machine Learning (ML) algorithms in chemical sciences, particularly computational chemistry, is a vastly emerging area of modern research. While many applications of ML techniques have already been in place to use ML based potential energies in various dynamical simulation studies, specific applications are also being successfully tested. In this work, the ML algorithms are tested to calculate the unimolecular dissociation time of benzene-hexachlorobenzene, benzene-trichlorobenzene, and benzene-monochlorobenzene complexes. Three ML algorithms, namely, Decision-Tree-Regression (DTR), Multi-Layer Perceptron, and Support Vector Regression are considered. The algorithms are trained with simulated dissociation times as functions (attributes) of complexes' intramolecular and intermolecular vibrational energies. The simulation data are used for an excitation temperature of 1500 K. Considering that the converged result is obtained with 1500 trajectories, an ML algorithm trained with 700 simulation points provides the same dissociation rate constant within statistical uncertainty as obtained from the converged 1500 trajectory result. The DTR algorithm is also used to predict 1000 K simulation results using 1500 K simulation data.

One-Step High-Temperature Electrodeposition of Fe-Based Films as Efficient Water Oxidation Catalysts.

Electrolysis of water to produce hydrogen requires an efficient catalyst preferably made of cheap and abundant metal ions for the improved water oxidation reaction. An Fe-based film has been deposited in a single step by electrochemical deposition at temperatures higher than the room temperature. Until now, the electrodeposition of iron oxide has been carried out at 298 K or at lower temperatures under a controlled atmosphere to prohibit atmospheric oxidation of Fe2+ of the iron precursor. A metal inorganic complex, ferrocene, and non-aqueous electrolyte medium propylene carbonate have been used to achieve electrodeposition of iron oxide without the need of any inert or controlled atmosphere. At 298 K, the amorphous film was formed, whereas at 313 K and at higher temperatures, the hematite film was grown, as confirmed by X-ray diffraction. The transformation of iron of the ferrocene into a higher oxidation state under the experimental conditions used was further confirmed by X-ray photoelectron spectroscopy, ultraviolet-visible, and electron paramagnetic resonance spectroscopic methods. The films deposited at 313 K showed the best performance for water oxidation with remarkable long-term electrocatalytic stability and an impressive turnover frequency of 0.028 s-1 which was 4.5 times higher than that of films deposited at 298 K (0.006 s-1). The observed overpotential to achieve a current density of 10 mA cm-2 was found to be 100 mV less for the film deposited at 313 K compared to room-temperature-derived films under similar experimental conditions. Furthermore, electrochemical impedance data revealed that films obtained at 313 K have the least charge transfer resistance (114 Ω) among all, supporting the most efficient electron transport in the film. To the best of our knowledge, this is the first-ever report where the crystalline iron-based film has been shown to be electrodeposited without any post-deposition additional treatment for alkaline oxygen evolution reaction application.

Visiblelight-induced ternary electron donor-acceptor complex enabled synthesis of 2-(2-hydrazinyl) thiazole derivatives and the assessment of their antioxidant and antidiabetic therapeutic potential.

A mild and eco-friendly visible-light-induced synthesis of 2-(2-hydrazinyl) thiazole from readily accessible thiosemicarbazide, carbonyl, and phenacyl bromide in the absence of a metal catalyst and/or any extrinsic photosensitizer is reported. This approach only requires a source of visible light and a green solvent at room temperature to produce the medicinally privileged scaffolds of hydrazinyl-thiazole derivatives in good to outstanding yields. Experimental studies support the in situ formation of a visible-light-absorbing, photosensitized colored ternary EDA complex. The next step is to prepare a pair of radicals in an excited state, which makes it easier to prepare thiazole derivatives through a SET and PCET process. DFT calculations additionally supported the mechanistic analysis of the course of the reaction. The antioxidant and antidiabetic properties of some of the compounds in the synthesized library were tested in vitro. All the investigated compounds demonstrated appreciable antioxidant activity, as evidenced by the reducing power experiment and the IC50 values of the DPPH radical scavenging experiment. Furthermore, the IC50 values for 4c, 4d, and 4g also demonstrated a strong α-amylase inhibitory effect.

Bioinspired Design of an Uncharged Ambipolar Helical Scaffold To Achieve Efficient Solid-State Proton Conduction.

This work demonstrates highly efficient solid-state proton conduction in helical organic scaffolds inspired by the biomolecule gramicidin A. The scaffold, 1, derived from a pyridine-2,6-dicarboxamide (PDC) residue adopts a helical conformation that is stabilized by a network of strong bifurcated intramolecular H-bonds between the polar residues that align the inner (concave) face of the molecule, while the aromatic units in 1 are oriented outwards. As a result, the helix attains an ambipolar nature just like gramicidin A. Two different solid forms of 1 could be isolated: a yellow solid from high-polarity solvents and an orange solid from low-polarity solvents. Single-crystal X-ray diffraction (SCXRD) studies showed that in the former, molecules of 1 are stacked in a homochiral fashion, while in the latter heterochiral stacks of 1 were present. The yellow form exhibited an almost ∼300-fold higher conductivity (of up to 0.12 mS cm-1 at 95 °C and 95 % relative humidity) than the orange form as a result of closer intermolecular proximity and lower activation energy of 0.098 eV, thus indicating a Grotthus mechanism of proton transport. This study establishes the key role of bioinspired design and controlled stereo-organization of such discrete uncharged organic molecules in achieving efficient solid-state proton conduction.

Caveolin-1 is a primary determinant of endothelial stiffening associated with dyslipidemia, disturbed flow, and ageing.

Endothelial stiffness is emerging as a major determinant in endothelial function. Here, we analyzed the role of caveolin-1 (Cav-1) in determining the stiffness of endothelial cells (EC) exposed to oxidized low density lipoprotein (oxLDL) under static and hemodynamic conditions in vitro and of aortic endothelium in vivo in mouse models of dyslipidemia and ageing. Elastic moduli of cultured ECs and of the endothelial monolayer of freshly isolated mouse aortas were measured using atomic force microscopy (AFM). We found that a loss of Cav-1 abrogates the uptake of oxLDL and oxLDL-induced endothelial stiffening, as well as endothelial stiffening induced by disturbed flow (DF), which was also oxLDL dependent. Mechanistically, Cav-1 is required for the expression of CD36 (cluster of differentiation 36) scavenger receptor. Genetic deletion of Cav-1 abrogated endothelial stiffening observed in the DF region of the aortic arch, and induced by a high fat diet (4-6 weeks) and significantly blunted endothelial stiffening that develops with advanced age. This effect was independent of stiffening of the sub-endothelium layer. Additionally, Cav-1 expression significantly increased with age. No differences in elastic modulus were observed between the sexes in advanced aged wild type and Cav-1 knockout mice. Taken together, this study demonstrates that Cav-1 plays a critical role in endothelial stiffening induced by oxLDL in vitro and by dyslipidemia, disturbed flow and ageing in vivo.

Decoding Carbon-Based Materials' Properties for High CO2 Capture and Selectivity.

Carbon-based materials are well established as low-cost, easily synthesizable, and low regeneration energy adsorbents against harmful greenhouse gases such as CO2. However, the development of such materials with exceptional CO2 uptake capacity needs well-described research, wherein various factors influencing CO2 adsorption need to be investigated. Therefore, five cost-effective carbon-based materials that have similar textural properties, functional groups, and porous characteristics were selected. Among these materials, biordered ultramicroporous graphitic carbon had shown an excellent CO2 capture capacity of 7.81 mmol/g at 273 K /1 bar with an excellent CO2 vs N2 selectivity of 15 owing to its ultramicroporous nature and unique biordered graphitic morphology. On the other hand, reduced graphene revealed a remarkable CO2 vs N2 selectivity of 57 with a CO2 uptake of 2.36 mmol/g at 273 K/1 bar. In order to understand the high CO2 capture capacity, important properties derived from adsorption/desorption, Raman spectroscopy, and X-ray photoelectron spectroscopy were correlated with CO2 adsorption. This study revealed that an increase in ultramicropore volume and sp2 carbon (graphitic) content of nanomaterials could enhance CO2 capture significantly. FTIR studies revealed the importance of oxygen functionalities in improving CO2 vs N2 selectivity in reduced graphene due to higher quadruple-dipole interactions between CO2 and oxygen functionalization of the material. Apart from high CO2 adsorption capacity, biordered ultramicroporous graphitic carbon also offered low regeneration energy and excellent pressure swing regeneration ability for five consecutive cycles.

An advanced bath model to simulate association followed by ensuing dissociation dynamics of benzene + benzene system: a comparative study of gas and condensed phase results.

The role of the environment (N2 molecules) on the association followed by the ensuing dissociation reaction of benzene + benzene system is studied here with the help of a new code setup. Chemical dynamics simulations are performed to investigate this reaction in vacuum as well as in a bath of 1000 N2 molecules, equilibrated at 300 K. Bath densities of 20 and 324 kg m-3 are considered with a few results from the latter density. The simulations are performed at three different excitation temperatures of benzene, namely, 1000, 1500, and 2000 K, with an impact parameter range of 0-12 Å for both vacuum and bath models. Higher association probabilities and hence, higher temperature dependent association rate constants are obtained in the condensed phase. In the condensed phase, when a trajectory takes a longer time for the monomers to associate, the associated complex is formed with a longer lifetime and provides a lower rate of ensuing dissociation. Higher association rate and lower dissociation rate in condensed phase dynamics are due to the energy transfer process. Hence, the energy transfer phenomenon plays a decisive role in the association/dissociation dynamics, which is completely ignored in the same reaction when studied in vacuum.

Non-directed Pd-catalysed electrooxidative olefination of arenes.

The Fujiwara-Moritani reaction is a powerful tool for the olefination of arenes by Pd-catalysed C-H activation. However, the need for superstoichiometric amounts of toxic chemical oxidants makes the reaction unattractive from an environmental and atom-economical view. Herein, we report the first non-directed and regioselective olefination of simple arenes via an electrooxidative Fujiwara-Moritani reaction. The versatility of this operator-friendly approach was demonstrated by a broad substrate scope which includes arenes, heteroarenes and a variety of olefins. Electroanalytical studies suggest the involvement of a Pd(ii)/Pd(iv) catalytic cycle via a Pd(iii) intermediate.

Post-Transition-State Direct Dynamics Simulations on the Ozonolysis of Catechol.

On-the-fly dynamics simulations are performed for the reaction of catechol + O3. The post transition state (TS) dynamics is studied at temperatures of 400 and 500 K. The PM7 semiempirical method is employed for calculating the potential energy gradient needed for integrating Hamilton's equations of motion. This semiempirical method provides excellent agreement in terms of energy and geometry of the TSs as well as minimum energy states of the system with respect to B3LYP/6-311+G (2df, 2p) calculated results. In the dynamics, first, a peroxyacid is formed, which further dissociates to different fragments. Four major channels forming CO, CO2, H2O, and small carboxylic acid (SCA) fragments are seen in this reaction. Rates of each of the channels and the overall unimolecular reaction are calculated at both temperatures. Branching ratios of all these product channels are calculated and compared with experiment. The minimum energy profile of CO2, CO, and H2O channels are calculated. A qualitative estimate of activation energies for all the channels are obtained and compared with the explicit TS energies of three product channels, which ultimately correlate with the reaction probabilities.

Proton reduction by a bimetallic zinc selenolate electrocatalyst.

The development of alternative energy sources is the utmost priority of developing society. Unlike many prior homogeneous electrocatalysts that rely on a change in the oxidation state of the metal center and/or electrochemically active ligand, here we report the synthesis and structural characterization of a bimetallic zinc selenolate complex consisting of a redox silent zinc metal ion and a tridentate ligand that catalyzes the reduction of protons into hydrogen gas electrochemically and displays one of the highest reported TOF for a homogeneous TM-metal free ligand centered HER catalyst, 509 s-1. The current-voltage analysis confirms the onset overpotential of 0.86 V vs. Ag/AgCl for the HER process. Constant potential electrolysis (CPE) has been carried out to study the bulk electrolysis of our developed protocol, which reveals that the bimetallic zinc selenolate catalyst is stable under cathodic as well as anodic potentials and generates hydrogen gas with a faradaic efficiency of 75%. Preliminary studies on the heterogeneous catalyst were conducted by depositing the bimetallic zinc selenolate catalyst on the electrode surface.

Dynamical Behavior of Aromatic Trimer Complexes in Unimolecular Dissociation Reaction at High Temperatures. Case Studies on C6H6-C6F6-C6H6 and C6H6 Trimer Complexes.

The intramolecular vibrational energy redistribution (IVR) dynamics during unimolecular dissociation of aromatic trimers at high temperatures is the primary interest of this study. Chemical dynamics simulations are performed for the unimolecular dissociation of benzene-hexafluorobenzene-benzene (Bz-HFB-Bz) and benzene trimer (Bz-trimer) complexes at a temperature range of 1000-2000 K. Partial dissociation of both the complexes is observed, which leads to a dimer and a monomer in the dynamics. However, the probability of such dissociation was found much lower in the case of the Bz-trimer, which further decreases with the increase of temperature. The rate of partial dissociation of Bz-HFB-Bz is faster at 1500, 1800, and 2000 K, whereas the rate of complete dissociation of the Bz-trimer is significantly faster than Bz-HFB-Bz at all temperatures. This is just the opposite of the corresponding dimer's dissociation, where benzene-hexafluorobenzene (Bz-HFB) dissociates at a faster rate than the benzene dimer (Bz-dimer). Thus, the dissociation dynamics of the trimer is different than that of the dimer. Simulations with excited intramolecular and intermolecular modes of the trimer complexes reveal that energy flows from intermolecular to intramolecular modes of Bz-HFB-Bz more freely than the Bz-trimer, and the dissociation process becomes slower for the former. Calculated activation energies for both types of dynamics are much lower than the corresponding binding energies, which may be due to the anharmonicity. The Arrhenius equation with an anharmonic correction factor is considered to recalculate the activation energy and pre-exponential factor.

Paradigms of endothelial stiffening in cardiovascular disease and vascular aging.

Endothelial cells, the inner lining of the blood vessels, are well-known to play a critical role in vascular function, while endothelial dysfunction due to different cardiovascular risk factors or accumulation of disruptive mechanisms that arise with aging lead to cardiovascular disease. In this review, we focus on endothelial stiffness, a fundamental biomechanical property that reflects cell resistance to deformation. In the first part of the review, we describe the mechanisms that determine endothelial stiffness, including RhoA-dependent contractile response, actin architecture and crosslinking, as well as the contributions of the intermediate filaments, vimentin and lamin. Then, we review the factors that induce endothelial stiffening, with the emphasis on mechanical signals, such as fluid shear stress, stretch and stiffness of the extracellular matrix, which are well-known to control endothelial biomechanics. We also describe in detail the contribution of lipid factors, particularly oxidized lipids, that were also shown to be crucial in regulation of endothelial stiffness. Furthermore, we discuss the relative contributions of these two mechanisms of endothelial stiffening in vasculature in cardiovascular disease and aging. Finally, we present the current state of knowledge about the role of endothelial stiffening in the disruption of endothelial cell-cell junctions that are responsible for the maintenance of the endothelial barrier.

Oxidative electro-organic synthesis of dimeric hexahydropyrrolo-[2,3-b]indole alkaloids involving PCET: total synthesis of (±)-folicanthine.

An efficient electrochemical oxidation strategy for the total synthesis of a dimeric hexahydropyrrolo[2,3-b]indole alkaloid, (±)-folicanthine (1b), has been envisioned. Control experiments suggest that a PCET pathway involving stepwise electron transfer followed by proton transfer (ET-PT) was involved in the key oxidative dimerization process.

Unimolecular Dissociation of C6H6-C6Cl6 Complex and Effect of Mode-Mode Coupling.

The unimolecular dissociation dynamics of the C6H6-C6Cl6 (Bz-HCB) complex is studied with initial excitation of all vibrational modes for a temperature range of 1000-2000 K and with mode-specific excitations at 1500 K. The results are compared with those of the C6H6-C6F6 [Bz- HFB] complex. When all modes of Bz-HCB are initially excited, the rate of dissociation is slower with respect to Bz-HFB. However, the rate of dissociation is faster when simulations with nonrandom excitation of the specific vibrational modes are performed. The rate of dissociation of Bz-HCB is found to become slower when a few intramolecular modes are excited along with all inter-fragment modes compared to the simulation when only inter-fragment modes of the same complex are excited. Such an energy-transfer dynamics is absent if both intramolecular and inter-fragment modes are not initially excited. Thus, a "stimulated" resonance energy-transfer dynamics is observed in Bz-HCB dissociation dynamics.

A Photochemical Intramolecular C-N Coupling Toward the Synthesis of Benzimidazole-Fused Phenanthridines.

Herein, we report a direct photochemical dehydrogenative C-N coupling of unactivated C(sp2)-H and N(sp2)-H bonds. The catalysts or additive-free transformation of 2-([1,1'-biphenyl]-2-yl)-1H-benzo[d]imidazole to benzo[4,5]imidazo[1,2-f]phenanthridine was achieved at ∼350 nm of irradiation via ε-hydrogen abstraction. DFT calculations helped to understand that the N-H···π interaction was essential for the reaction to proceed at a lower energy than expected.

Electrochemical Synthesis of Dimeric 2-Oxindole Sharing Vicinal Quaternary Centers Employing Proton-Coupled Electron Transfer.

Dimerization of 3-substituted 2-oxindoles has been developed under a mild electrochemical condition, avoiding toxic chemical oxidants and metal by-products. This methodology forms a C(sp3)-C(sp3) bond at the pseudobenzylic position of two partners of 2-oxindoles with a broad substrate scope. These dimeric structural motifs are important building blocks for the total synthesis of pyrroloindoline alkaloids. Furthermore, this work demonstrates in-depth mechanistic insights employing electrochemistry, which suggests a stepwise one proton transfer (PT) and two electron transfer (ET) processes. Most significantly, reaction rate acceleration has been demonstrated by exploiting the base-assisted proton-coupled electron transfer (PCET) pathway. Hence, this work brings a new dimension in the field of electro-organic synthesis with the help of nature's favorite kinetic route, i.e., PCET, to lower the kinetic barrier.