Anharmonic Vibrational Frequencies of Water Borane and Associated Molecules

Water borane (BH3OH2) and borinic acid (BH2OH) have been proposed as intermediates along the pathway of hydrogen generation from simple reactants: water and borane. However, the vibrational spectra for neither water borane nor borinic acid has been investigaged experimentally due to the difficulty of isolating them in the gas phase, making accurate quantum chemical predictions for such properties the most viable means of their determination. This work presents theoretical predictions of the full rotational and fundamental vibrational spectra of these two potentially application-rich molecules using quartic force fields at the CCSD(T)-F12b/cc-pCVTZ-F12 level with additional corrections included for the effects of scalar relativity. This computational scheme is further benchmarked against the available gas-phase experimental data for the related borane and HBO molecules. The differences are found to be within 3 cm−1 for the fundamental vibrational frequencies and as close as 15 MHz in the B0 and C0 principal rotational constants. Both BH2OH and BH3OH2 have multiple vibrational modes with intensities greater than 100 km mol−1, namely ν2 and ν4 in BH2OH, and ν1, ν3, ν4, ν9, and ν13 in BH3OH2. Finally, BH3OH2 has a large dipole moment of 4.24 D, which should enable it to be observable by rotational spectroscopy, as well.     

Fluorescent Liquid Tetrazines

Tetrazines with branched alkoxy substituents are liquids at ambient temperature that despite the high chromophore density retain the bright orange fluorescence that is characteristic of this exceptional fluorophore. Here, we study the photophysical properties of a series of alkoxy-tetrazines in solution and as neat liquids. We also correlate the size of the alkoxy substituents with the viscosity of the liquids. We show using time-resolved spectroscopy that intersystem crossing is an important decay pathway competing with fluorescence, and that its rate is higher for 3,6-dialkoxy derivatives than for 3-chloro-6-alkoxytetrazines, explaining the higher fluorescence quantum yields for the latter. Quantum chemical calculations suggest that the difference in rate is due to the activation energy required to distort the tetrazine core such that the nπ*S1 and the higher-lying ππ*T2 states cross, at which point the spin-orbit coupling exceeding 10 cm−1 allows for efficient intersystem crossing to occur. Femtosecond time-resolved anisotropy studies in solution allow us to measure a positive relationship between the alkoxy chain lengths and their rotational correlation times, and studies in the neat liquids show a fast decay of the anisotropy consistent with fast exciton migration in the neat liquid films.     

Galvano-Fenton Engineering Solution with Spontaneous Catalyst’s Generation from Waste: Experimental Efficiency,Parametric Analysis and Modeling Interpretation Applied to a Clean Technology for Dyes Degradation in Water

In this paper, the degradation of the diazo dye naphthol blue black (NBB) using the Galvano-Fenton process is studied experimentally and numerically. The simulations are carried out based on the anodic, cathodic, and 34 elementary reactions evolving in the electrolyte, in addition to the oxidative attack of NBB by HO• at a constant rate of 3.35×107 mol−1·m3·s−1 during the initiation stage of the chain reactions. The selection of the operating conditions including the pH of the electrolyte, the stirring speed, and the electrodes disposition is performed by assessing the kinetics of NBB degradation; these parameters are set to 3, 350 rpm and a parallel disposition with a 3 cm inter-electrode distance, respectively. The kinetics of Fe(III) in the electrolyte were monitored using the principles of Fricke dosimetry and simulated numerically. The model showed more than a 96% correlation with the experimental results in both the blank test and the presence of the dye. The effects of H2O2 and NBB concentrations on the degradation of the dye were examined jointly with the evolution of the simulated H2O2, Fe2+, and HO• concentrations in the electrolyte. The model demonstrated a good correlation with the experimental results in terms of the initial degradation rates, with correlation coefficients exceeding 98%.     

Metastable Kitaev Magnets

Nearly two decades ago, Alexei Kitaev proposed a model for spin-1/2 particles with bond-directional interactions on a two-dimensional honeycomb lattice which had the potential to host a quantum spin-liquid ground state. This work initiated numerous investigations to design and synthesize materials that would physically realize the Kitaev Hamiltonian. The first generation of such materials, such as Na2IrO3, α-Li2IrO3, and α-RuCl3, revealed the presence of non-Kitaev interactions such as the Heisenberg and off-diagonal exchange. Both physical pressure and chemical doping were used to tune the relative strength of the Kitaev and competing interactions; however, little progress was made towards achieving a purely Kitaev system. Here, we review the recent breakthrough in modifying Kitaev magnets via topochemical methods that has led to the second generation of Kitaev materials. We show how structural modifications due to the topotactic exchange reactions can alter the magnetic interactions in favor of a quantum spin-liquid phase.     

Optical Dynamic Nuclear Polarization of 13C Spins in Diamond at a Low Field with Multi-Tone Microwave Irradiation

Majority of dynamic nuclear polarization (DNP) experiments have been requiring helium cryogenics and strong magnetic fields for a high degree of nuclear polarization. In this work, we instead demonstrate an optical hyperpolarization of naturally abundant 13C nuclei in a diamond crystal at a low magnetic field and the room temperature. It exploits continuous laser irradiation for polarizing electronic spins of nitrogen vacancy centers and microwave irradiation for transferring the electronic polarization to 13C nuclear spins. We have studied the dependence of 13C polarization on laser and microwave powers. For the first time, a triplet structure corresponding to the 14N hyperfine splitting has been observed in the 13C polarization spectrum. By simultaneously exciting three microwave frequencies at the peaks of the triplet, we have achieved 13C bulk polarization of 0.113 %, leading to an enhancement of 90,000 over the thermal polarization at 17.6 mT. We believe that the multi-tone irradiation can be extended to further enhance the 13C polarization at a low magnetic field.     

Exogenous Glutathione Protects IPEC-J2 Cells against Oxidative Stress through a Mitochondrial Mechanism

The accumulation of reactive oxygen species (ROS) triggers oxidative stress in cells by oxidizing and modifying various cellular components, preventing them from performing their inherent functions, ultimately leading to apoptosis and autophagy. Glutathione (GSH) is a ubiquitous intracellular peptide with multiple functions. In this study, a hydrogen peroxide (H2O2)-induced oxidative damage model in IPEC-J2 cells was used to investigate the cellular protection mechanism of exogenous GSH against oxidative stress. The results showed that GSH supplement improved the cell viability reduced by H2O2-induced oxidative damage model in IPEC-J2 cells in a dose-dependent manner. Moreover, supplement with GSH also attenuated the H2O2-induced MMP loss, and effectively decreased the H2O2-induced mitochondrial dysfunction by increasing the content of mtDNA and upregulating the expression TFAM. Exogenous GSH treatment significantly decreased the ROS and MDA levels, improved SOD activity in H2O2-treated cells and reduced H2O2-induced early apoptosis in IPEC-J2 cells. This study showed that exogenous GSH can protect IPEC-J2 cells against apoptosis induced by oxidative stress through mitochondrial mechanisms.     

Interaction Energy Analysis of Monovalent Inorganic Anions in Bulk Water Versus Air/Water Interface

Soft anions exhibit surface activity at the air/water interface that can be probed using surface-sensitive vibrational spectroscopy, but the structural implications of this surface activity remain a matter of debate. Here, we examine the nature of anion–water interactions at the air/water interface using a combination of molecular dynamics simulations and quantum-mechanical energy decomposition analysis based on symmetry-adapted perturbation theory. Results are presented for a set of monovalent anions, including Cl⁻, Br⁻, I⁻, CN⁻, OCN⁻, SCN⁻, NO2−, NO3−, and ClOn− (n=1,2,3,4), several of which are archetypal examples of surface-active species. In all cases, we find that average anion–water interaction energies are systematically larger in bulk water although the difference (with respect to the same quantity computed in the interfacial environment) is well within the magnitude of the instantaneous fluctuations. Specifically for the surface-active species Br⁻(aq), I⁻(aq), ClO4−(aq), and SCN⁻(aq), and also for ClO⁻(aq), the charge-transfer (CT) energy is found to be larger at the interface than it is in bulk water, by an amount that is greater than the standard deviation of the fluctuations. The Cl⁻(aq) ion has a slightly larger CT energy at the interface, but NO3−(aq) does not; these two species are borderline cases where consensus is lacking regarding their surface activity. However, CT stabilization amounts to <20% of the total induction energy for each of the ions considered here, and CT-free polarization energies are systematically larger in bulk water in all cases. As such, the role of these effects in the surface activity of soft anions remains unclear. This analysis complements our recent work suggesting that the short-range solvation structure around these ions is scarcely different at the air/water interface from what it is in bulk water. Together, these observations suggest that changes in first-shell hydration structure around soft anions cannot explain observed surface activities.     

Influence of Liquid Crystallinity and Mechanical Deformation on the Molecular Relaxations of an Auxetic Liquid Crystal Elastomer

Liquid Crystal Elastomers (LCEs) combine the anisotropic ordering of liquid crystals with the elastic properties of elastomers, providing unique physical properties, such as stimuli responsiveness and a recently discovered molecular auxetic response. Here, we determine how the molecular relaxation dynamics in an acrylate LCE are affected by its phase using broadband dielectric relaxation spectroscopy, calorimetry and rheology. Our LCE is an excellent model system since it exhibits a molecular auxetic response in its nematic state, and chemically identical nematic or isotropic samples can be prepared by cross-linking. We find that the glass transition temperatures (Tg) and dynamic fragilities are similar in both phases, and the T-dependence of the α relaxation shows a crossover at the same T* for both phases. However, for T>T*, the behavior becomes Arrhenius for the nematic LCE, but only more Arrhenius-like for the isotropic sample. We provide evidence that the latter behavior is related to the existence of pre-transitional nematic fluctuations in the isotropic LCE, which are locked in by polymerization. The role of applied strain on the relaxation dynamics and mechanical response of the LCE is investigated; this is particularly important since the molecular auxetic response is linked to a mechanical Fréedericksz transition that is not fully understood. We demonstrate that the complex Young’s modulus and the α relaxation time remain relatively unchanged for small deformations, whereas for strains for which the auxetic response is achieved, significant increases are observed. We suggest that the observed molecular auxetic response is coupled to the strain-induced out-of-plane rotation of the mesogen units, in turn driven by the increasing constraints on polymer configurations, as reflected in increasing elastic moduli and α relaxation times; this is consistent with our recent results showing that the auxetic response coincides with the emergence of biaxial order.     

Photochemistry of Thymine in Protic Polar Nanomeric Droplets Using Electrostatic Embeding TD-DFT/MM

Thymine photochemistry is important for understanding DNA photodamage. In the gas phase, thymine undergoes a fast non-radiative decay from S 2 to S 1 . In the S 1 state, it gets trapped for several picoseconds until returning to the ground-state S 0 . Here, we explore the electrostatic effects of nanomeric droplets of methanol and water on the excited states of thymine. For this purpose, we develop and implement an electrostatic embedding TD-DFT/MM method based on a QM/MM coupling defined through electrostatic potential fitting charges. We show that both in methanol and water, the mechanism is similar to the gas phase. The solvent molecules participate in defining the branching plane of S 0 /S 1 intersection and have a negligible effect on the S 1 /S 2 intersection. Despite the wrong topology of the ground/excited state intersections, electrostatic embedding TD-DFT/MM allows for a fast exploration of the potential energy surfaces and a qualitative picture of the photophysics of thymine in solvent droplets.     

An Exchange Mechanism for the Magnetic Behavior of Er3+ Complexes

We study the magnetic properties of the erbium based compounds, Na9[Er(W5O18)2] and [(Pc)Er{Pc{N(C4H9)2}8}]·/−, in the framework of an effective spin exchange model involving delocalized electrons occupying molecular orbitals. The calculations successfully reproduce the experimental data available in the literature for the magnetic spectrum, magnetization and molar susceptibility in dc and ac fields. Owing to their similar molecular geometry, the compounds’ magnetic behaviors are interpreted in terms of the same set of active orbitals and thus the same effective spin coupling scheme. For all three complexes, the model predicts a prompt change in the ground state from a Kramer’s doublet at zero fields to a fully polarized quartet one brought about by the action of an external magnetic field without Zeeman splitting. This alteration is attributed to the enhancement of the effect of orbital interactions over the spin exchange as the magnitude of the external magnetic field increases.     

Photophysical Deactivation Mechanisms of the Pyrimidine Analogue 1-Cyclohexyluracil

The photophysical relaxation mechanisms of 1-cyclohexyluracil, in vacuum and water, were investigated by employing the Multi-State CASPT2 (MS-CASPT2, Multi-State Complete Active-Space Second-Order Perturbation Theory) quantum chemical method and Dunning’s cc-pVDZ basis sets. In both environments, our results suggest that the primary photophysical event is the population of the S11(ππ*) bright state. Afterwards, two likely deactivation pathways can take place, which is sustained by linear interpolation in internal coordinates defined via Z-Matrix scans connecting the most important characteristic points. The first one (Route 1) is the same relaxation mechanism observed for uracil, its canonical analogue, i.e., internal conversion to the ground state through an ethylenic-like conical intersection. The other route (Route 2) is the direct population transfer from the S11(ππ*) bright state to the T23(nπ*) triplet state via an intersystem crossing process involving the (S11(ππ*)/T23(nπ*))STCP singlet-triplet crossing point. As the spin-orbit coupling is not too large in either environment, we propose that most of the electronic population initially on the S11(ππ*) state returns to the ground following the same ultrafast deactivation mechanism observed in uracil (Route 1), while a smaller percentage goes to the triplet manifold. The presence of a minimum on the S11(ππ*) potential energy hypersurface in water can help to understand why experimentally it is noticed suppression of the triplet states population in polar protic solvent.     

Detection of Heavy Metals in Water Using Graphene Oxide Quantum Dots: An Experimental and Theoretical Study

In this work, we investigate by ab initio calculations and optical experiments the sensitivity of graphene quantum dots in their use as devices to measure the presence, and concentration, of heavy metals in water. We demonstrate that the quenching or enhancement in the optical response (absorption, emission) depends on the metallic ion considered. In particular, two cases of opposite behaviour are considered in detail: Cd2+, where we observe an increase in the emission optical response for increasing concentration, and Pb2+ whose emission spectra, vice versa, are quenched along the concentration rise. The experimental trends reported comply nicely with the different hydration patterns suggested by the models that are also capable of reproducing the minor quenching/enhancing effects observed in other ions. We envisage that quantum dots of graphene may be routinely used as cheap detectors to measure the degree of poisoning ions in water.     

Hydrogen-Bonded and Halogen-Bonded: Orthogonal Interactions for the Chloride Anion of a Pyrazolium Salt

In the hydrochloride of a pyrazolyl-substituted acetylacetone, the chloride anion is hydrogen-bonded to the protonated pyrazolyl moiety. Equimolar co-crystallization with tetrafluorodiiodobenzene (TFDIB) leads to a supramolecular aggregate in which TFDIB is situated on a crystallographic center of inversion. The iodine atom in the asymmetric unit acts as halogen bond donor, and the chloride acceptor approaches the σ-hole of this TFDIB iodine subtending an almost linear halogen bond, with Cl···I = 3.1653(11) Å and Cl···I–C = 179.32(6)°. This contact is roughly orthogonal to the N–H···Cl hydrogen bond. An analysis of the electron density according to Bader’s Quantum Theory of Atoms in Molecules confirms bond critical points (bcps) for both short contacts, with ρbcp = 0.129 for the halogen and 0.321 eÅ−3 for the hydrogen bond. Our halogen-bonded adduct represents the prototype for a future class of co-crystals with tunable electron density distribution about the σ-hole contact.     

The Spectroscopic Characterization of Halogenated Pollutants through the Interplay between Theory and Experiment: Application to R1122

In the last decade, halogenated ethenes have seen an increasing interest for different applications; in particular, in refrigeration, air-conditioning and heat pumping. At the same time, their adverse effects as atmospheric pollutants require environmental monitoring, especially by remote sensing spectroscopic techniques. For this purpose, an accurate characterization of the spectroscopic fingerprint—in particular, those of relevance for rotational–vibrational spectroscopy—of the target molecules is strongly needed. This work provides an integrated computational–theoretical investigation on R1122 (2-Chloro-1,1-difluoro-ethylene, ClHC=CF2), a compound widely employed as a key intermediate in different chemical processes. State-of-the-art quantum chemical calculations relying on CCSD(T)-based composite schemes and hybrid CCSD(T)/DFT approaches are used to obtain an accurate prediction of the structural, rotational and vibrational spectroscopic properties. In addition, the equilibrium geometry is obtained by exploiting the semi-experimental method. The theoretical predictions are used to guide the analysis of the experimentally recorded gas-phase infrared spectrum, which is assigned in the 400–6500 cm−1 region. Furthermore, absorption cross sections are accurately determined over the same spectral range. Finally, by using the obtained spectroscopic data, a first estimate of the global warming potential of R1122 vibrational spectra is obtained.     

Carbon Nanotubes Hybrid Hydrogels for Environmental Remediation: Evaluation of Adsorption Efficiency under Electric Field

The performance of Carbon Nanotubes hybrid hydrogels for environmental remediation was investigated using Methylene Blue (MB), Rhodamine B (RD), and Bengal Rose (BR) as model contaminating dyes. An acrylate hydrogel network with incorporated CNT was synthesized by photo-polymerization without any preliminary derivatization of CNT surface. Thermodynamics, isothermal and kinetic studies showed favorable sorption processes with the application of an external 12 V electric field found to be able to influence the amount of adsorbed dyes: stronger interactions with cationic MB molecules (qexp and qexp12 of 19.72 and 33.45 mg g⁻¹, respectively) and reduced affinity for anionic RD (qexp and qexp12 of 28.93 and 13.06 mg g⁻¹, respectively) and neutral BR (qexp and qexp12 of 36.75 and 15.85 mg g⁻¹, respectively) molecules were recorded. The influence of pH variation on dyes adsorption was finally highlighted by reusability studies, with the negligible variation of adsorption capacity after five repeated sorption cycles claiming for the suitability of the proposed systems as effective sorbent for wastewater treatment.     

A Platform Approach to Protein Encapsulates with Controllable Surface Chemistry

The encapsulation of proteins into core-shell structures is a widely utilised strategy for controlling protein stability, delivery and release. Despite the recognised utility of these microstructures, however, core-shell fabrication routes are often too costly or poorly scalable to allow for industrial translation. Furthermore, many scalable routes rely upon emulsion-techniques implicating denaturing or environmentally harmful organic solvents. Herein, we investigate core-shell protein encapsulation through single-feed, aqueous spray drying: a cheap, industrially ubiquitous particle-formation technology in the absence of organic solvents. We show that an excipient’s preference for the surface of the spray dried particle is well-predicted by its hydrodynamic diameter (Dh) under relevant feed buffer conditions (pH and ionic strength) and that the predictive power of Dh is improved when measured at the spray dryer outlet temperature compared to room temperature (R2 = 0.64 vs. 0.59). Lastly, we leverage these findings to propose an adaptable design framework for fabricating core-shell protein encapsulates by single-feed aqueous spray drying.     

TiCl4 Dissolved in Ionic Liquid Mixtures from Аb Initio Molecular Dynamics Simulations

To gain a deeper understanding of the TiCl4 solvation effects in multi-component ionic liquids, we performed ab initio molecular dynamics simulations of 1-butyl-3-methylimidazolium [C4C1Im]+, tetrafluoroborate [BF4]−, chloride [Cl]− both with and without water and titanium tetrachloride TiCl4. Complex interactions between cations and anions are observed in all investigated systems. By further addition of water and TiCl4 this complex interaction network is extended. Observations of the radial distribution functions and number integrals show that water and TiCl4 not only compete with each other to interact mainly with [Cl]−, which strongly influences the cation-[BF4]− interaction, but also interact with each other, which leads to the fact that in certain systems the cation-anion interaction is enhanced. Further investigations of the Voronoi polyhedra analysis have demonstrated that water has a greater impact on the nanosegregated system than TiCl4 which is also due to the fact of the shear amount of water relative to all other components and its higher mobility compared to TiCl4. Overall, the polar network of the IL mixture collapses by including water and TiCl4. In the case of [Cl]− chloride enters the water continuum, while [BF4]− remains largely unaffected, which deeply affects the interaction of the ionic liquid (IL) network.     

A Path Integral Molecular Dynamics Simulation of a Harpoon-Type Redox Reaction in a Helium Nanodroplet

We present path integral molecular dynamics (PIMD) calculations of an electron transfer from a heliophobic Cs2 dimer in its (3Σu) state, located on the surface of a He droplet, to a heliophilic, fully immersed C60 molecule. Supported by electron ionization mass spectroscopy measurements (Renzler et al., J. Chem. Phys. 2016, 145, 181101), this spatially quenched reaction was characterized as a harpoon-type or long-range electron transfer in a previous high-level ab initio study (de Lara-Castells et al., J. Phys. Chem. Lett. 2017, 8, 4284). To go beyond the static approach, classical and quantum PIMD simulations are performed at 2 K, slightly below the critical temperature for helium superfluidity (2.172 K). Calculations are executed in the NVT ensemble as well as the NVE ensemble to provide insights into real-time dynamics. A droplet size of 2090 atoms is assumed to study the impact of spatial hindrance on reactivity. By changing the number of beads in the PIMD simulations, the impact of quantization can be studied in greater detail and without an implicit assumption of superfluidity. We find that the reaction probability increases with higher levels of quantization. Our findings confirm earlier, static predictions of a rotational motion of the Cs2 dimer upon reacting with the fullerene, involving a substantial displacement of helium. However, it also raises the new question of whether the interacting species are driven out-of-equilibrium after impurity uptake, since reactivity is strongly quenched if a full thermal equilibration is assumed. More generally, our work points towards a novel mechanism for long-range electron transfer through an interplay between nuclear quantum delocalization within the confining medium and delocalized electronic dispersion forces acting on the two reactants.