Thermodynamics of binding of Zn2+ to carbonic anhydrase inhibitors

The Becke3LYP functional of DFT theory and the two-layered ONIOM (B3LYP/6–311 + G(d,p): MNDO) method were used to characterize 46 gas-phase complexes of 34 neutral and anionic ligands (H₂O, CH₃OH, CH₃COOH, CH₃CONH₂, HOSO₂NH₂, CO₂, HSO₂NH₂, CH₃SO₂NH₂, CH₃C(= O)NHOH, imidazole, NH₂SO₂NH₂, anions of 4-aminobenzenesulphonamide, saccharin, 1I9L, brinzolamide, dorzolamide, acetazolamide, further HO^(?), CH₃CO^(?), CH₃COO^(?), CH₃CONH^(?), N = N = N^(?), S = C = N^(?), CH₃C(= O)NHO^(?), HOCOO^(?), imidazoleN^(?), phenol-O^(?), HOSO₂NH^(?), ^(?)OSO₂NH^(?), ^(?)OSO₂NH₂, H₂NSO₂NH^(?), HSO₂NH^(?), CH₃SO₂NH^(?), and CF₃SO₂NH^(?), respectively) with Zn²⁺. Proton dissociation enthalpies and Gibbs energies of acidic inhibitors in the presence of zinc were computed. Their gas-phase acidity considerably increases upon chelation. Of the bases investigated, the weakest zinc affinity is exhibited by carbon dioxide (- 313.5 kJ mol^?1). Deprotonated inhibitors have higher affinities for zinc than the neutral ones. Compared to the other mono-deprotonated ligands the acetohydroxamic acid anion has the highest affinity for zinc (- 1872.7 kJ mol^?1). The zinc affinity of the acetazolamide anion computed using the hybrid ONIOM (B3LYP/6-311 + G(d,p): MNDO) method is in very good agreement with the full DFT ones and this method can be adopted to model large complexes of inhibitors with the active site of carbonic anhydrase.     

Rotational Spectra of CH3CCH–NH3, NCCCH–NH3, and NCCCH–OH2

Microwave spectra of NCCCH–NH₃, CH₃CCH–NH₃, and NCCCH–OH₂have been recorded using a pulsed-nozzle Fourier-transform microwave spectrometer. The complexes NCCCH–NH₃and CH₃CCH–NH₃are found to have symmetric-top structures with the acetylenic proton hydrogen bonded to the nitrogen of the NH₃. The data for CH₃CCH–NH₃are further consistent with free or nearly free internal rotation of the methyl top against the ammonia top. For NCCCH–OH₂, the acetylenic proton is hydrogen bonded to the oxygen of the water. The complex has a dynamicalC_2vstructure, as evidenced by the presence of two nuclear-spin modifications of the complex. The hydrogen bond lengths and hydrogen-bond stretching force constants are 2.212 Å and 10.8 N/m, 2.322 Å and 6.0 N/m, and 2.125 Å and 9.6 N/m for NCCCH–NH₃, CH₃CCH–NH₃, and NCCCH–OH₂, respectively. For the cyanoacetylene complexes, these bond lengths and force constants lie between the values for the related hydrogen cyanide and acetylene complexes of NH₃and H₂O. The NH₃bending and weak-bond stretching force constants for CH₃CCH–NH₃are less than those found in NCCCH–NH₃, NCH–NH₃, and HCCH–NH₃, suggesting that the hydrogen bonding interaction is particularly weak in CH₃CCH–NH₃. The weakness of this hydrogen bond is partially a consequence of the orientation of the monomer electric dipole moments in the complex. In CH₃CCH–NH₃the antialigned monomer dipole moments lead to a repulsive dipole–dipole interaction energy, while in NCH–NH₃and NCCCH–NH₃the aligned dipoles give an attraction interaction.     

Elastic constants,acoustic mode vibrational anharmonicity and Grüneisen parameters of hexahalometallate crystals

The room-temperature elastic constants of a number of hexahalometallate A₂MX₆ single crystals [K₂SnCl₆, K₂ReCl₆, (NH₄)₂SnCl₆, (NH₄)₂SnBr₆, (NH₄)₂SiF₆, Rb₂SnBr₆, K₂SeBr₆, (NH₄)₂TeBr₆, K₂PtBr₆ and (NH₄)2PtBr₆] have been measured either by Brillouin scattering or by the ultrasonic pulse echo overlap technique. Refractive indices have also been determined. These antifluorite structure compounds contain large MX^2?₆ ions and the interionic spacings are much greater than those of the alkaline-earth fluorite structure halides: their elastic stiffnesses are correspondingly smaller. Hydrostatic pressure derivatives of the elastic stiffness constants have been measured for K₂SnCl₆, (NH₄)₂SnBr₆ and (NH₄)₂SnCl₆ and are found to be positive; there is no marked softening of the long-wavelength acoustic-phonon modes at room temperature. The vibrational anharmonicities of these long-wavelength modes are discussed in terms of the acousticmode Grüneisen parameters, which are compared with the thermal Grüneisen parameters. For K₂SnCl₆ a mean of optic- and acoustic-mode Grüneisen parameters is shown to correlate well with the thermal Grüneisen parameter.     

A one-step procedure to prepare LiAsF6 and other allied lithium-based fluoro compounds used as electrolyte in lithium cells

A low-temperature all-solid-state thermal method has been developed to synthesize electrolytes like LiAsF₆, LiPF₆ and allied lithium-based fluoro-chemicals useful for lithium secondary cells. This developed procedure is simple and environmentally friendly compared with the existing procedures, which are poisonous and hazardous to health due to the use of obnoxious gases or liquids like F₂, AsF₃, PF₃, BF₃, AsF₃, or AsF₅, which are difficult to handle. In this proposed procedure, all chemicals are taken as analytical grade. Lithium salts and all other required salts are mixed well in required proportions and heated in between 300–400 °C to get the products examined by X-ray. The chemical reactions proposed for the preparation are given below.

1. 2LiOH + As₂O₅ + 12NH₄F → 2LiAsF₆ + 12NH₃ + 7H₂O
2. LiOH + (NH₄)₂HPO₄ + 6NH₄F → LiPF₆ + 8NH₃ + 5H₂O
3. 2LiOH + B₂O₃ + 8NH₄F → 2LiBF₄ + 8NH₃ + 5H₂O

     

Acoustic mode vibrational anharmonicity of hexahelometallate crystals

The vibrational anharmonicity and Grüneisen parameters of hexahelometallate A₂MX₆ single crystals have been determined theoretically by making use of phonon lattice theory. The potential model employed to calculate these properties consists of long range coulomb, three body interactions, short range overlap repulsion effective upto the nearest neighbour ions and phonon-lattice interactions. These antifluorite structure compounds contain large MX²⁻₆- ions and as the interionic spacings are much greater than those of the alkaline-earth fluorite structure halides, their elastic constants are correspondingly smaller. The hydrostatic pressure derivatives of the second order elastic constants (SOEC) calculated for K₂SnCl₆, K₂ReCl₆, (NH₄)₂SnCl₆, (NH₄)₂TeCl₆, (NH₄)₂SnBr₆, and (NH₄)₂TeBr₆, are found to be positive and close to the experimental values. The vibrational anharmonicities of the long-wavelength modes are explained in terms of the acoustic mode Grüneisen parameters.     

A photoelectron and energy-loss spectroscopy study of Ti and its interaction with H2, O2, N2 and NH3

A unified electron spectroscopic study of polycrystalline Ti and its interaction with H₂, O₂, N₂, and NH₃ are described. Auger electron spectroscopy (AES), electron energy-loss spectroscopy (ELS), ultraviolet and X-ray photoelectron spectroscopy (UPS and XPS) are combined to provide detailed information about the electronic structure of the titanium surface and its interaction with these adsorbates. X-ray and ultraviolet photoelectron spectra and electron energy-loss spectra are presented for the clean titanium surface, and following exposure to H₂, O₂, N₂ and NH₃. Spectral assignments are provided in each case. The electron spectra of oxygen exposed Ti and nitrogen sputtered Ti are quite similar, and are interpreted with reference to band structure calculations for TiO and TiN. Electron spectroscopy indicates essentially complete dissociative adsorption of NH₃ on the clean titanium surface.     

The structure and the analytical potential energy function of NH2 （X^2B1）

This paper reports that the equilibrium structure of NH2 has been optimized at the QCISD/6-311＋＋G （3df, 3pd） level. The ground-state NH2 has a bent （C2v, X^2B1） structure with an angle of 103.0582°. The geometrical structure is in good agreement with the other calculational and experimental results. The harmonic frequencies and the force constants have also been calculated. Based on the group theory and the principle of microscopic reversibility, the dissociation limits of NH2（C2v, X^2B1） have been derived. The potential energy surface of NH2（X^2B1） is reasonable. The contour lines are constructed, the structure and energy of NH2 reappear on the potential energy surface.     

Lattice variation and thermal parameters of gel grown KDP crystals added with some ammonium compounds

Pure and impurity added (with NH₄Cl, NH₄NO₃, NH₄H₂PO₄, and (NH₄)₂SO₄) KDP single crystals were grown by the gel method using silica gels. X-ray diffraction data were collected for powder samples and used for the estimation of lattice variation and thermal parameters like Debye-Waller factor, mean-square amplitude of vibration, Debye temperature and Debye frequency. The thermal parameters do not vary in a particular order with respect to impurity concentration. The results obtained are reported and discussed.     

The inversion potential for NH3 and its isotopic species

Usingab initio data of the potential surface for the ground state of NH₃ a function is obtained to represent, with a very high precision, the potential along the inversion coordinate. The inversion spectra of NH₃, ND₃, NH₂D and NHD₂ are found by numerically solving the Schrödinger equation for this potential. Comparison is made of the calculated inversion frequencies and the experimental values, and the molecular constants of NH₃ are also compared to those found in the literature.     

Anomalous magnetic susceptibilities of the alkaline earth hexammines

The magnetic susceptibility of the metallic compounds Ca(NH₃)₆, Sr(NH₃)₆ and Ba(NH₃)₆ has been measured by the Faraday method in the range 2–200 K. The susceptibility of Ca(NH₃)₆ is strongly dependent on temperature and exhibits a broad minimum near 120 K and a peak near 10 K. In contrast to Ca(NH₃)₆, the susceptibilities of Sr(NH₃)₆ and Ba(NH₃)₆ are diamagnetic and decrease rapidly as the temperature is lowered. At low temperatures Ba(NH₃)₆ has the largest mass susceptibility of any nonsuperconducting metal.     

Vibrational Behavior of Transition Metal Cupferronato Complexes: Raman Studies on Cobalt(II) Cupferronato Derivatives

The FT-Raman spectrum of cupferron, [PhN₂O₂]NH₄ and the micro-Raman spectra of the new corresponding cobalt(II) cupferronato complexes, CoL₂A₂, L = PhN₂O₂, a = H₂O, MeOH, o-C₆H₄(NH₂)₂, p-C₆H₄(NH₂)₂ and CoL₂A, a = (-C₆H₄NH₂-p)₂ were recorded and discussed. All the complexes show a Raman band at about 1302 cm¹ and the characteristic v(N-N) and δ(ONNO) modes of the anionic ligand. the vibrational analysis of the title compounds reveals the electron delocalisation over the N-nitroso-N-hydroxylaminato (ONNO) unit, as well as the bidentate coordination of the cupferronato ligand to the metal center through the oxygen atoms.     

Optical diagnostics on coal ignition and gas-phase combustion in co-firing ammonia with pulverized coal on a two-stage flat flame burner

Gradual substitution of coal with green ammonia is a practical approach for the coal power phasedown at a minimal cost of modification, but the ignition and gas-phase reaction during co-firing NH₃ with coal remain largely unclear. In this work, we investigate the co-combustion behaviors of NH₃ and a high-volatile coal on a two-stage flat flame burner. Remarkably, the post-flame oxygen mole fraction X_i,O2 of the inner stage can be manipulated to reproduce a proper reducing-to-oxidizing environment that coal particles experience in the practical combustor. We first reveal that, under certain values of X_i,O2 and NH₃ co-firing energy ratios E_NH3, the reaction intensity (manifested by OH-PLIF signals) in the NH₃-coal flame is stronger than burning either pure coal or NH₃. This synergetic effect originates from an NH₃-combustion-induced enhancement of volatile release. We then propose a characteristic time scale τ_OH from the OH signals for the initiation of overall reactions in the system. In the case of X_i,O2=0, τ_OH monotonically increases with E_NH3, while for X_i,O2=0.2, the trend transitions to a decreasing one. It can be interpreted by comparing τ_OH with the characteristic O₂ diffusion time, coal particle heating time, and the coal pyrolysis time under different X_i,O2. Furthermore, the coal particle ignition in coal-NH₃ flames can no longer be determined by visual images. Instead, we apply CH* chemiluminescence to identify the stages of coal particle ignition and volatile combustion in the NH₃-coal flame. While NH₃ addition has both positive (elevating temperatures & diluting coal particles) and negative (consuming O₂) effects on coal ignition, the combined influence of E_NH3 is marginal on coal ignition delay time. On the other hand, the volatile combustion time decreases linearly with E_NH3, suggesting a pure effect of reduced coal feed rate.     

Opto-galvanic spectroscopy of some molecules in discharges: NH2, NO2, H2 and N2

The change of the discharge voltage when laser light crossing the discharge is tuned to a molecular transition has been measured. Experiments have been performed in the wavelength region between 570 nm and 620 nm with discharges in NH₃, NO₂, H₂, N₂, O₂ and argon. Transitions from the ground states of NH₂ and NO₂ and transitions from metastable states of N₂ and H₂ have been detected. The spacial dependence of the opto galvanic in a low pressure dc-discharge of H₂ and N₂ has been studied.     

The infra-red spectra of some ferroelectric compounds with short hydrogen bonds

The infra-red spectra of KH₂PO₄, NH₄H₂PO₄, NaH₂PO₄, KH₂AsO₄, NH₂H₂AsO₄, Ag₂H₃IO₆ and (NH₄)₂H₃IO₆ and of their deuterated analogues have been recorded at room temperature and some of them also at low temperature in the ferroelectric phase. The interpretation of the particularly interesting spectral region between 3000 and 1500 cm^?1, containing several OH bands, has been made in terms of the tunnelling of the protons between two minima of potential energy. These were taken to be of equal depth in the non-ferroelectric phase and unsymmetrical in the ferroelectric form. A quantum-mechanical treatment of the vibrational problem of the latter type has been carried out and is presented in the Appendix. Good agreement has been found between the theoretically predicted energy levels and the experimental data.     

The photoelectron spectra of unstable intermediates : Dibromamine

The He(I) photoelectron spectrum of dibromamine, NHBr₂, has been obtained from observation of the products of the room temperature gas-phase reaction of NH₃ and Br₂. Due to its extreme reactivity, only a small proportion of NHBr₂ is present in various mixtures containing NH₂Br and N₂ as well as unreacted NH₃ and Br₂. Careful spectrum stripping is required to obtain a spectrum of NHBr₂ which is identified by the relationship of its spectrum to those of NH₂Br, NH₂Cl and NHCl₂.     

Vibrational analysis of ethylamines: Trans and gauche forms

Starting from force constant values calculated by an ab initio MO method ($\text{4-31G(N}{}^1\text{)}$), and by adjusting the diagonal elements, a practical force constant matrix (F) has been reached which could explain the observed infrared and Raman spectra (in the frequency range lower than 2000 cm^?1) of the gauche form of the ethylamine CH₃CH₂NH₂ molecule and five isotopic species CH₃¹³CH₂NH₂, CH₃CH₂¹⁵NH₂, CH₃CD₂NH₂, CH₃CH₂ND₂, and CD₃CD₂NH₂. The F matrix for the trans form of ethylamine was constructed by transferring ab initio $\text{4-31G(N}{}^1\text{)}$ values and by revising diagonal elements with conversion factors whose values are equal to the corresponding values of gauche form. A nearly complete set of assignments was achieved of the vibrational bands of ethylamines, observed so far in the spectral range 2000–100 cm^?1. In matrix isolation spectroscopy, two bands assignable to the NH₂ wagging vibrations of gauche and trans forms have been found at 775 and 782 cm^?1, respectively, for CH₃CH₂NH₂. They are at 768 and 774 cm^?1, respectively, for CD₃CD₂NH₂. From the intensity changes of these bands observed on changing the nozzle temperature in the matrix formation, the energy difference ΔE (gauche-trans) of these two conformers has been estimated to be 100 ± 10 cm^?1.     

An experimental and modeling study on auto-ignition of ammonia in an RCM with N2O and H2 addition

Deep insights into the combustion kinetics of ammonia (NH₃) can facilitate its application as a promising carbon-free fuel. Due to the low reactivity of NH₃, experimental data of NH₃ combustion can only be obtained within a limited range. In this work, nitrous oxide (N₂O) and hydrogen (H₂) were used as additives to investigate NH₃ auto-ignition in a rapid compression machine (RCM). Ignition delay times for NH₃, NH₃/N₂O blends, and NH₃/H₂ blends were measured at 30 bar, temperatures from 950 to 1437 K. The addition of N₂O and H₂ ranged from 0 to 50% and 0 to 25% of NH₃ mole fraction, respectively. Time-resolved species profiles were recorded during the auto-ignition process using a fast sampling system combined with a gas chromatograph (GC). An NH₃ combustion model was developed, in which the rate constants of key reactions were constrained by current experimental data. The addition of N₂O affected the ignition of NH₃ primarily through the decomposition of N₂O (N₂O (+M) = N₂ + O (+M), R1) and direct reaction between N₂O and NH₂ (N₂H₂ + NO = NH₂ + N₂O, R2). The rate constant of R2 was constrained effectively by experimental data of NH₃/N₂O mixtures. Two-stage ignition behaviors were observed for NH₃/H₂ mixtures, and the corresponding first-stage ignition delay times were reported for the first time. Experimental species profiles suggested the first-stage ignition resulted from the consumption of H₂. The oxidation of H₂ provided extra HO₂ radicals, which promoted the production of OH radicals and initiated first-stage ignition. Reactions between HO₂ radicals and NH₃/NH₂ dominated the first-ignition delay times of NH₃/H₂ mixtures. Moreover, the first-stage ignition led to the fast production of NO₂, which acted as a key intermediate and affected the following total ignition. Consequently, the reaction NH₂ + NO₂ = H₂NO + NO (R3) was constrained by total ignition delay times.     

Atomic and molecular adsorption on Pd(111)

The adsorption properties of a variety of atomic species (H, O, N, S, and C), molecular species (N₂, HCN, CO, NO, and NH₃) and molecular fragments (CN, NH₂, NH, CH₃, CH₂, CH, HNO, NOH, and OH) are calculated on the (111) facet of palladium using periodic self-consistent density functional theory (DFT–GGA) calculations at ¼ ML coverage. For each species, we determine the optimal binding geometry and corresponding binding energy. The vibrational frequencies of these adsorbed species are calculated and are found to be in good agreement with experimental values that have been reported in literature. From the binding energies, we calculate potential energy surfaces for the decomposition of NO, CO, N₂, NH₃, and CH₄ on Pd(111), showing that only the decomposition of NO is thermochemically preferred to its molecular desorption.     

Hole blocking PbI2/CH3NH3PbI3 interface

Modulated charge separation across (MO)/CH₃NH₃PbI₃ and (MO)/PbI₂/CH₃NH₃PbI₃ (MO = TiO₂, MoO₃) interfaces was investigated by surface photovoltage (SPV) spectroscopy. Perovskite layers were deposited by solution‐based one‐step preparation and two‐step preparation methods. An unreacted PbI₂ layer remained at the interface between the metal oxide and CH₃NH₃PbI₃ for two‐step preparation. For the two‐step preparation on TiO₂, the SPV signal related to absorption in CH₃NH₃PbI₃ increased in comparison to the one‐step preparation due to electron transfer from CH₃NH₃PbI₃ via PbI₂ into TiO₂ whereas the SPV signal related to defect transitions decreased. For the one‐step preparation on MoO₃, holes photogenerated in CH₃NH₃PbI₃ recombined with electrons in MoO₃. In contrast, a hole transfer from CH₃NH₃PbI₃ towards MoO₃ was blocked by the PbI₂ interlayer for the two‐step preparation on MoO₃. (© 2014 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Oxygen as promoter or poison in the catalytic dissociation of H2, C2H4, C2H2, and NH3 on Palladium

The dissociation rates of H₂, C₂H₄, C₂H₄, and NH₃ have been studied on oxygen covered Pd surfaces by measuring the water desorption rates during exposure to each of the molecules. These results are correlated with the hydrogen response of a Pd-MOS structure. The measurements show a trend (at 473 K) where oxygen blocks H₂ dissociation, blocks C₂H₄ dissociation only above a certain oxygen coverage, has no influence on C₂H₂ dissociation, and promotes NH₃ dissociation.