Analysis of ochres from Clearwell Caves: the role of particle size in determining colour

Three ochre samples (A (orange-red in colour), B (red) and C (purple)) from Clearwell Caves, (Gloucestershire, UK) have been examined using an integrated analytical methodology based on the techniques of IR and diffuse reflectance UV-visible-NIR spectroscopy, X-ray diffraction, elemental analysis by ICP-AES and particle size analysis. It is shown that the chromophore in each case is haematite. The differences in colour may be accounted for by (i) different mineralogical and chemical composition in the case of the orange ochre, where higher levels of dolomite and copper are seen and (ii) an unusual particle size distribution in the case of the purple ochre. When the purple ochre was ground to give the same particle size distribution as the red ochre then the colours of the two samples became indistinguishable. An analysis has now been completed of a range of ochre samples with colours from yellow to purple from the important site of Clearwell Caves.     

Near-i.r. Absorption of H2O and D2O in the liquid and supercooled range

Summary Results are reported on near-i.r. absorption spectra of H₂O and D₂O down to the temperature region of supercooled liquid. No anomalous behaviour is observed when the absorbance at any given frequency is studied as a function of temperature. A critical-exponent behaviour strikingly correlating with that exhibited by transport properties is instead observed when spectral deconvolution methods are used. Results are discussed in relation with current views on water structure, based on molecular-dynamics simulation results and connectivity calculations.

---

Riassunto Si riportano risultati sugli spettri di assorbimento i.r. di H₂O e D₂O fino alla regione di temperature del liquido sopraraffreddato. L'andamento dell'assorbanza a frequenza costante in funzione della temperatura non mostra alcuna indicazione di comportamento anomalo. Al contrario, quando gli spettri sono analizzati con metodo di deconvoluzione, si osserva un comportamento di tipo esponente critico, che correla straordinariamente bene con quello mostrato dalle proprietà di trasporto. I risultati sono discussi anche in relazione ai piú recenti modelli di struttura dell'acqua, derivanti dai risultati di simulazione e dai calcoli di connettività.

---

Резюме Приводятся результаты для спектров инфракрасного поглощения H₂O и D₂O для температур переохлажденной жидкости. Не обнаружено аномального поведения, когда поглощательная способность при заданной частоте изучается как функция темпетатуры. Напротив, при анализе спектров с помощью спектральных методов конволюции наблюдается поведение типа критической экспоненты, которое коррелирует с поведением, определяемым транспортыми свойствами. Полученные результаты обсуждаются в связи с недавними моделями структуры воды, полученными на основе моделирования молекулярной динамики и нычислений связности.

     

Two-color cross-correlation of fs-laser pulses by two-photon induced photoconductivity for near and far field optical measurements

Two-color two-photon induced photoconductivity in a GaAsP diffusion type photodiode is demonstrated by measuring femtosecond cross-correlation functions for widely separated wavelength pairs of 775 and 1300 nm. Results are obtained for a range of tunable wavelengths and average powers of the incident lasers by measuring the two-photon induced photocurrent as a function of the optical delay between the pulses. The temporal autocorrelation of femtosecond laser pulses in the near-field of a small diameter aluminum coated optical fiber tip is also obtained with the same photodiode method for single colors.     

Core percolation and onset of complexity in boolean networks

The determination and classification of fixed points of large Boolean networks is addressed in terms of a constraint-satisfaction problem. We develop a general simplification scheme that, removing all those variables and functions belonging to trivial logical cascades, returns the computational core of the network. The transition line from an easy to a complex regulatory phase is described as a function of the parameters of the model, identifying thereby both theoretically and algorithmically the relevant regulatory variables.     

High-resolution apertureless near-field optical imaging using gold nanosphere probes

An apertureless near-field scanning optical microscope (ANSOM) that utilizes the enhanced field around a gold nanosphere, which is attached to the end of an atomic force microscope (AFM) tip, is used to image the local dielectric constant of the patterned metallic surfaces and local electric field around plasmonic nanosphere samples. A colloidal gold nanosphere (approximately 50 nm diameter) is linked to the extremity of the conventional etched-silicon probe. The scattering of laser radiation (633 or 532 nm) is modulated by the oscillating nanosphere-functionalized silicon tip, and the scattered radiation is detected. The approach curve (scattering intensity as a function of the tip-sample distance), the polarization dependence (scattering intensity as a function of the excitation polarization direction), and ANSOM image contrast confirm that the spherical nanosphere attached to the silicon tip acts as a point dipole that interacts with the sample surface via a dipole-dipole coupling, in which the dipole created by the field at the tip interacts with its own image dipole in the sample. The image obtained with the nanoparticle functionalized tip provides a dielectric map of the sample surface with a spatial resolution better than 80 nm. In addition, we show that the functionalized tip is capable of imaging the local electric field distribution above the plasmonic nanosphere samples. Overall, the result shows that high-resolution ANSOM is possible without the aid of the lightning-rod effect. With an improved tip-fabrication method, we believe that the method can provide a versatile high-resolution chemical imaging that is not available from usual forms of ANSOM.     

Comparison of the discriminating power of Raman and surface‐enhanced Raman spectroscopy with established techniques for the examination of liquid and gel inks

The ability to discriminate between inks is important for forensic document analysis. Here, Raman spectroscopy (RS) and surface‐enhanced RS have been compared to the traditional document examination techniques of video spectral comparison and thin layer chromatography on a population of blue and black‐coloured liquid and gel inks. It was found that in most cases, the Raman techniques provided a similar or better discriminating power than the conventional methods. Importantly, this study allowed us to determine whether the same underlying changes in composition were being exploited by the different methods to discriminate between samples. It was found that there was indeed a high degree of commonality in the sample pairs being discriminated by the various techniques. This work can therefore underpin introduction of Raman methods into standard operating procedures for ink analysis since it not only measures the extent of discrimination between samples but can also explain the origin of the spectral changes that are used to distinguish between them. © 2013 John Wiley & Sons Ltd and Crown copyright     

Next-generation quantum theory of atoms in molecules for the photochemical ring-opening reactions of oxirane

The conical intersections corresponding to the C─O and C─C ring opening were optimized and the reaction paths traversing these intersections were obtained. Investigation of the C─O ring opening revealed that when traversing the lowest energy conical intersection, the reaction path returns to the closed ring geometry. The C─O path traversing the intersection featuring torsion of terminal CH₂ group however, led to a ring-opened geometry, an H-shift and the formation of acetaldehyde that can undergo further dissociation. The observation of different reaction paths was explained by the 3-D paths from quantum theory of atoms in molecules (QTAIM) that defined the most preferred direction of electronic motion that precisely tracked the mechanisms of bond breaking and formation throughout the photo-reactions. The size, orientation, and location of these most preferred 3-D paths indicated the extent and direction of motion of atoms, bonds, and the degree of torsion or planarity of a bond indicating a predictive ability.     

Electronically varied manganese tris-arylacetamide tripodal complexes

Abstract

This report details the synthesis and characterization of six new Mn(II) complexes coordinated to systematically varied 2,2',2''-nitrilotris(N-arylacetamidate) ligands (L^R; R?=?NO₂, Cl, Br, H, Me, and OMe). The complexes are synthesized as the di-tetramethylammonium salts [Me₄N]₂[MnL^R(OAc)]. The nitro variant Mn^NO2 afforded crystals suitable for X-ray diffraction and its molecular structure is reported. We previously reported the crystal structures of Fe^NO2 and Zn^NO2 and additionally report herein the synthesis and characterization of Co^NO2. Using these four molecules, we conduct a brief comparison of the bond metrics to demonstrate that the primary difference governing structural changes is likely due to ionic crystal radii changes rather than electronic properties. The electrochemical properties of the Mn^R complexes were additionally explored with cyclic voltammetry, which revealed that the series is modulated by the various electronic substituents on the aryl groups of the ligands. The electrochemical studies also revealed, consistent with our previous report, that the acetate ligand on the Mn^R complexes is labile. Finally, a Hammett plot was constructed using the potentials obtained from cyclic voltammetry, which is compared with a few other similar transition metal complexes.     

Taxonomy of correlations of wind velocity — an application to the Sicilian area

We present an algorithm that allows us to analyze the cross-correlation of wind velocity measured in different locations; this algorithm is applied to 29 recording stations in Sicily. The results show that such correlations present a significant and persistent ultrametric structure that is influenced by the geographical neighborhood as well as by the presence of mountain and the sea. The algorithm presented, that is also able to reveal weak correlations, can be used as a starting point for the development of multivariate models of wind.