NMR depth profiles as a non-invasive analytical tool to probe the penetration depth of hydrophobic treatments and inhomogeneities in treated porous stones

Hydrophobic treatment is one of the most important interventions usually carried out in the conservation of stone artifacts and monuments. The analytical study reported in this paper was aimed at answering general questions such as the penetration depth of a hydrophobic treatment into a porous material, its capability to impair the water absorption, how the presence of a treatment may change the open porosity available to the water, and how a treatment may affect the diffusion of water inside a porous structure. Also, inhomogeneities in treated stones due to sharp variations of the amount of the absorbed product in the porous material were evidenced and scaled. The results of this fully non-invasive analytical study were rationalized in terms of new parameters obtained by a suitable process of nuclear magnetic resonance data. These analytical parameters reported here for the first time, namely the hydrophobic efficiency, the penetration depth, and angles describing changes in slope in depth profiles, gave important information in assessing the performance of a treatment.     

Unilateral NMR, 13C CPMAS NMR spectroscopy and micro-analytical techniques for studying the materials and state of conservation of an ancient Egyptian wooden sarcophagus

A multi-technique approach was employed to study a decorated Egyptian wooden sarcophagus (XXV–XXVI dynasty, Third Intermediate Period), belonging to the Museo del Vicino Oriente of the Sapienza University of Rome. Portable non-invasive unilateral NMR was applied to evaluate the conservation state of the sarcophagus. Moreover, using unilateral NMR, a non-invasive analytical protocol was established to detect the presence of organic substances on the surface and/or embedded in the wooden matrix. This protocol allowed for an educated sampling campaign aimed at further investigating the state of degradation of the wood and the presence of organic substances by ¹³C cross polarization magic angle spinning (CPMAS) NMR spectroscopy. The composition of the painted layer was analysed by optical microscopy (OM), scanning electron microscopy–energy dispersive spectroscopy (SEM–EDS), Raman and surface enhanced (resonance) Raman spectroscopy (SERS/SERRS), infrared and GC–MS techniques, evidencing original components such as clay minerals, Egyptian green, indigo, natural gums, and also highlighting restoration pigments and alteration compounds. The identification of the wood, of great value for the reconstruction of the history of the artwork, was achieved by means of optical microscopy.     

C-H and C-C bond activations of terminal alkynes in the presence of a butterfly-shaped heteronuclear Ru3Au cluster

The reaction of compound [Ru₃(CO)₁₀(μ-Cl)(μ-AuPPh₃)] (1) with terminal alkynes HCCR; (R = C₆H₄-4-CH₃, C₆H₃-2,5-(CH₃)₂, C₆H₂-2,4,5-(CH₃)₃, C(CH₃) = CH₂, Si(CH₃)₃), under very mild conditions yielded isostructural compounds [Ru₃(CO)₉(μ-AuPPh₃)(μ₃-η²-⊥-CCR)] (R = C₆H₄-4-CH₃ (2), C₆H₃-2,5-(CH₃)₂ (3), C₆H₂-2,4,5-(CH₃)₃ (4), C(CH₃)CH₂ (5), Si(CH₃)₃) (6)) respectively; where the alkynes suffer oxidative additions to the metallic fragment coordinating as acetylide groups in a μ₃-η²-perpendicular fashion by breaking the C_(sp)-H bond of the alkynes. The AuPPh₃ fragment remains without change in all compounds. All of these clusters have been characterized in solution by i.r. and n.m.r. spectroscopy and their structures have been established by single crystal X-ray diffraction studies.     

Synthesis and complete assignment of the 1H and 13C NMR spectra of 6-substituted and 2,6-disubstituted pyridazin-3(2H)-ones

Several pyridazin-3(2H)-one derivatives were synthesized starting from alkyl furans using oxidation with singlet oxygen to give 4-methoxy or 4-hydroxybutenolides, key intermediates of the synthetic strategy followed. For all pyridazinones reported, a complete assignment of the (1)H and (13)C NMR spectra using one- and two-dimensional NMR spectroscopic methods, which included NOE, DEPT, COSY, HSQC and HMBC experiments, was accomplished. Correlations between the chemical shifts of the heterocyclic ring atoms and substituents at N-2 and C-6 were analyzed.     

Differential resin-dentin bonds created after caries removal with polymer burs

The objective of this article was to investigate the effect of carbide and polymer burs caries removal methods on the bond strength of different adhesives to dentin. Resin restorations were performed in sound and caries-affected dentin, after using polymer or carbide burs and bonding with four different adhesive (Single bond, SB; Clearfil SE bond, SEB; FL-Bond II, FLB; and Fuji II-LC, FUJI). Microtensile bond strength (MTBS) was measured. Data were analyzed with ANOVA and Student-Newman-Keuls tests. Debonded surfaces were observed by scanning electron microscopy. Bonded interfaces were examined using light microscopy (Masson's trichrome staining). In sound dentin, MTBS was similar for SEB and SB, and higher than that of FLB and FUJI. Bond strength to carbide bur prepared dentin was similar for SB, SEB, and FLB; FUJI presented the lowest. SB applied on polymer bur excavated dentin presented similar values to those of the carbide bur group; MTBS attained by SEB, FLB, and FUJI decreased when bonding to dentin treated with polymer burs; FUJI yielded pretesting failures in all specimens. Polymer burs created a thick smear layer that was not infiltrated by tested self-etching agents. The bonding effectiveness of self-etching and glass-ionomer-like adhesives to dentin decreased when polymer burs were used.     

Nuclear magnetic resonance in contemporary art: the case of “Moon Surface” by Turcato

Nuclear Magnetic Resonance (NMR) methodologies were applied to characterize the constitutive materials and the state of degradation of a contemporary painting. The investigation was mandatory to plan a suitable restoration. Noninvasive, portable NMR allowed the detection of degraded regions of the painting based on the measurement of longitudinal relaxation time. A few samples were investigated by high resolution solid state NMR and NMR in solution, which allowed us to identify the polyurethane constituting the artefact, to investigate the microstructure in detail, and to assess that the degradation process mostly affected the ethylene units used to cap the polypropylene oxide polymeric chain. As a matter of fact, a shortening of longitudinal relaxation time was accompanied by a degradation of ethylene units. The degradation of the inorganic loading was investigated by ²⁷Al MAS, which evidenced the absence of penta-coordinated aluminum in degraded samples.     

π-Complementation in the Unitisation and Multiplication Algebras of a Semiprime Algebra

π-complemented algebras are defined as those (not necessarily associative or unital) algebras such that each annihilator ideal is complemented by other annihilator ideal. For a given semiprime algebra A, we discuss the π-complementation of the unitisation algebra A ¹ of A. Moreover, if in addition the multiplication algebra ?(A) of A is also semiprime, we study the π-complementation in the algebras ?(A) and ?^?(A) (the multiplication ideal of A). In associative setting, we prove that A is π-complemented if and only if ?^?(A) is π-complemented, and that A ¹ π-complemented if and only if ?(A) is π-complemented.     

Hardness of Approximation for Crossing Number

We show that, if $\mathrm{P}\not=\mathrm{NP}$ , there is a constant c ₀>1 such that there is no c ₀-approximation algorithm for the crossing number, even when restricted to 3-regular graphs.