An integrated study for mapping the moisture distribution in an ancient damaged wall painting.

An integrated study of microclimate monitoring, IR thermography (IRT), gravimetric tests and portable unilateral nuclear magnetic resonance (NMR) was applied in the framework of planning emergency intervention on a very deteriorated wall painting in San Rocco church, Cornaredo (Milan, Italy). The IRT investigation supported by gravimetric tests showed that the worst damage, due to water infiltration, was localized on the wall painting of the northern wall. Unilateral NMR, a new non-destructive technique which measures the hydrogen signal of the moisture and that was applied directly to the wall, allowed a detailed map of the distribution of the moisture in the plaster underlying the wall panting to be obtained. With a proper calibration of the integral of the recorded signal with suitable specimens, each area of the map corresponded to an accurate amount of moisture. IRT, gravimetric tests and unilateral NMR applied to investigate the northern wall painting showed the presence of two wet areas separated by a dry area. The moisture found in the lower area was ascribed to the occurrence of rising damp at the bottom of the wall due to the slope of the garden soil towards the northern exterior. The moisture found in the upper area was ascribed to condensation phenomena associated with the presence of a considerable amount of soluble, hygroscopic salts. In the framework of this integrated study, IRT investigation and gravimetric methods validated portable unilateral NMR as a new analytical tool for measuring in situ and without any sampling of the distribution and amount of moisture in wall paintings.

Histomorphometric, ultrastructural and microhardness evaluation of the osseointegration of a nanostructured titanium oxide coating by metal-organic chemical vapour deposition: an in vivo study.

Over the past decade the increase of elderly population has determined a rise in the incidence of bone fractures, and the improvement of the implant-bone interface remains an open problem. Metal-organic chemical vapour deposition (MOCVD) has recently been proposed as a technique to coat orthopaedic and dental prostheses with metal nanostructured oxide films either through the decomposition of oxygenated compounds (single-source precursors) or the reaction of oxygen-free metal compounds with oxygenating agents. The present study was performed to assess the in vivo biocompatibility of commercially pure Ti (control material: TI/MA) implants ( psi 2 mm x 5 mm length) coated with nanostructured TiO2 films by MOCVD (Ti/MOCVD) and then inserted into rabbit femoral cortical (middhiaphysis) and cancellous (distal epiphysis) bone. Histomorphometric, ultrastructural and microhardness investigations were carried out. Four and 12 weeks after surgery, significant (p<0.0005) increases in AI of Ti/MOCVD implants were observed as compared to Ti/MA implants (distal femoral epiphysis: 4 weeks=8.2%, ns; 12 weeks=52.3%, p <0.005; femoral diaphysis: 4 weeks=20.2%, p <0.0005; 12 weeks=10.7%, p <0.005). Bone microhardness results showed significant increases for the Ti/MOCVD versus Ti/MA implants at 200 microm in the femoral diaphysis (4 weeks=14.2, p <0.005) and distal femoral epiphysis (12 weeks=14.5, p <0.01) at 4 and 12 weeks, respectively. In conclusion, the current findings demonstrate that the nanostructured TiO2 coating positively affects the osseointegration rate of commercially pure Ti implants and the bone mineralization at the bone-biomaterial interface in both cortical and cancellous bone.

Heterodinuclear Ln[bond]Na complexes with an asymmetrical macrocyclic compartmental Schiff base.

Heterodinuclear lanthanide(III)-sodium(I) complexes [LnNa(L)(Cl)(2)(CH(3)OH)] (Ln=La[bond]Nd, Sm[bond]Lu), where H(2)L is a [1+1] asymmetric compartmental macrocyclic ligand containing a N(3)O(2) Schiff base and a O(3)O(2) crown-ether-like coordination site, have been prepared and characterized by IR, (1)H, (13)C, and (23)Na NMR spectroscopy, mass spectrometry, and electron microscopy. In the solid state, the lanthanide(III) ions coordinate the Schiff-base N(3)O(2) site, and the sodium ion occupies the O(3)O(2) crownlike cavity, as shown by the X-ray crystal structures of the Nd, Eu, Gd, and Yb derivatives. In these complexes, the lanthanide(III) ion is coordinated by two chlorine atoms in the trans position and by three nitrogen and two negatively charged phenol oxygen atoms of the Schiff base, and the ion is heptacoordinated with a pentagonal bipyramidal geometry. The sodium ion is coordinated by three etheric oxygen atoms and the two phenolic oxygens that act as a bridge. A methanol molecule is also coordinated in the apical position of the resulting pentagonal pyramidal polyhedron. A detailed (1)H and (13)C NMR study was carried out in CD(3)OD for both diamagnetic and paramagnetic heterodinuclear complexes [LnNa(L)(Cl)(2)(CH(3)OH)]. The complexes are also isostructural in solution, and their structures parallel those found in the solid state. Moreover, some significative distances determined in the solid state and in solution are comparable. Finally, the potential use of these complexes as molecular probes for the selective recognition of specific metal ions has been tested. In particular, their ability to act as shift reagents and the selectivity of the O(3)O(2) site towards Li(+), Ca(2+), and K(+) were investigated by (23)Na NMR spectroscopy.

Synthesis, X-ray Structure, and Solution NMR Studies of Ln(III) Complexes with a Macrocyclic Asymmetric Compartmental Schiff Base. Preference of the Ln(III) Ions for a Crown-Like Coordination Site.

The compartmental ligand H(2)L(A), containing an N(3)O(2) Schiff base and an O(2)O(3) crown like coordination site, has been prepared by reaction of 3,3'-(3-oxapentane-1,5-diyldioxy)bis(2-hydroxybenzaldehyde) with 1,5-diamino-3-azamethylpentane. The formation of a [1+1] macrocycle was inferred by IR, NMR, and mass spectrometry. When reacted with the rare-earth hydrate chlorides, LnCl(3).nH(2)O (Ln = La, Ce, Pr, Nd, Eu, Tb, Dy, Ho, Er, Tm, Yb, Lu, Y), H(2)L(A) or its precursors (template reaction) form the mononuclear complexes [Ln(H(2)L(A))(H(2)O)(4)]Cl(3).nH(2)O where the lanthanide ion coordinates the O(2)O(3) crown like site. The solid-state X-ray structures of [Ln(H(2)L(A))(H(2)O)(4)]Cl(3).nH(2)O (Ln = Ce, Dy, Lu) have been determined. [Lu(H(2)L(A))(H(2)O)(4)]Cl(3).3H(2)O is monoclinic space group P2(1)/n (Z = 4) with a = 15.269(5) Å, b = 11.484(5) Å, c = 19.389(6) Å, beta = 102.85(5) degrees; [Ce(H(2)L(A))(H(2)O)(4)]Cl(3).H(2)O and [Dy(H(2)L(A))(H(2)O)(4)]Cl(3).H(2)O are isomorphous, space group P2(1) (Z = 2), with a = 10.959(5) Å, b = 16.978(5) Å, c = 9.017(4) Å, beta = 97.73(5) degrees, and a = 10.874(5) Å, b = 16.797(5) Å, c = 9.046(4) Å, beta = 97.86(5) degrees for the cerium and dysprosium complexes, respectively. In the three compounds the metal ion is coordinated in a similar manner by the five oxygens (two phenolic and three etheric) of the cyclic ligand and the nine coordination around the central atom is reached by the oxygen atoms of four coordinated water molecules. Three chlorine ions are present in the asymmetric unit. A detailed (1)H NMR study was carried out in CD(3)OD for both the diamagnetic and paramagnetic [Ln(H(2)L(A))(H(2)O)(4)]Cl(3) complexes in order to compare their structure in solution with that found in the solid state. The quantitative analysis of the paramagnetic proton shifts indicates that the complexes from La to Tm are isostructural, maintain in solution the same type of coordination polyhedron found at the solid state, with the metal ion invariably coordinated in the O(2)O(3) compartment, and present a high degree of stereochemical nonrigidity. In the case of the Lu complex, the decreased fluxionality due to the reduced ionic radius allows the observation of two isomeric species in the (1)H NMR spectrum at low temperature.