FIR Laser Lines from CH3OD: A Review

The methanol isotopic species CH₃OD has also proved to be an efficient and powerful medium to generate radiation in the far infrared (FIR) region. After the critical review of 1994, six papers have been published dealing with new FIR laser lines from this molecule. As a consequence of the use of wide tunability waveguide CO₂ lasers as well as a new pulsed CO₂ laser operating at hot and sequential bands, as of optical pumping sources, the total number of the FIR laser lines increased from 122 in 1994 to 227 today. In this communication we present an updated and complete catalogue of FIR laser lines generated from CH₃OD. Information on wavelength, offset, relative polarization, intensity, and optimum operation pressure is generally available.     

Energy flow in negative index materials

From Maxwell's equations, we compute the speed and the direction of propagation of active power refractedfrom air into a negative index material. We prove, both analytically and numerically that the power mayrefract positively even if phase fronts refract negatively. Considerations on the usage of ray optics inproblems involving negative index materials are drawn.     

Axiomatic properties of inconsistency indices for pairwise comparisons

Pairwise comparisons are a well-known method for the representation of the subjective preferences of a decision maker. Evaluating their inconsistency has been a widely studied and discussed topic and several indices have been proposed in the literature to perform this task. As an acceptable level of consistency is closely related to the reliability of preferences, a suitable choice of an inconsistency index is a crucial phase in decision-making processes. The use of different methods for measuring consistency must be carefully evaluated, as it can affect the decision outcome in practical applications. In this paper, we present five axioms aimed at characterizing inconsistency indices. In addition, we prove that some of the indices proposed in the literature satisfy these axioms, whereas others do not, and therefore, in our view, they may fail to correctly evaluate inconsistency.     

Second Generation Nitrogen Doped Titania Nanoparticles: A Comprehensive Electronic and Microstructural Picture

A state‐of‐the‐art overview of N‐dopant characterizations in nano‐TiO₂ second‐generation photocatalysts is provided. The related literature is very rich and sometimes offers contrasting interpretations. Here we critically discuss up‐to‐date literature results and our own findings, as retrieved by several experimental (BET, HR‐TEM, XPS, DRS, HR‐XRPD, EXAFS, electrochemical tools) and theoretical (periodic DFT) techniques. Our intent is to pull together outcomes from very different and complementary sources to make an as much as possible coherent picture of the morphological, electrochemical and electronic properties of N‐TiO₂ materials. It is commonly accepted that critical issues to be considered in the design of high‐performing N‐TiO₂ photocatalysts are synthetic strategy, defect concentration and chemical nature of the lattice point defects. We focus on the latter two issues, with emphasis on sol‐gel prepared materials, according to the specific area of expertise of our group. The problem of the chemical nature of guest N species into the lattice is crucial, as substitutional (N_s) or interstitial (N_i) nitrogen place their valence states just above the valence band or deeper into the band gap. Overall, we show how synergism among experimental and theoretical techniques is decisive to disentangle structural, electronic and morphological effects in complex N‐doped TiO₂ matrices.     

Reactive Oxygen Species Explicit Dosimetry for Photofrin-mediated Pleural Photodynamic Therapy

Explicit dosimetry of treatment light fluence and implicit dosimetry of photosensitizer photobleaching are commonly used methods to guide dose delivery during clinical PDT. Tissue oxygen, however, is not routinely monitored intraoperatively even though it is one of the three major components of treatment. Quantitative information about in vivo tissue oxygenation during PDT is desirable, because it enables reactive oxygen species explicit dosimetry (ROSED) for prediction of treatment outcome based on PDT-induced changes in tumor oxygen level. Here, we demonstrate ROSED in a clinical setting, Photofrin-mediated pleural photodynamic therapy, by utilizing tumor blood flow information measured by diffuse correlation spectroscopy (DCS). A DCS contact probe was sutured to the pleural cavity wall after surgical resection of pleural mesothelioma tumor to monitor tissue blood flow (blood flow index) during intraoperative PDT treatment. Isotropic detectors were used to measure treatment light fluence and photosensitizer concentration. Blood-flow-derived tumor oxygen concentration, estimated by applying a preclinically determined conversion factor of 1.5 × 10⁹ μMs cm⁻² to the blood flow index, was used in the ROSED model to calculate the total reacted reactive oxygen species [ROS]rx. Seven patients and 12 different pleural sites were assessed and large inter- and intrapatient heterogeneities in [ROS]rx were observed although an identical light dose of 60 J cm⁻² was prescribed to all patients.     

Ferrofluid Impregnation Efficiency and Its Spatial Variability in Natural and Synthetic Porous Media: Implications for Magnetic Pore Fabric Studies

Transport in Porous Media - Magnetic pore fabrics (MPF) are an efficient way to characterize pore space anisotropy, i.e., the average pore shape and orientation. They are determined by impregnating...     

Co-doped ZnO nanoparticles synthesized by an adapted sol–gel method: effects on the structural,optical, photocatalytic and antibacterial properties

Pure and Co-doped ZnO nanoparticles were synthesized with different cobalt levels (1–10 mol%) via adapted sol–gel method using water as solvent and characterized by X-ray diffraction, transmission electron microscopy, Raman spectroscopy and photoacoustic absorption spectroscopy. The results showed that all the samples have hexagonal wurtzite structure, with no evidence of any secondary phases until 10 mol% of the dopant. The average crystallite size of the samples was in the range of 25–50 nm, do not showing significant differences with the increase of the dopant level. However, the band gap energy of the nanoparticles decreases from 2.98 eV (pure ZnO) to 1.95 eV (10 mol% of Co). The photocatalytic activity of the samples was evaluated on the removal of methylene blue under visible light irradiation, which revealed an efficiency reduction by Co-doping ZnO. The antibacterial property was carried out indicating activity of the prepared samples against gram-positive bacteria.     

Synthesis and Electronic Properties of 1,2‐Hemisquarimines and Their Encapsulation in a Cucurbit[7]uril Host

The synthesis of a new class of robust squaraine dyes, colloquially named 1,2‐hemisquarimines (1,2‐HSQiMs), through the microwave‐assisted condensation of aniline derivatives with the 1,2‐squaraine core is reported. In CH₃CN, 1,2‐HSQiMs show a broad absorption band with a high extinction coefficient and a maximum at around λ=530 nm, as well as an emission band centered at about λ=574 nm, that are pH dependent. Protonation of the imine nitrogen causes a redshift of both absorption and emission maxima, with a concomitant increase in the lifetime of the emitting excited state. Encapsulation of the chromophore into a cucurbit[7]uril host revealed fluorescence enhancement and increased photostability in water. The redox characteristics of 1,2‐HSQiMs indicate that charge injection into TiO₂ is possible; this opens up promising perspectives for their use as photosensitizers for solar energy conversion.     

Access to β‐Lactams by Enantioselective Palladium(0)‐Catalyzed C(sp3)H Alkylation

β‐Lactams are very important structural motifs because of their broad biological activities as well as their propensity to engage in ring‐opening reactions. Transition‐metal‐catalyzed C? H functionalizations have emerged as strategy enabling yet uncommon highly efficient disconnections. In contrast to the significant progress of Pd⁰‐catalyzed C? H functionalization for aryl–aryl couplings, related reactions involving the formation of saturated C(sp³)? C(sp³) bonds are elusive. Reported here is an asymmetric C? H functionalization approach to β‐lactams using readily accessible chloroacetamide substrates. Important aspects of this transformation are challenging C(sp³)? C(sp³) and strain‐building reductive eliminations to for the four‐membered ring. In general, the β‐lactams are formed in excellent yields and enantioselectivities using a bulky taddol phosphoramidite ligand in combination with adamantyl carboxylic acid as cocatalyst.     

XAS analysis of iron and palladium bonded to a polysaccharide produced anaerobically by a strain of Klebsiella oxytoca

Klebsiella oxytoca BAS‐10 ferments citrate to acetic acid and CO₂, and secretes a specific exopolysaccharide (EPS), which is able to bind different metallic species. These biomaterials may be used for different biotechnological purposes, including applications as innovative green biogenerated catalysts. In production of biogenerated Pd species, the Fe(III) as ferric citrate is added to anaerobic culture of K. oxytoca BAS‐10, in the presence of palladium species, to increase the EPS secretion and improve Pd‐EPS yield. In this process, bi‐metallic (FePd‐EPS) biomaterials were produced for the first time. The morphology of bi‐metallic EPS, and the chemical state of the two metals in the FePd‐EPS, are investigated by transmission electron microscopy, Fourier transform infra‐red spectroscopy, micro‐X‐ray fluorescence, and X‐ray absorption spectroscopy methods (XANES and EXAFS), and compared with mono‐metallic Pd‐EPS and Fe‐EPS complexes. Iron in FePd‐EPS is in the mineralized form of iron oxides/hydroxides, predominantly in the form of Fe³⁺, with a small amount of Fe²⁺ in the structure, most probably a mixture of different nano‐crystalline iron oxides and hydroxides, as in mono‐metallic Fe‐EPS. Palladium is found as Pd(0) in the form of metallic nanoparticles with face‐centred cubic structure in both bi‐metallic (FePd‐EPS) and mono‐metallic (Pd‐EPS) species. In bi‐metallic species, Pd and Fe nanoparticles agglomerate in larger clusters, but they remain spatially separated. The catalytic ability of bi‐metallic species (FePd‐EPS) in a hydrodechlorination reaction is improved in comparison with mono‐metallic Pd‐EPS.