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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

Comparison of intermolecular energy transfer from vibrationally excited benzene in mixed nitrogen-benzene baths at 140 K and 300 K.

Gas phase intermolecular energy transfer (IET) is a fundamental component of accurately explaining the behavior of gas phase systems in which the internal energy of particular modes of molecules is greatly out of equilibrium. In this work, chemical dynamics simulations of mixed benzene/N2 baths with one highly vibrationally excited benzene molecule (Bz*) are compared to experimental results at 140 K. Two mixed bath models are considered. In one, the bath consists of 190 N2 and 10 Bz, whereas in the other bath, 396 N2 and 4 Bz are utilized. The results are compared to results from 300 K simulations and experiments, revealing that Bz*-Bz vibration-vibration IET efficiency increased at low temperatures consistent with longer lived "chattering" collisions at lower temperatures. In the simulations, at the Bz* excitation energy of 150 kcal/mol, the averaged energy transferred per collision, ⟨ΔEc⟩, for Bz*-Bz collisions is found to be ∼2.4 times larger in 140 K than in 300 K bath, whereas this value is ∼1.3 times lower for Bz*-N2 collisions. The overall ⟨ΔEc⟩, for all collisions, is found to be almost two times larger at 140 K compared to the one obtained from the 300 K bath. Such an enhancement of IET efficiency at 140 K is qualitatively consistent with the experimental observation. However, the possible reasons for not attaining a quantitative agreement are discussed. These results imply that the bath temperature and molecular composition as well as the magnitude of vibrational energy of a highly vibrationally excited molecule can shift the overall timescale of rethermalization.

A Competition between Dissociation Pathway and Energy Transfer Pathway: Unimolecular Dissociation of a Benzene-Hexafluorobenzene Complex in Nitrogen Bath.

The unimolecular dissociation of a benzene-hexafluorobenzene complex at 1000, 1500, and 2000 K is studied inside a bath of 1000 N2 molecules kept at 300 K using chemical dynamics simulation. Three bath densities of 20, 324, and 750 kg/m3 are considered. The dissociation dynamics of the complex at a 20 kg/m3 bath density is found to be similar to that in the gas phase, whereas the dynamics is drastically different at higher bath densities. The microcanonical/canonical dissociation rate constants for the three bath densities are calculated and fitted to the Arrhenius equation. The activation energies are found to be similar to the gas-phase one. However, the pre-exponential factor is lower and decreases with the increase in bath density. The vibrational degree of freedom of the complex more effectively participates in the collisional energy transfer to the N2 bath, whereas the translational and rotational degrees of freedom of N2 receive the transferred energy. The energy transfer efficiency increases with the increase in bath density. The time scale of the energy transfer pathway is more than that of the dissociation pathway, and negligible direct dissociation of the complex is observed from the simulation at the highest bath density.

A Better Understanding of the Unimolecular Dissociation Dynamics of Weakly Bound Aromatic Compounds at High Temperature: A Study on C6H6-C6F6 and Comparison with C6H6 Dimer.

Chemical dynamics simulations are performed to study the unimolecular dissociation of the benzene (Bz)-hexafluorobenzene (HFB) complex at five different temperatures ranging from 1000 to 2000 K, and the results are compared with that of the Bz dimer at common simulation temperatures. Bz-HFB, in comparison with Bz dimer, possesses a much attractive intermolecular interaction, a very different equilibrium geometry, and a lower average quantum vibrational excitation energy at a given temperature. Six low-frequency modes of Bz-HFB are formed by Bz + HFB association which are weakly coupled with the vibrational modes of Bz and HFB. However, this coupling is found much stronger in Bz-HFB compared to the same in the Bz dimer. The simulations are done with very good potential energy parameters taken from the literature. Considering the canonical (TST) model, the unimolecular dissociation rate constant at each temperature is calculated and fitted to the Arrhenius equation. An activation energy of 5.0 kcal/mol and a pre-exponential factor of 2.39 × 1012 s-1 are obtained, which are of expected magnitudes. The responsible vibrational mode for dissociation is identified by performing normal-mode analysis. Simulations with random excitations of high-frequency Bz and HFB modes and low-frequency inter-Bz-HFB vibrational modes of the Bz-HFB complex are also performed. The intramolecular vibrational energy redistribution (IVR) time and the unimolecular dissociation rate constants are calculated from these simulations. The latter shows good agreement with the same obtained from simulation with random excitation of all vibrational modes.

Chemical Dynamics Simulations on Association and Ensuing Dissociation of a Benzene-Hexafluorobenzene Molecular System.

Chemical dynamics simulations are performed to study the association of benzene (Bz) and hexafluorobenzene (HFB) followed by the ensuing dissociation of the Bz-HFB complex. The calculations are done for 1000, 1500, and 2000 K with an impact parameter ( b) range of 0-10 Å at each temperature. Almost no complexes are observed to form at b = 8 and 10 Å. Following three different methods of calculation of the temperature-dependent association rate constant kasso( T), the values obtained are 1.67 × 10-10, 1.86 × 10-10, and 2.05 × 10-10 cm3/molecule·s with a standard deviation of approximately 0.1 × 10-10 cm3/molecule·s for T = 1500 K. Among those values of kasso( T), the middle one is obtained by considering a relative translational energy of 3 RT/2 at T = 1500 K, and the same is followed to calculate kasso( T) at 1000 and 2000 K. The Arrhenius parameters, using the kasso( T) values at three temperatures, are 0.203 × 10-10 cm3/molecule·s for the pre-exponential factor and -5.79 kcal/mol for the activation energy. The absolute value of the latter is similar to the Bz + HFB association energy of 5.93 kcal/mol. The ensuing dissociation dynamics of the complex is significantly different from the unimolecular dissociation dynamics, and an exponential function fits the N( t - t0)/ N( t0) curves comparatively well. The ensuing dissociation is also observed to be independent of time for a statistically large sample size.

Cholesterol-Dependent Modulation of Stem Cell Biomechanics: Application to Adipogenesis.

Cell mechanics has been shown to regulate stem cell differentiation. We have previously reported that altered cell stiffness of mesenchymal stem cells can delay or facilitate biochemically directed differentiation. One of the factors that can affect the cell stiffness is cholesterol. However, the effect of cholesterol on differentiation of human mesenchymal stem cells remains elusive. In this paper, we demonstrate that cholesterol is involved in the modulation of the cell stiffness and subsequent adipogenic differentiation. Rapid cytoskeletal actin reorganization was evident and correlated with the cell's Young's modulus measured using atomic force microscopy. In addition, the level of membrane-bound cholesterol was found to increase during adipogenic differentiation and inversely varied with the cell stiffness. Furthermore, cholesterol played a key role in the regulation of the cell morphology and biomechanics, suggesting its crucial involvement in mechanotransduction. To better understand the underlying mechanisms, we investigated the effect of cholesterol on the membrane-cytoskeleton linker proteins (ezrin and moesin). Cholesterol depletion was found to upregulate the ezrin expression which promoted cell spreading, increased Young's modulus, and hindered adipogenesis. In contrast, cholesterol enrichment increased the moesin expression, decreased Young's modulus, and induced cell rounding and facilitated adipogenesis. Taken together, cholesterol appears to regulate the stem cell mechanics and adipogenesis through the membrane-associated linker proteins.

Non-statistical intermolecular energy transfer from vibrationally excited benzene in a mixed nitrogen-benzene bath.

A chemical dynamics simulation was performed to model experiments [N. A. West et al., J. Chem. Phys. 145, 014308 (2016)] in which benzene molecules are vibrationally excited to 148.1 kcal/mol within a N2-benzene bath. A significant fraction of the benzene molecules are excited, resulting in heating of the bath, which is accurately represented by the simulation. The interesting finding from the simulations is the non-statistical collisional energy transfer from the vibrationally excited benzene C6H6 * molecules to the bath. The simulations find that at ∼10-7 s and 1 atm pressure there are four different final temperatures for C6H6 * and the bath. N2 vibration is not excited and remains at the original bath temperature of 300 K. Rotation and translation degrees of freedom of both N2 and C6H6 in the bath are excited to a final temperature of ∼340 K. Energy transfer from the excited C6H6 * molecules is more efficient to vibration of the C6H6 bath than its rotation and translation degrees of freedom, and the final vibrational temperature of the C6H6 bath is ∼453 K, if the average energy of each C6H6 vibration mode is assumed to be RT. There is no vibrational equilibration between C6H6 * and the C6H6 bath molecules. When the simulations are terminated, the vibrational temperatures of the C6H6 * and C6H6 bath molecules are ∼537 K and ∼453 K, respectively. An important question is the time scale for complete energy equilibration of the C6H6 * and N2 and C6H6 bath system. At 1 atm and 300 K, the experimental V-T (vibration-translation) relaxation time for N2 is ∼10-4 s. The simulation time was too short for equilibrium to be attained, and the time for complete equilibration of C6H6 * vibration with translation, rotation, and vibration of the bath was not determined.