A first-principles density-functional calculation of the electronic and vibrational structure of the key melanin monomers

We report first-principles density-functional calculations for hydroquinone (HQ), indolequinone (IQ), and semiquinone (SQ). These molecules are believed to be the basic building blocks of the eumelanins, a class of biomacromolecules with important biological functions (including photoprotection) and with the potential for certain bioengineering applications. We have used the difference of self-consistent fields method to study the energy gap between the highest occupied molecular orbital and the lowest unoccupied molecular orbital, Delta(HL). We show that Delta(HL) is similar in IQ and SQ, but approximately twice as large in HQ. This may have important implications for our understanding of the observed broadband optical absorption of the eumelanins. The possibility of using this difference in Delta(HL) to molecularly engineer the electronic properties of eumelanins is discussed. We calculate the infrared and Raman spectra of the three redox forms from first principles. Each of the molecules have significantly different infrared and Raman signatures, and so these spectra could be used in situ to nondestructively identify the monomeric content of macromolecules. It is hoped that this may be a helpful analytical tool in determining the structure of eumelanin macromolecules and hence in helping to determine the structure-property-function relationships that control the behavior of the eumelanins.     

Observation of compensation effects during the thermal dissolution of aluminum oxide layers on tungsten and molybdenum 〈111〉 and on tungsten {110} in the presence of electric fields

Aluminum oxide layer dissolution was studied between 700 and 1200 K in the substrate areas of W〈111〉, Mo〈111〉, and on W{110} by means of FEM. Varying the electric field strength, F, between +45 and $\text{+105}\text{MV}\text{cm}$, two types of dissolution could be observed: dissolution by surface diffusion (low F's) and dissolution by ion desorption (high F's). It is assumed that aluminum suboxides — preferentially AlO — are involved in the dissolution processes. The preexponential factors, A_F, of an Arrhenius-Frenkel type equation were measured as a function of F. The field dependence of A_F is determined by the dissolution mechanism: (a) dissolution by diffusion: $\text{log}\text{A}{}^0{}_{\mathrm{F}}\text{=}\text{log}\text{A}{}^0{}_0\text{?}\text{ΔμF}\text{2.3k}{}^1\text{T}$ (μ  molecular dipole moment, ¹T ≡ isokinetic for W〈111〉, log A⁰₀ = ? 6.0 and ${}^1\text{T = 940}\text{K}$; for Mo〈111〉, log A⁰₀ = ? 3.1 and ${}^1\text{T = 860}\text{K}$; and (b) dissolution by ion desorption: $\text{log}\text{A}{}^{\mathrm{+}}{}_{\mathrm{F}}\text{=}\text{log}\text{A}{}^{\mathrm{+}}{}_0\text{+}\text{n}{}^{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}\text{e}{}^{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}\text{F}{}^{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{2.3k}{}^1\text{T}$; for A⁺₀ = ? 22 and ${}^1\text{T = 1200}\text{K}$; for W〈111〉, log A⁺₀ = ? 21 and ${}^1\text{T = 1200}\text{K}$. Using earlier proposed safeguards, isokinetic relationships (compensation effects) could be established for each of the two dissolution processes. The coordinates of the isokinetic points have the following average values: $\text{log}{}^1\text{A}{}^0{}_0\text{= 2.5}$ and ${}^1\text{T = 920}\text{K}$ for diffusion; $\text{log}{}^1\text{A}{}^{\mathrm{+}}{}_0\text{= ? 1}$ and ${}^1\text{T = 1240}\text{K}$ for ion desorption. The entropy changes (at $\text{T =}{}^1\text{T}$, zero field strength, and unit pressure) for the phase changes: solid layer → diffusion layer and solid layer → ion gas, are of the order of $\text{30}\text{cal}\text{K}$ · mol and $\text{90}\text{cal}\text{K}$ · mol, respectively. The two dissolution mechanisms can be described by the following Arrhenius-Frenkel type equations:

$\text{τ}{}^0{}_{\mathrm{F}}\text{=}{}^1\text{A}{}^0{}_0\text{exp}\text{[}\text{? (E}{}^0{}_0\text{+ ΔμF)}\text{k}{}^1\text{T}\text{]}\text{exp}\text{[(}\text{E}{}^0{}_0\text{+ ΔμF)}\text{kT}\text{]}$

for diffusion and

$\text{τ}{}^{\mathrm{+}}{}_{\mathrm{F}}\text{=}{}^1\text{A}{}^{\mathrm{+}}{}_0\text{exp}\text{[}\text{? (E}{}^{\mathrm{+}}{}_0\text{? n}{}^{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}\text{e}{}^{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}\text{F}{}^{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{)}\text{k}{}^1\text{T}\text{]}\text{exp}\text{[(}\text{E}{}^{\mathrm{+}}{}_0\text{? n}{}^{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}\text{e}{}^{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}\text{F}{}^{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{)}\text{kT}\text{]}$

for ion desorption.     

Electronic structure, vibrational stability, and predicted infrared-Raman spectra of the As20, As @ Ni12, and As @ Ni12 @ As20 clusters

Recently an inorganic fullerine-like [As@Ni(12)@As(20)](3-) onion with near-perfect icosahedral symmetry in the crystalline phase was reported [M. J. Moses, J. C. Fettinger, and B. W. Eichhorn, Science 300, 778 (2003)]. This paper presents a detailed computational study in the framework of density functional theory on various aspects of this molecule. The electronic structure of the As@Ni(12)@As(20) is investigated in its neutral as well as -3 charged state together with its subunits As(20) and As@Ni(12) by the all electron linear combination of Gaussian-type orbitals method. The bonding is studied by examining the integrated charge within atomic sphere, the electron localization function, changes in the electron density distribution, and from vibrational modes. We find that strong covalent As-As bonds seen in isolated As(20) become weaker in the As@Ni(12)@As(20) and strong covalent As-Ni bonds are formed. The structural stability of all four clusters is examined by analyzing the energetics and by calculating the vibrational frequencies. Further, the infrared and Raman spectra is predicted for both the neutral and charged As@Ni(12)@As(20) clusters. Finally, the energy barrier for removal of a single arsenic atom is calculated for the neutral As@Ni(12)@As(20) cluster.     

(Z)-3-p-tolylsulfinylacrylonitrile as a chiral dienophile: diels-alder reactions with furan and acyclic dienes

The behavior of (Z)-3-p-tolylsulfinylacrylonitrile (1) as a chiral dienophile has been evaluated from its reactions with furan and acyclic dienes. Electrostatic interactions of the cyano group with the sulfinyl one restrict the conformational mobility around the C-S bond, thus controlling the pi-facial selectivity, which is almost complete in all cases, the approach of the diene from the less-hindered face of the dienophile (that bearing the lone electron pair) in the predominant rotamer being the favored one. The regioselectivity is also completely controlled by the cyano group. Additionally, the reactivity of compound 1 as well as its endo-selectivity are both higher than those observed for the corresponding (Z)-3-sulfinylacrylates, thus proving the potential of sulfinylnitriles as chiral dienophiles.     

Narrow band quantitative and multivariate electroencephalogram analysis of peri-adolescent period

ABSTRACT: BACKGROUND: The peri-adolescent period is a crucial developmental moment of transition from childhood to emergent adulthood. The present report analyses the differences in Power Spectrum (PS) of the Electroencephalogram (EEG) between late childhood (24 children between 8 and 13 years old) and young adulthood (24 young adults between 18 and 23 years old). RESULTS: The narrow band analysis of the Electroencephalogram was computed in the frequency range of 0--20 Hz. The analysis of mean and variance suggested that six frequency ranges presented a different rate of maturation at these ages, namely: low delta, delta-theta, low alpha, high alpha, low beta and high beta. For most of these bands the maturation seems to occur later in anterior sites than posterior sites. Correlational analysis showed a lower pattern of correlation between different frequencies in children than in young adults, suggesting a certain asynchrony in the maturation of different rhythms. The topographical analysis revealed similar topographies of the different rhythms in children and young adults. Principal Component Analysis (PCA) demonstrated the same internal structure for the Electroencephalogram of both age groups. Principal Component Analysis allowed to separate four subcomponents in the alpha range. All these subcomponents peaked at a lower frequency in children than in young adults. CONCLUSIONS: The present approaches complement and solve some of the incertitudes when the classical brain broad rhythm analysis is applied. Children have a higher absolute power than young adults for frequency ranges between 0-20 Hz, the correlation of Power Spectrum (PS) with age and the variance age comparison showed that there are six ranges of frequencies that can distinguish the level of EEG maturation in children and adults. The establishment of maturational order of different frequencies and its possible maturational interdependence would require a complete series including all the different ages.     

Adventitious isolation of a pseudorotaxane complex of a trans-bis(Hydroxymethylbenzo)-27-crown-9 pyridyl cryptand and a viologen

ABSTRACT

The adventitious isolation and crystal structure of a pseudorotaxane complex of a trans-substituted dibenzo-27-crown-9-based pyridyl cryptand (6) and N,N’-dimethyl-4,4?-bipyridinium bis(hexafluorophosphate) (5) are reported.