Chemical composition of contemporary black printing inks based on infrared spectroscopy: basic information for the characterization and discrimination of artistic prints

This article aims to provide the basic information necessary to afford the discrimination of artistic prints based on chemical information. The presence of original and non-original prints in the art market is a real problem, especially for contemporary artists. Most of the non-original elements can be distinguished on the basis of their stylistics and printing characteristics, but sometimes this information is not enough. To facilitate discrimination in these cases, we propose to add, to the previously indicated aspects, the chemical information of the materials involved in the production of the original series (inks, paper and pencil). Comparison of the composition of any element with that established for the original series will permit the attribution of any doubtful element. This article is focused on the evaluation of this approach by determining the chemical composition of contemporary black printing inks by infrared spectroscopy and by searching, on the basis of the information obtained, for criteria capable to discriminate between prints made of different inks. The success of the approach with this set of inks could easily be extended to the study of colour inks. The study also includes the characterization and discrimination of black pigments because they are the most characteristic component of these inks and because this information can also be useful for other artistic studies. The procedure proposed permits the analysis of inks with minimum deterioration of the artwork. Results indicate the capability of the approach because, following the procedure, it is possible to distinguish between black pigments attending to the presence of hydroxyapatite, silicate and some other specific bands, whereas black inks can be discriminated by paying attention to the inclusion in their composition of such pigments as bone black, Prussian blue, mars brown or other specific bands. Scanning electron microscopy analyses have corroborated the results obtained.     

An all-atom force field for metallocenes

A new all-atom force field, for the molecular modeling of metallocenes was constructed. Quantum chemical calculations were performed to obtain several force field terms not yet defined in the literature. The remainder were transferred from the OPLS-AA/AMBER framework. The parametrization work included the obtention of geometrical parameters, torsion energy profiles, and distributions of atomic charges that blend smoothly with the OPLS-AA specification for a variety of organic molecular fragments. Validation was carried out by comparing simulated and experimental data for five different ferrocene derivatives in the crystalline phase. The present model can be regarded as a step toward a general force field for metallocenes, built in a systematic way, easily integrated with OPLS-AA, and transferable between different metal-ligand combinations.     

A Ligand System for the Flexible Functionalization of Quantum Dots via Click Chemistry

We present a novel ligand, 5‐norbornene‐2‐nonanoic acid, which can be directly added during established quantum dot (QD) syntheses in organic solvents to generate “clickable” QDs at a few hundred nmol scale. This ligand has a carboxyl group at one terminus to bind to the surface of QDs and a norbornene group at the opposite end that enables straightforward phase transfer of QDs into aqueous solutions via efficient norbornene/tetrazine click chemistry. Our ligand system removes the traditional ligand‐exchange step and can produce water‐soluble QDs with a high quantum yield and a small hydrodynamic diameter of approximately 12 nm at an order of magnitude higher scale than previous methods. We demonstrate the effectiveness of our approach by incubating azido‐functionalized CdSe/CdS QDs with 4T1 cancer cells that are metabolically labeled with a dibenzocyclooctyne‐bearing unnatural sugar. The QDs exhibit high targeting efficiency and minimal nonspecific binding.     

Large volume injection of water in gas chromatography–mass spectrometry using the Through Oven Transfer Adsorption Desorption interface: Application to multiresidue analysis of pesticides

In the present work, the potential of the Through Oven Transfer Adsorption Desorption (TOTAD) interface for the large volume injection (LVI) of aqueous samples in gas chromatography (GC) using a mass spectrometry (MS) detector is demonstrated. To this end, a new method for the determination of pesticides in water is presented, being the first developed method in which injection of large amounts of polar solvents using the TOTAD interface and an MS detector are combined, is applied to the determination of pesticides in water. Water samples, as large as 5 ml, were directly injected into a capillary GC. No sample pre-treatment step other than simple filtration was needed. The TOTAD interface allows the introduction of several millilitres of water, while maintaining good chromatographic characteristics. The water is almost entirely eliminated, so that LVI of aqueous samples and an MS detector can be used without problems. Organophosphorus, organochlorine, and triazine pesticides were determined in one run. Calibration curves were linear in the range tested and the sensitivity achieved injecting 5 ml of water sample was sufficient for most of the target pesticides but not for all of them. Sensitivity of the analysis can be improved by increasing the sample volume. No variability was observed in the retention times and relative standard deviations from absolute peak areas were good, considering that they corresponded to the overall analysis. The method was applied to the analysis of pesticide residues in real water samples.     

Formation of Pd/Au nanostructures from Pd nanowires via galvanic replacement reaction

Bimetallic nanostructures with non-random metal atoms distribution are very important for various applications. To synthesize such structures via benign wet chemistry approach remains challenging. This paper reports a synthesis of a Au/Pd alloy nanostructure through the galvanic replacement reaction between Pd ultrathin nanowires (2.4 +/- 0.2 nm in width, over 30 nm in length) and AuCl3 in toluene. Both morphological and structural changes were monitored during the reaction up to 10 h. Continuous changes of chemical composition and crystalline structure from Pd nanowires to Pd68Au32 and Pd45Au55 alloys, and to Au nanoparticles were observed. More interestingly, by using combined techniques such as high-resolution transmission electron microscopy (HRTEM), X-ray diffraction (XRD), energy dispersive X-ray spectrometry (EDS), UV-vis absorption, and extended X-ray absorption fine structure (EXAFS) spectroscopy, we found the formation of Pd68Au32 non-random alloy with Au-rich core and Pd-rich shell, and random Pd45Au55 alloy with uniformly mixed Pd and Au atom inside the nanoparticles, respectively. Density functional theory (DFT) calculations indicated that alkylamine will strongly stabilize Pd to the surface, resulting in diffusion of Au atoms into the core region to form a non-random alloy. We believe such benign synthetic techniques can also enable the large scale preparation of various types of non-random alloys for several technically important catalysis applications.     

Comparing historical and contemporary opera singers with historical and contemporary Jewish cantors

This study is an attempt to ascertain if singers from different traditions and milieus follow similar aesthetic trends regardless of training and/or background. Cantors who sang the Jewish synagogue liturgy during the Golden Age of cantorial singing prior to World War II came from Eastern and Central Europe. For the most part, they were not trained in the classical Western opera tradition. They received training from choir leaders and other cantors and the training was primarily in the modes of synagogue chant. Cantors today receive the same kinds of training that opera singers receive, often from the same teachers. Four groups of singers, consisting of four singers in each group, were utilized in this study. The four groups are: historical opera singers, contemporary opera singers, historical cantors, and contemporary cantors. The historical opera singer recordings date from as early as 1909 to as late as 1939. It was not possible to determine the dates of the historical cantor recordings. However, the four cantors chosen for this group were active only to the 1940s. Contemporary samples were taken from CDs and/or live recordings and all the singers from the contemporary groups are either still active or were active in the 1960s through the 1980s and all of them are considered to be premier-level singers in their respective areas. The variables analyzed were: vibrato pulse rate, frequency variation of the vibrato pulse above and below the mean sustained sung frequency in percent, the mean amplitude variation of the amplitude vibrato pulse above and below the mean sustained amplitude in percent and the fast Fourier transform (FFT) power spectrum of the sustained samples. Results indicate that most of the significant differences were found between eras and not between groups within a time period.     

Formal Group Laws for Affine Kac-Moody groups and group quantization

We describe a method for obtaining Formal Group Laws from the structure constants of Affine Kac-Moody groups and then apply a group manifold quantization procedure which permits construction of physical representations by using only canonical structures on the group. As an intermediate step we get an explicit expression for two-cocycles on Loop Groups. The programme is applied to the AffineSU(2) group.Research partially supported by the Conselleria de Cultura de la Generalitat Valenciana, the Plan de Formacion del Personal Investigador, and the Comision Asesora de Investigacion Cientifica y Tecnica (CAICYT)On leave of absence from the IFIC, Centro Mixto Universidad de Valencia — C.S.I.C. and the Departamento de Fisica Teorica de la Universidad de Valencia     

Interpolation of Vector-Valued Real Analytic Functions

Let R^d be an open domain. The sequentially complete DF-spacesE are characterized such that for each (some) discrete sequence(z_n) , a sequence of natural numbers (k_n) and any family the infinite system of equations has an E-valued real analytic solution f.     

Linearization of a class of non-linear systems modelled by multibond graphs

Based on non-linear systems described by multibond graphs, a procedure designed to present symbolic linearization of these multibond graphs, is presented in this paper. Firstly, a junction structure of a multibond graph with multiport gyrators that represent Eulerian junction structures is proposed. In addition, non-linear multiport resistors are considered. By knowing the non-linear causal paths and loops of the non-linear multibond graph, the linearization is obtained by two steps: (1) The original multibond graph on the nominal operating point is evaluated; (2) New and additional paths based on the non-linear causal paths and loops are included. The state space representation of the linearized multibond graph using the corresponding junction structure is presented. An advantage of this methodology is its ability to allow the user to define a nominal operating point in which the linearization will be carried out.

In order to apply the proposed methodology, two physical systems are modelled and linearized by multibond graphs: a synchronous generator and a two degrees of freedom PUMA. Simulation results of these non-linear and linearized systems are shown.     

Inflation with $$f(R,\phi )$$ in Jordan frame

We consider an f(R) action that is non-minimally coupled to a massive scalar field. The model closely resembles scalar–tensor theory and by conformal transformation can be transformed to Einstein frame. To avoid the ambiguity of the frame dependence, we obtain an exact analytical solution in Jordan frame and show that the model leads to a period of accelerated expansion with an exit. Further, we compute the scalar and tensor power spectrum for the model and compare them with observations.