Conformation of bicyclo[n.1.0] derivatives: Part 2. Norcarane and cyclohexene epoxide

The conformation al geometries and the possible interconversion paths for bicyclo[4.1.0] heptane (norcarane) and cyclohexene epoxide have been studied by both quantum mechanical and molecular mechanics calculations. The half-chair conformation is the most stable in the two compounds even if conformational equilibria with other forms cannot be excluded. Theoretical results are compared with the experimental data of molecular geometry, heat of formation, rotational constants, dipole moment, molar Kerr constant and proton coupling constants. The results obtained by the force-field method are satisfactory and consequently the extension of the method to derivatives of this kind seems possible.     

The analytical characterization of municipal solid waste incinerator fly ash: methods and preliminary results

ICP/OES, AES, ETAAS, TXRF, IC, XRPD, XPS, SEM/EDX, FT-IR, Raman, Mössbauer and ESR have been used to characterize inorganic components in a fly ash sample. It has been possible to determine silicates and aluminium silicates (gehlenite, gismondine and cabasite) in addition to many inorganic compounds (halite, sylvite, anhydrite, bassanite, gypsum, syngenite, ettringite, haematite, calcite and rutile).     

Families of log canonically polarized varieties

Determining the number of singular fibers in a family of varieties over a curve is a generalization of Shafarevich’s Conjecture and has implications for the types of subvarieties that can appear in the corresponding moduli stack. We consider families of log canonically polarized varieties over \({\mathbb {P}^1}\) , i.e. families \({g:(Y, D) \to \mathbb {P}^1}\) where D is an effective snc divisor and the sheaf \({\omega_{Y/\mathbb {P}^1}(D)}\) is g-ample. After first defining what it means for fibers of such a family to be singular, we show that with the addition of certain mild hypotheses (the fibers have finite automorphism group, \({\mathcal {O}_Y(D)}\) is semi-ample, and the components of D must avoid the singular locus of the fibers and intersect the fibers transversely), such a family must either be isotrivial or contain at least 3 singular fibers.     

Computational modelling of de novo synthesis of Dibenzofuran: oxidative pathways of Pyrene and Benzodibenzofuran

The dominating route to polychlorinated Dibenzo-p-dioxin and Dibenzofuran formation in the “cold zones” of flue gas cleaning systems of municipal solid waste incinerators is the so-called de novo synthesis, that is, carbonaceous matrix burnoff with simultaneous oxidation and chlorination reactions. Pyrene (1) and Benzodibenzofuran (2) were chosen as the model compounds of carbonaceous material present in fly ash. Possible routes of Dibenzofuran formation by oxidative pathways of compounds (1) and (2) were investigated by theoretical calculations at the density functional theory level. The key intermediate peroxy radical, formed by reaction with molecular oxygen, can follow three main paths leading to Dibenzofuran. In the kinetically favourite path, the highest energetic barriers (25–30 kcal mol⁻¹) are encountered in the steps where CO molecules are released from ketene-like structures. These findings agree with previously reported temperature-programmed desorption results on CO desorption. Moreover, along this path, phenanthrene and biphenyl intermediates are formed, in agreement with the detection of these products in previously reported experimental Pyrene oxidation. Along the preferred path, different steric constraints in compounds (1) and (2) play a role in determining the relative stability of the intermediates, while they have less influence on the energetic barriers. As a consequence, compounds (1) and (2) should present similar kinetic behaviour as they present similar energetic barriers.     

Entanglement thresholds for displaying the quantum nature of teleportation

A protocol for transferring an unknown single qubit state evidences quantum features when the average fidelity of the outcomes is, in principle, greater than 2/3$2/3$. We propose to use the probabilistic and unambiguous state extraction scheme   as a mechanism to redistribute the fidelity in the outcome of the standard teleportation when the process is performed with an X$X$-state as a noisy quantum channel. We show that the entanglement of the channel is necessary but not sufficient in order for the average fidelity f_X$f_X$ to display quantum features, i.e., we find a threshold C_X$C_X$ for the concurrence of the channel. On the other hand, if the mechanism for redistributing fidelity is successful then we find a filterable outcome with average fidelity f_X,0$f_{X,0}$ that can be greater than f_X$f_X$. In addition, we find the threshold concurrence of the channel C_X,0$C_{X,0}$ in order for the average fidelity f_X,0$f_{X,0}$ to display quantum features and surprisingly, the threshold concurrence C_X,0$C_{X,0}$ can be less than C_X$C_X$. Even more, we find some special cases for which the threshold values become zero.     

Introducing a Linear Empirical Correlation for Predicting the Mass Heat Capacity of Biomaterials

This study correlated biomass heat capacity (Cp) with the chemistry (sulfur and ash content), crystallinity index, and temperature of various samples. A five-parameter linear correlation predicted 576 biomass Cp samples from four different origins with the absolute average relative deviation (AARD%) of ~1.1%. The proportional reduction in error (REE) approved that ash and sulfur contents only enlarge the correlation and have little effect on the accuracy. Furthermore, the REE showed that the temperature effect on biomass heat capacity was stronger than on the crystallinity index. Consequently, a new three-parameter correlation utilizing crystallinity index and temperature was developed. This model was more straightforward than the five-parameter correlation and provided better predictions (AARD = 0.98%). The proposed three-parameter correlation predicted the heat capacity of four different biomass classes with residual errors between −0.02 to 0.02 J/g∙K. The literature related biomass Cp to temperature using quadratic and linear correlations, and ignored the effect of the chemistry of the samples. These quadratic and linear correlations predicted the biomass Cp of the available database with an AARD of 39.19% and 1.29%, respectively. Our proposed model was the first work incorporating sample chemistry in biomass Cp estimation.     

Entropic Separations of Mixtures of Aromatics by Selective Face‐to‐Face Molecular Stacking in One‐Dimensional Channels of Metal–Organic Frameworks and Zeolites

Separation of challenging mixtures using metal–organic frameworks can be achieved by an entropy‐driven mechanism, where one of the components can arrange into a “face‐to‐face” stacking, thus reducing its “footprint” and reaching a higher saturation loading.     

Conformational characterization of lanthanide(III)-DOTA complexes by ab initio investigation in vacuo and in aqueous solution

The conformational behavior of four [Ln(DOTA)(H(2)O)](-) systems (Ln = La, Gd, Ho, and Lu) has been characterized by means of ab initio calculations performed in vacuo and in aqueous solution, the latter by using the polarizable continuum model (PCM). Calculated molecular geometries and conformational energies of the [Ln(DOTA)(H(2)O)](-) systems, and interconversion mechanisms, barriers, and (13)C NMR spectra of the [Lu(DOTA)](-) complex are compared with experimental values. For each system, geometry optimizations, performed in vacuo and in solution at the HF/3-21G level and using a 46+4f(n) core electron effective core potential (ECP) for lanthanides, provide two minima corresponding to a square antiprismatic (A) and an inverted antiprismatic (IA) coordination geometry. All the systems are nonacoordinated, with the exception of the IA isomer of the Lu complex that, from in solution calculations, is octacoordinated, in agreement with experimental data. On comparing the in vacuo relative free energies calculated at different theory levels it can be seen that the nonacoordinated species dominates at the beginning of the lanthanide series while the octacoordinated one does so at the end. Furthermore, on passing along the series the IA isomer becomes less and less favored with respect to A and for the Lu complex a stabilization of the IAisomer is observed in solution (but not in vacuo), in agreement with the experimental data. Investigation of the A<-->IA isomerization process in the [Lu(DOTA)](-) system provides two different interconversion mechanisms: a single-step process, involving the simultaneous rotation of the acetate arms, and a multistep path, involving the inversion of the cyclen cycle configuration. While in vacuo the energy barrier for the acetate arm rotation is higher than that involved in the ring inversion (23.1 and 13.1 kcal mol(-)(1) at the B3LYP/6-311G level, respectively), in solution the two mechanisms present comparable barriers (14.7 and 13.5 kcal mol(-)(1)), in fairly good agreement with the experimental values. The NMR shielding constants for the two isomers of the [Lu(DOTA)](-) complex have been calculated by means of the ab initio GIAO and CSGT methods, and using a 46-core-electron ECP for Lu. The calculated (13)C NMR chemical shifts are in close agreement with the experimental values (rms 3.3 ppm, at the HF/6-311G level) and confirm the structural assignment of the two isomers based on experimental NMR spectra in solution. The results demonstrate that our computational approach is able to predict several physicochemical properties of lanthanide complexes, allowing a better characterization of this class of compounds for their application as contrast agents in medical magnetic resonance imaging (MRI).     

Insights into amine-based CO<Subscript>2</Subscript> capture: an ab initio self-consistent reaction field investigation

Ab initio many-body perturbation theory (MP2/6-311++G(,dp)), density functional theory (B3LYP/6-31++G(d,p)) and self-consistent reaction field (IEF-PCM UA HF/6-31G(d)) calculations have been used to study the CO₂ capture reagents NH₃, 2-hydroxyethylamine (MEA), diaminoethane (EN), 2-amino-1-propanol (2A1P), diethanolamine (DEA), N-methyl-2-hydroxyethylamine (N-methylMEA), 2-amino-2-methyl-1-propanol (AMP), trishydroxymethylaminomethane (tris), piperazine (PZ) and piperidine (PD). This study involved full conformational searches of the capture amines in their native and protonated forms, and their carbamic acid and carbamate derivatives. Using this data, we were able to compute Boltzmann-averaged thermodynamic values for the amines, carbamates and carbamic acid derivatives, as well as equilibrium constants for a series of ‘universal’ aqueous capture reactions. Important findings include (i) relative pK _a values for the carbamic acid derivatives are a useful measure of carbamate stability, due to a particular chemical resonance which is also manifest in short computed N–CO₂H bonds at both levels of theory, (ii) the computational results for sterically hindered amines such as AMP and tris are consistent with these species forming carbamates which readily hydrolyse and (iii) the amine-catalysed reaction between OH⁻ and CO₂ to generate bicarbonate correlates with amine pK _a. Thermodynamic data from the ab initio computations predicts that the heterocycles PD and PZ and the acyclic sorbent EN are good choices for a capture solvent. AMP and tris perform poorly in comparison.     

Kinetic analysis of the phenyl-shift reaction in β-O-4 lignin model compounds: a computational study

The phenyl-shift reaction for the β-radical of phenethyl phenyl ether (PhCH(2)C?HOPh, β-PPE) is an integral step in the pyrolysis of PPE, which is a model compound for the β-O-4 linkage in lignin. We investigated the influence of natural occurring substituents (hydroxy, methoxy) on the reaction rate by calculating relative rate constants using density functional theory in combination with transition state theory, including anharmonic correction for low-frequency modes. The phenyl-shift reaction proceeds through an oxaspiro[2.5]octadienyl radical intermediate and the overall rate constants were computed invoking the steady-state approximation (its validity was confirmed). Substituents on the phenethyl ring have only little influence on the rate constants. If a methoxy substituent is located in the para position of the phenyl ring adjacent to the ether oxygen, the energies of the intermediate and second transition state are lowered, but the overall rate constant is not significantly altered. This is a consequence of the dominating first transition from reactant to intermediate in the overall rate constant. In contrast, o- and di-o-methoxy substituents significantly accelerate the phenyl-migration rate compared to β-PPE.