Spectroscopic study of the degradation products in the holy water fonts in Santa Maria della Steccata Church in Parma (Italy)

Two holy water fonts (dated at the beginning of the XVII century) in the Santa Maria della Steccata Church in Parma (Italy) have recently been restored. Before the intervention, a detailed investigation on their degradation products was carried out to understand the mechanisms of alteration of the materials and to suggest appropriate restoration procedures.The analyses were performed by means of powder X-ray diffraction (XRD), micro-Fourier transform infrared (FTIR) and micro-Raman spectroscopies. Calcite, iron oxides, silicates and sodium chloride (from salted holy water) were found in the red coloured calcarenite. On and under the lead coverings, different lead oxides (mainly massicot), other lead salts (lead basic carbonate, cerussite, plumbonacrite Pb₁₀O(OH)₆(CO₃)₆ and lead-chlorine compounds as laurionite PbOHCl and phosgenite Pb₂CO₃Cl₂) were identified by Raman spectroscopy and XRD. Haematite α-Fe₂O₃, goethite α-FeO(OH) and lepidocrocite γ-FeO(OH) were found on and around the iron hinges.Lead compounds and sodium chloride, through crystallization and solubilization cycles, were responsible for the stone's degradation, whereas the iron corrosion materials on the hinges produced mechanical stress and cracks in the stone.Various suggestions have been given on how to restore these fonts and to remove the causes of damage.     

A chemometric approach to the investigation of major and minor ion chemistry in Lake Como (Lombardia, Northern Italy

A chemometric approach based on Principal Component Analysis (PCA) has been proposed, in order to study chemical features (major and minor ions, total alkalinity, dissolved silica) of surface and deep waters of Lake Como (Northern Italy). The method allowed us to investigate the correlations between the analyzed ions in an easy-to-see way, using bi-dimensional graphs. In wintertime, the ionic composition of Lake Como waters seems to be mainly related to the geological composition of the lake basin, with a crystalline bedrock on the northern side and a sedimentary cover in the southern part. The presence of contaminants such as bromide and nitrite in water columns is also evidenced and discussed.     

Theoretical and infrared spectroscopic investigation of the O(2) (-).benzene and O(4) (-).benzene complexes

The infrared spectra of the O(2) (-).benzene and O(4) (-).benzene complexes are determined by means of Ar predissociation spectroscopy. Several transitions due to CH stretch fundamentals and various combination bands are observed in the 2700-3100 cm(-1) region. The experimental results are interpreted with the aid of electronic structure calculations. A comparison of the calculated and experimental spectra reveals that the spectrum of O(2) (-).benzene most likely arises from an isomer where the superoxide molecule binds preferentially to one CH group of benzene. In contrast, the spectrum of O(4) (-).benzene yields a CH pattern remarkably similar to that displayed by the C(2nu) X(-).benzene (X=halogen) complexes, consistent with a structure with two CH groups equally involved in the bonding. The lower energy vibrational fundamental transitions of the O(4) (-) anion are recovered with a slight redshift in the O(4) (-).benzene spectrum, establishing that this charge-delocalized dimer ion retains its identity upon complexation.     

Ligation of alkoxymethylimidazoles towards cadmium(II) and zinc(II). X-ray,spectroscopic, thermal and potentiometric investigation

The stability constants and structure of the complexes of Cd^II and Zn^II with 1-ethoxymethylimidazole (ExMeIm), 1-propoxymethylimidazole (PxMeIm), 1-ethoxymethyl-2-methylimidazole (ExMe-2-MeIm) and 1-propoxymethyl-2-methylimidazole (PxMe-2-MeIm) in aqueous solution have been determined by potentiometric methods. Zn^II form both tetrahedral and octahedral species with the cited ligands according to the configurational equilibrium type: octahedron tetrahedron, but Cd^II prefers octahedral coordination of alkoxymethylimidazole complexes in aqueous solution. Retention of the six-coordination form of Cd^II has also been confirmed by the data obtained for two novel compounds which have been synthesized in the solid state. The crystal and molecular structure of [Cd(ExMeIm)₄(NO₃)₂] (1) has been determined by X-ray diffraction. The coordination geometry around the Cd^II ion can be considered as slightly distorted tetragonal bipyramidal (CdN₄O₂). Additionally, another six-coordinate Cd^II compound with ethoxymethyl-2-methylimidazole [Cd(ExMe-2-MeIm)₄(H₂O)](NO₃)₂ (2) has been characterized by spectroscopic (i.r., far i.r., Raman) ES–MS and t.g.a. methods.     

Rare earth elements,thorium and uranium in ores of the North-Latium (Italy)

In geochemistry, the distribution of the Rare Earth Elements (REEs) in earth crust and mantle allows to understand geochemical cycles and origin and age of igneous rocks. In this article REEs (Ce, Dy, Eu, La, Nd, Sm, Tb, and Yb), Th and U in ores of the North-Latium (Bracciano area, Ceriti Mt., Fate Mt., Sabatini Mt., Vulsini Mt., Acqua Rossa basin), have been investigated for evaluating the extraction feasibility for industrial applications. 107 samples were irradiated in the rotating rack of the TRIGA Mark II reactor of the R.C. Casaccia (ENEA) at neutron flux of 2.6 × 10¹² n × cm⁻² × s⁻¹ for 12 h together with primary and secondary standards. The gamma spectrometry measurements were performed after 8 h, 3 and 30 days of decay by means of HPGe detector (FWHM 1.75 keV at 1332.5 keV, peak/Compton ratio 55.1, relative efficiency of 22%) connected to a multi-channel analyzer. The total REE mean content is 105 μg g⁻¹, ranging widely between 2.23 and 410.5 μg g⁻¹ (average coefficient of variation 112%). A similar behavior is found for Th and U: their average levels are 13.5 and 6.0 μg g⁻¹, respectively. A quite good correlation between REEs and Th (and U) is found for Ceriti Mt. (r ² > 0.8) whereas for the other areas the correlation is <0.7. The results obtained evidence the low U content in the investigated locations.     

New insight on the investigation of the role of water in the solid-state structures of potassium croconate, K(2)C(5)O(5).2H(2)O, and its anhydrate

This work presents a comparative study of dihydrated and anhydrous forms of potassium croconate crystals by vibrational spectroscopy, X-ray powder diffraction, and thermogravimetry. These compounds have different colors (dihydrated is orange, and dehydrated is yellow) due to the presence of coordinated water molecules. X-ray diffraction patterns show that the unit cell of the yellow compound is smaller than that of the orange analogue, suggesting that the croconate ion layers are more closely bonded in this salt. The loss of water is reversible due to the potassium cation size which is intermediate between small (Li+ and Na+) and large (Rb+ and Cs+) alkaline metal ions. However, the hydrated compound (orange) is more stable, and with a small quantity of water the yellow compound is quickly converted to the orange compound. A diagnostic feature of the Raman spectrum for the orange (hydrated) and yellow (anhydrous) analogues is the singlet at 1240 cm(-1) in the former, assigned to a nu(CC) + delta(CCC) + nu(CO) + beta(CO) mode of E'2 symmetry, which splits in the yellow form to a doublet at 1256 and 1232 cm(-1).     

Underground waters quality in the province of Lecce (Apulia, Southern Italy)

This paper shows the results of underground waters last monitoring in the province of Lecce (Apulia, Southern Italy). We carried out the physical-chemical characterization of the aquifers and their classification in accordance to limit values sanctioned by Italian legislation in force, by European directives and by FAO, in order to define their quality and to establish their possible use for drinkable and irrigation purposes. The attention has been focused on salinity evaluation and underground waters contamination phenomena, due to sea-water intrusion and to the use of fertilizers. Salinity and nitrates concentrations are high in a few wells. Iron and manganese concentrations are very high for almost every sample and this is due to corrosion phenomena of artesian wells metallic structure. For a better interpretation of data, multivariate statistical analysis has been used, in order to obtain the correlation among analytical results, soils hydro-geological properties and anthropic conditions.     

The medicinal Umbelliferae plant Fennel (Foeniculum vulgare Mill.): Cultivation,traditional uses,phytopharmacological properties,and application in animal husbandry

Foeniculum vulgare Mill., commonly called fennel is one of the most popular perennial herbaceous plants used as herbal medicine and spices worldwide. It belongs to the family Umbelliferae or Apiaceae and is characterized by a distinct floral arrangement with an umbrella-like shape. In addition to other well-known Umbelliferae plants, such as carrot, celery, and angelica, fennel has been utilized ethnobotanically to cure various ailments, including gastrointestinal issues, hormonal disorders, reproductive, and respiratory diseases. This review aims to update the information on conventional usage, cultivation, phytopharmacological properties, and other applications of F. vulgare Mill. in animal husbandry. Ethnobotanical studies have shown its medicinal uses worldwide; some tribes have reported its medicinal uses and how they use different parts of the plant. Alkaloids, essential oils, phenols, fatty acids, and amino acids are examples of natural phytochemicals that have been characterized and biologically tested for their medicinal potential. Fennel has been used to treat ten categories of diseases over the last two decades. Pharmacological studies revealed that the Umbelliferae plant has antiviral, antimicrobial, antioxidant, anti-inflammatory, anti-anxiety, gastro-protective, estrogenic-like, cardiovascular, lipid, anti-mutagenic, anti-diabetic, anti-cancer activity, hepatoprotective, and memory-protective properties. Fennel extract is used as a potential phytogenic agent to enhance the productivity and quality of animal husbandry. Finally, the present study may provide up-to-date information on the medicinal application of F. vulgare from ethnobotanical and phytopharmacological perspectives and could be further explored to provide a broader benefit to humankind.     

Determination of Cytochrome C,in Solution and in The Adsorbed State,by Differential Pulse Voltammetry (DPV).

Abstract

We carried out the determination of cytochrome C, in solution and in the adsorbed state, using differential pulse voltammetry (DPV). The results obtained with DPV were compared with those obtained using cyclic voltammetry (CV). The influence of the nature of the electrodic material and of the different promoters was shown. It was also demonstrated that the electron transfer in solution and in the adsorbed state is quasi-reversible.

Cytochrome C was determined at a concentration of 1.0 × 10^?5 mol L^?1 which was more one decade lower than that obtained by cyclic voltammetry. The linearity range was more than two decades.     

The effect of irradiation in the preservation of pink pepper (Schinus terebinthifolius Raddi)

Pink peppers, also known as “pimenta-rosa” and “poivre rose”, are the fruit of Schinus terebinthifolius Raddi, a species of pepper cultivated in Brazil, and have great potential for the exploration of uses. In efforts to lengthen the shelf life of this pepper, the purpose of this study was to evaluate the effect of different doses of radiation on its physical composition and color. The pink pepper samples were irradiated with doses of 0, 0.2, 0.4, 0.8 and 1.6 kGy, and the moisture, ash and lipid contents, pH and color were analyzed. The moisture content, lipid content and pH analysis indicated effects due to the irradiation (p>0.05) in which the higher doses resulted in decreases in the attribute. In contrast, there were no significant differences for the ash analysis (p<0.05) among the studied doses. The color of the pink peppers were affected by the irradiation: the parameters a^? and b^? were the most affected by the intermediate doses (0.2 and 0.8 kGy), which induced their elevation, enhancing the reddish and yellowish colors. Based on the presented data, irradiation is as an alternative preservation process for pink peppers.     

Interpretation of the IR spectra of aluminum, gallium, and indium tris(acetylacetonates)

The IR spectra of M(Acac)₃ (M = Al, Ga, and In; Acac^?1 is the acetylacetonate ion) and their isotope-substituted analogs were calculated by the Hartree-Fock-Roothaan method. The results obtained and available literature data were used to assign the absorption bands. A correlation was found between the force constants of the M-O bond and the stability constants of the complexes M(Acac)₃.     

The esterolytic activity of poly(N-alkylimidazoles). The effect of ester chain length in the substrate and alkyl chain length in the catalyst on the esterolytic activity of poly(N-alkylimidazoles).

In an effort to exploit the enhancement in catalytic activity which might be derived through hydrophobic interactions between polymeric catalyst and substrate, 1-methyl-5-vinylimidazole (1-Me-5-VIm), 1-methyl-4-vinylimidazole (1-Me-4-VIm), 1-butyl-5-vinylimidazole (1-Bu-5-VIm), and 1-butyl-4-vinylimidazole (1-Bu-4-VIm) have been synthesized and polymerized. In 28.5% ethanol-water, poly(1-alkyl-5-vinylimidazoles)proved to be efficient catalysts for the hydrolysis of various 3-nitro-4-acyloxybenzoic acids (Sn-, where n denotes the acyl chain length). Order of magnitude rate enhancements, as compared to the model compound, 1,5-dimethylimidazole (1,5-DMIm) were observed in the poly(1-alkyl-5-vinylimidazole)-catalyzed solvolysis of S12- and S18-. Poly(1-Me-5-VIm) catalyzes the hydrolysis of S18-88 times faster than does 1,5-DMIm. The poly(1-Me-5-VIm)-catalyzed hydrolysis of S18- in ethanol-water was analyzed in terms of a simple Michaelis-Menten type mechanism. Vmax and Km were determined to be 40.2 X 10(-7) M min-1 and 2.20 X 10(-5) M, respectively.     

Theoretical investigation of the (hyper)polarizabilities of pyrrole homologues C4H4XH (X = N, P, As, Sb, Bi). A coupled-cluster and density functional theory study

Geometries, inversion barriers, static and dynamic electronic and vibrational dipole polarizability (alpha), and first (beta) and second (gamma) hyperpolarizability of the pyrrole homologues C(4)H(4)XH (X = N, P, As, Sb, Bi) have been calculated by Hartree-Fock, M?ller-Plesset second-order perturbation theory, coupled-cluster theory accounting for singles, doubles, and noniterative triple excitations methods, as well as density functional theory using B3LYP and PBE1PBE functionals and Sadlej's Pol and 6-311G basis sets. Relativistic effects on the heavier homologues stibole and bismole have been taken into account within effective core potential approximation. The results show that the electronic (hyper)polarizabilities monotonically increase with the atomic number of the heteroatom, consistent with the decrease in the molecular hardness. Ring planarization reduces the carbon-carbon bond length alternation of the cis-butadienic unit, enhancing the electronic polarizability values (alpha(e)) by 4-12% and the (hyper)polarizability values (and gamma(e)) by 30-90%. Pure vibrational and zero-point vibrational average contributions to the (hyper)polarizabilities have been determined within the clamped nucleus approach. In the static limit, the pure vibrational hyperpolarizabilities have a major contribution. Anharmonic corrections dominate the pure vibrational hyperpolarizabilities of pyrrole, while they are less important for the heavier homologues. Static and dynamic electronic response properties of the pyrrole homologues are comparable to or larger than the corresponding properties of the furan and cyclopentadiene homologue series.     

The role of swelling methods in surfactant phase science: past,present, and future

The foundation for surfactant phase science was established largely using isoplethal phase study methods, but some use has been made of qualitative isothermal penetration experiments. In 1987 a quantitative swelling method (the Diffusive Interfacial Transport method) was reported in which the analysis of phase compositions is based on refractive index data. Experience obtained to date during use of this DIT-NDX method is reviewed.These investigations have demonstrated the considerable value of swelling studies, but revealed serious flaws in the DIT-NDX method. Swelling studies are exceptionally efficient, reliable, and provide considerable information regarding the physical science of the system in addition to the phase diagram. Unfortunately, this method is incapable of accurately defining the compositions of many birefringent phases. A DIT-IR method, presently under development, should resolve this problem. Analysis of composition using the DIT-IR method will be based on infrared data obtained using a near-infrared microscope. In addition to providing better composition data, infrared studies are expected to provide information on conformational structure, crystal hydration, and hydration thermodynamics. The future of swelling methods is discussed.     

Nanostructuring, compositional fluctuations, and atomic ordering in the thermoelectric materials AgPb(m)SbTe(2+m). The myth of solid solutions

The nature of the thermoelectric materials Ag(1-x)Pb(m)SbTe(m+2) or LAST-m materials (LAST for Lead Antimony Silver Tellurium) with different m values at the atomic as well as nanoscale was studied with powder/single-crystal X-ray diffraction, electron diffraction, and high-resolution transmission electron microscopy. Powder diffraction patterns of different members (m = 0, 6, 12, 18, infinity) are consistent with pure phases crystallizing in the NaCl-structure-type (Fmm) and the proposition that the LAST family behaved as solid solutions between the PbTe and AgSbTe2 compounds. However, electron diffraction and high resolution transmission electron microscopy studies suggest the LAST phases are inhomogeneous at the nanoscale with at least two coexisting sets of well-defined phases. The minority phase which is richer in Ag and Sb is on the nanosized length scale, and it is endotaxially embedded in the majority phase which is poorer in Ag and Sb. Moreover, within each nanodomain we observe extensive long range ordering of Ag, Pb, and Sb atoms. The long range ordering can be confirmed by single crystal X-ray diffraction studies. Indeed, data collections of five different single crystals were successfully refined in space groups of lower symmetry than Fmm including P4/mmm and Rm. The results reported here provide experimental evidence for a conceptual basis that could be employed when designing high performance thermoelectric materials and dispel the decades long belief that the systems (AgSbTe2)(1-x)(PbTe)x are solid solutions.     

The role of the atomic charges on the ligands and platinum(II) in affecting the cis and trans influences in [PtXL(PPh3)2]+ complexes (X = NO3, Cl, Br, I; L = 4-substituted pyridines, amines, PPh3). A 31P NMR and DFT investigation

One bond Pt-P coupling constants (1)J(PtP) of a series of cationic complexes [PtXL(PPh(3))(2)](+) (X = NO(3), Cl, Br, I; L = 4-Z-pyridines, Z = electron withdrawing or releasing groups, 4a-k; or X = Cl, L = NH(3), PhCH(2)NH(2) and (i)PrNH(2), 5a-c) have been used to establish the trans and cis influence sequences of X and pyridines. The crystal structure of compound 4f(BF(4)) with Z = (t)Bu has been resolved. In the pyridine complexes 4a-d (Z = H, variable X), both the trans and cis influence series of the anionic ligands X decrease along the same sequence I > Br > Cl > NO(3), as previously found for [PtX(PPh(3))(3)](+) (X = NO(3), Cl, Br, I, 3a-d), however in 4a-d the cis influence turns out to be more important than the trans. On the contrary, in [PtCl(4-Z-py)(PPh(3))(2)](+) (4b,e-k) the sequence of the trans influence of the 4-Z-pyridines is opposite to that of the cis, the latter being Z = CN > CHO > Br > PhCO > H > Me > (t)Bu > NH(2), i.e. the most basic pyridine gives rise to the lowest cis influence. This correlation was found to hold also for complexes 5a-c (L = amines). All the observed trends have been fully reproduced by B3LYP/def2-SVP DFT calculations, by looking at the relevant optimized bond lengths of selected complexes of type 3, 4 and 5. Subsequent evaluation of the atomic charges, by resorting to two independent methods, i.e., the Natural Bond Order analysis of the wavefunction and the Bader's Quantum Theory of Atoms in Molecules, allowed for rationalization of the origin of the cis and trans influences. The negative charge on the nitrogen atoms of free pyridines becomes more negative upon protonation and even more so when coordinated to the [PtCl(PPh(3))(2)](+) moiety. The least negatively charged nitrogen atom of coordinated pyridines is that of 4-CN-py (the highest cis influencing pyridine derivative), which gives rise to the lowest positive charge on Pt, confirming the relationship between the lowering of the charge on the metal ion and a high cis influence. The trans influence can be described in terms of competition between the charges on the two trans donor atoms. In contrast with the behaviour of pyridines, the positive charge on the phosphorous atom of free PPh(3) increases upon coordination to Pt(II), moreover the PPh(3) ligands acquire a substantial positive charge, thus efficiently delocalising the charge of the cationic complex.     

Orbitals and the Interpretation of Photoelectron Spectroscopy and (e,2e) Ionization Experiments

Electron momentum spectroscopy, scanning tunneling microscopy, and photoelectron spectroscopy provide unique information about electronic structure, but their interpretation has been controversial. This essay discusses a framework for interpretation. Although this interpretation is not new, we believe it is important to present this framework in light of recent publications. The key point is that these experiments provide information about how the electron distribution changes upon ionization, not how electrons behave in the pre‐ionized state. Therefore, these experiments do not lead to a “selection of the correct orbitals” in chemistry and do not overturn the well‐known conclusion that both delocalized molecular orbitals and localized molecular orbitals are useful for interpreting chemical structure and dynamics. The two types of orbitals can produce identical total molecular electron densities and therefore molecular properties. Different types of orbitals are useful for different purposes.     

PM-10 and heavy metals in particulate matter of the province of Lecce (Apulia, Southern Italy)

This paper shows the results of a preliminary study of air monitoring in the province of Lecce (Apulia, Southern Italy). In particular, the attention has been focused on the determination of the PM-10 level and of the concentration of nine metals (Cd, Cr, Cu, Fe, Mn, Ni, Pb, V and Zn) present on the filters which were collected in two towns (Lecce and Campi Salentina) from 2002 until 2003. The metals have been chosen on the basis of their toxicity and of their possible use as chemical tracers. The results have proved that PM-10 values and metals concentrations did not show substantial difference between the two towns and that PM-10 level and lead concentration are below the limit established by Italian law in force. The experiments have demonstrated a high correlation between iron and manganese in both sampling sites; this could be attributed to pollution of metallurgical origin. Multivariate statistical analysis, carried out by HCA and PCA methods, has been used in order to differentiate samples in relation to sampling sites, sampling period and meteorological conditions.