High pressure‐assisted synthesis of 1,2,3‐trialkyldiaziridines from N‐chloroalkylamines

New method for the preparation of 1,2,3‐trialkyldiaziridines 1 in high yields, based on the transformation of N‐chloroalkylamines 3 without using carbonyl compounds in the presence of primary aliphatic amines with the same alkyl fragment, potassium carbonate and a small amount of water in CHCl₃ under high pressure (500 MPa), was developed. Diaziridines 1 can be synthesized in the same conditions using a larger amount of potassium carbonate instead of primary aliphatic amines however in lower yields. The kinetic investigations on the synthesis of 1,2‐diethyl‐3‐methyldiaziridine 1a from N‐chloroethylamine 3a have shown that the reaction leading to diaziridine 1a proceeds according to the law of the second order.     

Study on different pre-treatment procedures for metal determination in Orujo spirit samples by ICP-AES

In this work several pre-treatment methods were studied for metal (Na, K, Mg, Cu and Ca) determination in Orujo spirit samples using inductively coupled plasma atomic emission spectrometry (ICP-AES). Dilution, digestion, evaporation, and cryogenic desolvatation techniques were comparatively evaluated. Because of their analytical characteristics, digestion and evaporation with nitrogen current were found to be appropriate procedures for the determination of metals in alcoholic spirit samples. Yet, if simplicity and application time are to be considered, the latter—evaporation in a water bath with a nitrogen current—stands out as the optimum procedure for any further determinations in Orujo samples by ICP-AES. Low detection levels and wide linear ranges (sufficient to determine these metals in the samples studied) were achieved for each metal. The recoveries (in the 97.5-100.5% range) and the precision (R.S.D. lower than 5.6%) obtained were also satisfactory. The selected procedure was applied to determine the content of metals in 80 representative Galician Orujo spirit samples with and without a Certified Brand of Origin (CBO) which had been produced using different distillation systems. The metal concentrations ranged between 0.37 and 79.7 mg L⁻¹ for Na, <LOD to 12.4 mg L⁻¹ for K, 0.02-4.83 mg L⁻¹ for Mg content, <LOD to 37.3 mg L⁻¹ for Cu and 0.03-13.10 mg L⁻¹ for Ca.     

Benefits of applying combined diffuse reflectance FTIR spectroscopy and principal component analysis for the study of blue tempera historical painting

This paper explores the application of diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) to the examination of historic blue pigments and blue tempera paintings commonly found on works of art. The discussion is mainly focused on the practical benefits of using this technique joined to principal component analysis (PCA), a powerful multivariate analysis tool. Thanks to the study of several replica samples that contain either pure blue pigments (azurite, lapis lazuli and smalt), or pure binder (rabbit glue) and mixtures of each of the pigments with the binder (tempera samples), different aspects of these benefits are highlighted. Comparative results of direct spectra and multivariate analysis using transmittance-Fourier transform infrared spectroscopy (T-FTIR) are discussed throughout this study. Results showed an excellent ability of PCA on DRIFT spectra for discriminating replica samples according to differing composition. Several IR regions were tested with this aim; the fingerprint IR region exhibited the best ability for successfully clustering the samples. The presence of the binder was also discriminated. Only using this approach it was possible to completely separate all the studied replica samples. This demonstrates the potential benefits of this approach in identifying historical pigments and binders for conservation and restoration purposes in the field of Cultural Heritage.     

Molecular and electronic structures of mononuclear iron complexes using strongly electron-donating ligands and their oxidized forms

The ligand L (2-) (H 2L = N, N'-dimethyl- N, N'-bis(3,5-di- t-butyl-2-hydroxybenzyl)-1,2-diaminoethane) has been employed for the synthesis of two mononuclear Fe (III) complexes, namely, [LFe(eta (2)-NO 3)] and [LFeCl]. L (2-) is comprised of four strongly electron-donating groups (two tert-amines and two phenolates) that increase the electron density at the coordinated ferric ions. This property should facilitate oxidation of the complexes, that is, stabilization of the oxidized species. The molecular structures in the solid state have been established by X-ray diffraction studies. [LFeCl] is five-coordinate in a square-pyramidal coordination environment with the ligand adopting a trans-conformation, while [LFe(eta (2)-NO 3)] is six-coordinate in a distorted octahedral environment with the ligand in a beta-cis conformation. The electronic structures have been studied using magnetization, EPR, Mossbauer (with and without applied field), UV-vis-NIR, and X-ray absorption spectroscopies, which demonstrate highly anisotropic covalency from the strong sigma- and pi-donating phenolates. This analysis is supported by DFT calculations on [LFeCl]. The variations of the well-understood spectroscopic data in the solid state to the spectroscopic data in solution have been used to obtain insight in the molecular structure of the two complexes in solution. While the molecular structures of the solid states are retained in solutions of nonpolar aprotic solvents, there is, however, one common molecular structure in all protic polar solvents. The analysis of the LMCT transitions and the rhombicity E/ D clearly establish that both compounds exhibit a beta-cis conformation in these protic polar solvents. These two open coordination sites, cis to each other, allow access for two potential ligands in close proximity. Electrochemical analysis establishes two reversible oxidation waves for [LFeCl] at +0.55 V and +0.93 V vs Fc (+)/Fc and one reversible oxidation wave at +0.59 V with an irreversible oxidation at +1.07 V vs Fc (+)/Fc for [LFe(eta (2)-NO 3)]. The one- and the two-electron oxidations of [LFeCl] by chronoamperometry have been followed spectroscopically. The increase of a strong band centered at 420 nm indicates the formulation of [LFeCl] (+) as a Fe (III) monophenoxyl radical complex and of [LFeCl] (2+) as a Fe (III) bisphenoxyl radical complex. These studies imply that the ligand L (2-) is capable of providing a flexible coordination geometry with two binding sites for substrates and the allocation of two oxidation equivalents on the ligand.     

Ordering poly(trimethylsilyl styrene‐block‐D,L‐lactide) block copolymers in thin films by solvent annealing using a mixture of domain‐selective solvents

Controlling the morphology, domain orientation, and domain size of block copolymer (BCP) thin films is desirable for many applications in nanotechnology. These properties can be tuned during solvent annealing by varying the solvent choice and degree of swelling which affect the effective miscibility and volume fraction of the BCP domains. In this work, we demonstrate with a bulk lamellae‐forming BCP, poly(4‐trimethylsilylstyrene‐block‐D ,L ‐lactide) (PTMSS‐b‐PLA), that varying the composition of a mixture of solvent vapors containing cyclohexane (PTMSS‐selective) and acetone (PLA‐selective), enables formation of perpendicularly oriented lamellae with sub‐20‐nm pitch lines. The BCP domain periodicity was also observed to increase by 30%, compared to bulk, following solvent annealing. Furthermore, solvent annealing alone is shown to induce a transition from a disordered to an ordered BCP. We rationalize our observations by hypothesizing that the use of a combination of domain selective solvent mixtures serves to increase the effective repulsion between the blocks of the copolymer. We furnish results from self‐consistent field theory calculations to support the proposed mechanism. © 2013 Wiley Periodicals, Inc. J. Polym. Sci. Part B: Polym. Phys. 2014 , 52, 36–45     

Correlating polymer structure,dynamics, and function with atomic force microscopy

Since its development, atomic force microscopy (AFM) has become an indispensable tool for investigating fundamental and technological applications of polymer materials. The versatility of AFM imaging modes and operating conditions allows for nanoscale characterization of a range of dynamic processes, such as crystallization, phase separation, self assembly, and electronic transport. Advances in AFM technology, particularly high-speed and high-resolution imaging, enable investigation of polymer structure, function, and dynamics in real world conditions and across a range of relevant spatial and temporal scales. In this perspective, we highlight a collection of recent polymer studies that utilize AFM to correlate the function and structure of polymer films, with focus on its multiparametric imaging capabilities. As the complexity of polymer materials and morphologies continues to increase, AFM is well poised to meet the accompanying demand for nanoscale imaging and characterization.     

Rapid MALDI-MS Assays for Drug Quantification in Biological Matrices: Lessons Learned,New Developments,and Future Perspectives

Matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS) has rarely been used in the field of therapeutic drug monitoring, partly because of the complexity of the ionization processes between the compounds to be quantified and the many MALDI matrices available. The development of a viable MALDI-MS method that meets regulatory guidelines for bioanalytical method validation requires prior knowledge of the suitability of (i) the MALDI matrix with the analyte class and properties for ionization, (ii) the crystallization properties of the MALDI matrix with automation features, and (iii) the MS instrumentation used to achieve sensitive and specific measurements in order to determine low pharmacological drug concentrations in biological matrices. In the present hybrid article/white paper, we review the developments required for the establishment of MALDI-MS assays for the quantification of drugs in tissues and plasma, illustrated with concrete results for the different steps. We summarize the necessary parameters that need to be controlled for the successful development of fully validated MALDI-MS methods according to regulatory authorities, as well as currently unsolved problems and promising ways to address them. Finally, we propose an expert opinion on future perspectives and needs in order to establish MALDI-MS as a universal method for therapeutic drug monitoring.     

How to Look for Compounds: Predictive Screening and in situ Studies in Na−Zn−Bi System

Here, the combination of theoretical computations followed by rapid experimental screening and in situ diffraction studies is demonstrated as a powerful strategy for novel compounds discovery. When applied for the previously “empty” Na−Zn−Bi system, such an approach led to four novel phases. The compositional space of this system was rapidly screened via the hydride route method and the theoretically predicted NaZnBi (PbClF type, P4/nmm) and Na₁₁Zn₂Bi₅ (Na₁₁Cd₂Sb₅ type, P ) phases were successfully synthesized, while other computationally generated compounds on the list were rejected. In addition, single crystal X-ray diffraction studies of NaZnBi indicate minor deviations from the stoichiometric 1 : 1 : 1 molar ratio. As a result, two isostructural (PbClF type, P4/nmm) Zn-deficient phases with similar compositions, but distinctly different unit cell parameters were discovered. The vacancies on Zn sites and unit cell expansion were rationalized from bonding analysis using electronic structure calculations on stoichiometric “NaZnBi”. In-situ synchrotron powder X-ray diffraction studies shed light on complex equilibria in the Na−Zn−Bi system at elevated temperatures. In particular, the high-temperature polymorph HT-Na₃Bi (BiF₃ type, Fm m) was obtained as a product of Na₁₁Zn₂Bi₅ decomposition above 611 K. HT-Na₃Bi cannot be stabilized at room temperature by quenching, and this type of structure was earlier observed in the high-pressure polymorph HP-Na₃Bi above 0.5 GPa. The aforementioned approach of predictive synthesis can be extended to other multinary systems.