Tetrazene–Characterization of Its Polymorphs

The reinvestigation of tetrazene single crystalline material by means of X-ray methods resulted in a slightly different structure when compared to previously published data. Reaction conditions responsible for different crystalline modification formation were investigated. Newly described C form was found to be the primary reaction product and the combined action of temperature and the presence of water over time is required for the transition to the A form. Both forms were described by X-ray powder diffraction. Tetrazene was also subjected to infrared and Raman spectroscopy, which allowed differentiating between the forms. The molecule was isotopically labeled with 15N atoms at two different locations (ring and nitrogen sidechain) and employed in assigning vibrational modes to the resulting bands. Differences between sensitivities to mechanical stimuli of the two modifications were investigated and found industrially insignificant. In the same vein, the performance of either modification in primer composition and primer was identical.

Efficient Film Fabrication and Characterization of Poly(3,4-ethylenedioxythiophene):Poly(styrenesulfonate) (PEDOT:PSS)-Metalloporphine Nanocomposite and Its Application as Semiconductor Material

The use of composite films with semiconductor behavior is an alternative to enhance the efficiency of optoelectronic devices. Composite films of poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) and metalloporphines (MPs; M = Co, Cu, Pd) have been prepared by spin-coating. The PEDOT:PSS-MP films were treated with isopropanol (IPA) vapor to modify the polymer structure from benzoid to quinoid. The quinoid structure promotes improvements in the optical and electrical behavior of films. The composite films’ morphology and structure were characterized using infrared and Raman spectroscopy, scanning electron microscopy (SEM), and atomic force microscopy (AFM). Composite films were analyzed for their optical behavior by ultraviolet-visible spectroscopy: at λ < 450 nm, the films become transparent, indicating the capacity to be used as transparent electrodes in optoelectronic devices. At λ ≥ 450 nm, the absorbance in the films increased significantly. The CoP showed an 8 times larger current density compared to the CuP. A light induced change in the J-V curves was observed, and it is larger for the CoP. The conductivity values yielded between 1.23 × 102 and 1.92 × 103 Scm−1 and were higher in forward bias.

Electrospun Mats Based on PVA/NaDDBS/CNx Nanocomposite for Electrochemical Sensing

This study presents a nanocomposite developed with PVA, multiwall carbon nanotubes (CNTs) doped with nitrogen, and NaDDBS, which change the electrical properties of the polymer and its viscosity to be used in electrospinning process for obtaining mats of nano/macro fibers. The proposed nanocomposite was characterized using Fourier transform-infrared and Raman spectroscopy techniques, confirming the presence of the CNxs immersed in the polymer. High-resolution transmission electron microscopy was used to obtain the micrographs that showed the characteristic interplanar distances of the multiwall CNT in the polymeric matrix, with values of 3.63 Å. Finally, the CNx mats were exposed to various aqueous solutions in a potentiostat to demonstrate the effectiveness of the nanofibers for electrochemical analysis. The CNx-induced changes in the electrical properties of the polymer were identified using cyclic voltammograms, while the electrochemical analysis revealed supercapacitor behavior.

Adsorptive removal of chromium (VI) from synthetic waters using magnetic lignocellulosic composites

The removal of heavy metals from water is one of the major challenges that humanity must address to avoid negative potential impacts on the environment and human health. During the last few years, several adsorbents have been examined, in a search for highly efficient and cost-effective materials. In this work, we investigated the use of laurel, canelo and eucalyptus lignocellulosic sawdust residues (LRs) impregnated with magnetite nanoparticles (MNP), to remove Cr6+ ions. Each LR was added to an aqueous solution in which MNP were being synthesized by coprecipitation. Two composite adsorbents were obtained, with LR:MNP ratios of 1:1 and 3:1. The materials obtained were characterized by X-ray diffraction, scanning and transmission electron microscopy, and infrared and Raman spectroscopy. The results obtained showed that the laurel composite was the best adsorbent, reaching a maximum removal efficiency and capacity of 99.8 % and 30.5 mg/g, respectively. The optimal contact time was 30 min and the process fitted the Langmuir isotherm model, showing small effects of the fraction of sawdust residues used to support the MNP. Further studies will be performed to optimize the composition of the composites aiming to reduce the amount of costly MNP used while ensuring a high removal performance.

Submicron Non-contact Simultaneous Infrared and Raman Spectroscopy for Challenging Failure Analysis

We introduce a new infrared (IR) technique that provides submicron spatial resolution by making use of an infraredvisible, pump-probe arrangement that also offers a simultaneous Raman measurement in formerly challenging failure and contamination analyses. These challenges are typically due to the lack of spatial resolution and sample preparation restrictions from conventional FTIR, plus auto-fluorescence (AF) from Raman spectroscopy. Such a combined Optical PhotoThermal InfraRed (O-PTIR) and Raman instrumentation offers spatial resolution improvement over conventional IR measurements by 30 times at 1000 cm-1. The technique also improves sensitivity to exceptionally small quantities (? 400 femtogram) in reflection mode by sensing the photothermal response arising from absorbing infrared radiation (Fig. 1) [1]. The AF-free O-PTIR technique also delivers constant spatial resolution over the entire mid-IR range due to the use of a fixed wavelength probe beam at 532 nm [2]. Simultaneous Raman confirms and complements the O-PTIR measurements in cases with low AF. We will illustrate three examples that will highlight the advantage of the novel technique commonly observed in the failure and contamination analysis community.

Novel Insights into Corema album Berries: Vibrational Profile and Biological Activity

This study reports an evaluation of the biological properties of the edible berries from Corema album, an endemic shrub of the Portuguese coastline, aiming at its use as a nutraceutical. Different methanolic extracts were obtained from the pulp and seed of fresh berries: pulp extract, seed residue, and seed oil (extracted and characterized for the first time). For each of these, the antioxidant activity was assessed, by different methods, as well as the antimicrobial ability. Overall, the seeds were shown to be the most nutraceutical part of the berry since they showed higher antioxidant activity, while the pulp extract displayed a significant antimicrobial capacity against several clinically relevant bacterial strains. Furthermore, the extracts were fully characterized by complementary infrared and Raman spectroscopy, revealing the presence of phenolic acids, polysaccharides, sugars, and triterpenoids in the pulp, high content of unsaturated fatty acids in the seed oil, and significant amounts of phenolics and carotenoids in the seed residue. These results pave the way for a reliable correlation between chemical composition and biological activity, in edible fruit samples.

Synthesis, Single Crystal Structural Investigation, Hirshfeld Surface Analysis, Thermoanalysis and Spectroscopic Study of Two New Cu(II) and Co(II) Transition-Metal Complexes

Two new complexes, [Cu(dimpyr)2(H2O)2](NO3)2.2H2O (1) and (Hamdimpy)2[CoCl4].H2O (2), with the monodentate ligand 2-amino-6-methylpyrimidin-4-(1H)-one (dimpyr) and the countercation 4-amino-2,6-dimetylpyrimidium (Hamdimpy), respectively, were prepared and characterized by single crystal X-ray diffraction, elemental analysis and IR spectroscopy. In (1), the Cu(II) cation is tetracoordinated, in a square plan fashion, by two nitrogen atoms from the pyrimidine ring of the organic ligand and two oxygen atoms of two coordinated water molecules. In the atomic arrangement, the CuO2N2 square planes are interconnected via the formation of O-H…O hydrogen bonds involving both coordinated and free water molecules and NO3− nitrate anions to form inorganic layers parallel to the (a, b) plane at z = (2n + 1)/4. In (2), the central atom Co(II) is four-coordinated in a distorted tetrahedral fashion by four Cl− ions. The [CoCl4]2− tetrahedra are arranged parallel to the plane (110) at x = (2n + 1)/2 and the organic cations are grafted between them by establishing with them hydrogen bonds of CH…Cl and NH…Cl types. The vibrational absorption bands were identified by infrared and Raman spectroscopy. Intermolecular interactions were investigated via Hirshfeld surfaces and electronic properties such as HOMO and LUMO energies were derived. The two compounds were characterized by thermal analysis to determine their thermal behavior with respect to temperature.

Catalytic Dehydration of Fructose to 5-Hydroxymethylfurfural in Aqueous Medium over Nb2O5-Based Catalysts

The catalytic dehydration of fructose to 5-hydroxymethylfurfural (HMF) in water was performed in the presence of pristine Nb2O5 and composites containing Nb and Ti, Ce or Zr oxides. In all experiments, fructose was converted to HMF using water as the solvent. The catalysts were characterized by powder X-ray diffraction, scanning electron microscopy, N2 physical adsorption, infrared and Raman spectroscopy and temperature-programmed desorption of NH3. Experimental parameters such as fructose initial concentration, volume of the reacting suspension, operation temperature, reaction time and amount of catalyst were tuned in order to optimize the catalytic reaction process. The highest selectivity to HMF was ca. 80% in the presence of 0.5 g·L−1 of bare Nb2O5, Nb2O5-TiO2 or Nb2O5-CeO2 with a maximum fructose conversion of ca. 70%. However, the best compromise between high conversion and high selectivity was reached by using 1 g·L−1 of pristine Nb2O5. Indeed, the best result was obtained in the presence of Nb2O5, with a fructose conversion of 76% and a selectivity to HMF of 75%, corresponding to the highest HMF yield (57%). This result was obtained at a temperature of 165° in an autoclave after three hours of reaction by using 6 mL of 1 M fructose suspension with a catalyst amount equal to 1 g·L−1.