meso- and β-Pyrrole-Linked Chlorin-Bacteriochlorin Dyads for Promoting Far-Red FRET and Singlet Oxygen Production

A series of chlorin-bacteriochlorin dyads (derived from naturally occurring chlorophyll-a and bacteriochlorophyll-a), covalently connected either through the meso-aryl or β-pyrrole position (position-3) via an ester linkage have been synthesized and characterized as a new class of far-red emitting fluorescence resonance energy transfer (FRET) imaging, and heavy atom-lacking singlet oxygen-producing agents. From systematic absorption, fluorescence, electrochemical, and computational studies, the role of chlorin as an energy donor and bacteriochlorin as an energy acceptor in these wide-band-capturing dyads was established. Efficiency of FRET evaluated from spectral overlap was found to be 95 and 98 % for the meso-linked and β-pyrrole-linked dyads, respectively. Furthermore, evidence for the occurrence of FRET from singlet-excited chlorin to bacteriochlorin was secured from studies involving femtosecond transient absorption studies in toluene. The measured FRET rate constants, k_FRET, were in the order of 10¹¹ s⁻¹, suggesting the occurrence of ultrafast energy transfer in these dyads. Nanosecond transient absorption studies confirmed relaxation of the energy transfer product, ¹BChl*, to its triplet state, ³Bchl*. The ³Bchl* thus generated was capable of producing singlet oxygen with quantum yields comparable to their monomeric entities. The occurrence of efficient FRET emitting in the far-red region and the ability to produce singlet oxygen make the present series of dyads useful for photonic, imaging and therapy applications.     

A Practical Solution to a Cargo Loading Problem at Bethlehem Steel

The optimum assignment of structural steel shapes to rail cars is an important logistical problem in the steel industry. In this paper, we discuss an application at Bethlehem Steel that not only involves weight and dimensional constraints, but also customer unloading constraints. The formulation is a generalized bin packing problem which is solved by modifying and extending the first fit decreasing algorithm. The solution algorithm, SOLID (for Structural Optimal Loading IDentification), has been used extensively for one of Bethlehem's high tonnage customers providing very good practical (implementable) results that achieve the desired goals. Bethlehem has enhanced this approach for use with other customers.     

Openness of the Galois image for τ-modules of dimension 1

Let C be a smooth projective absolutely irreducible curve over a finite field , F its function field and A the subring of F of functions which are regular outside a fixed point ∞ of C. For every place ? of A, we denote the completion of A at ? by .In [Pi2], Pink proved the Mumford-Tate conjecture for Drinfeld modules. Let φ be a Drinfeld module of rank r defined over a finitely generated field K containing F. For every place ? of A, we denote by Γ_? the image of the representation

     

The use of Raman microscopy and laser desorption ionization mass spectrometry in the examination of synthetic organic pigments in modern works of art

Synthetic organic pigments are widely used in modern and contemporary works of art. They have been examined by a variety of techniques including spectroscopic methods such as Fourier transform infrared spectroscopy, Raman, and X‐ray powder diffraction as well as chromatographic or mass spectrometric techniques such as pyrolysis‐gas chromatography/mass spectrometry and laser desorption ionization mass spectrometry (LDI–MS). Often, a combination of techniques has been used to examine these pigments. This paper describes use of Raman spectroscopy to create a database of colorants including two pigments not previously reported, PO1 and PO2. Then, using Raman spectroscopy in combination with LDI–MS, samples from modern works of art by artists including Mark Rothko, Barnett Newman, and José de Rivera were examined in order to identify the pigments present. One finding was that Rothko used a variety of red pigments over the course of his career including PR11 which has not been previously reported in artwork, and PO2 found with its positional isomer PR1. Knowledge of the colorants serves to inform conservators about display and treatment decisions. Published 2014. This article is a U.S. Government work and is in the public domain in the USA.     

The Rate Constant for Dissociative Electron Attachment to Ozone Revisited

The rate constant for dissociative electron attachment to ozone has been derived over the energy range from about 0 to 10 eV using recently measured and also corrected cross section data. The new rate constant data sets for two partial dissociative channels, as well as for the total dissociative electron attachment, are compared with previously reported values, and existing discrepancies are discussed.     

Accuracy and variability of acoustic measures of voicing onset

Five commonly used methods for determining the onset of voicing of syllable-initial stop consonants were compared. The speech and glottal activity of 16 native speakers of Cantonese with normal voice quality were investigated during the production of consonant vowel (CV) syllables in Cantonese. Syllables consisted of the initial consonants /ph/, /th/, /kh/, /p/, /t/, and /k/ followed by the vowel /a/. All syllables had a high level tone, and were all real words in Cantonese. Measurements of voicing onset were made based on the onset of periodicity in the acoustic waveform, and on spectrographic measures of the onset of a voicing bar (f0), the onset of the first formant (F1), second formant (F2), and third formant (F3). These measurements were then compared against the onset of glottal opening as determined by electroglottography. Both accuracy and variability of each measure were calculated. Results suggest that the presence of aspiration in a syllable decreased the accuracy and increased the variability of spectrogram-based measurements, but did not strongly affect measurements made from the acoustic waveform. Overall, the acoustic waveform provided the most accurate estimate of voicing onset; measurements made from the amplitude waveform were also the least variable of the five measures. These results can be explained as a consequence of differences in spectral tilt of the voicing source in breathy versus modal phonation.     

Ionic liquid enhanced magnesium-based polymer electrolytes for electrical double-layer capacitors

This paper describes the preparation and characterization of poly(vinyl alcohol) (PVA)-added ionic liquid-based ion conductors. The polymer electrolyte is incorporated with magnesium triflate [Mg(CF₃SO₃)₂ or MgTf] as salt and 1-butyl-3-methylimidazolium bromide (BmImBr) as ionic liquid. Differential scanning calorimetry (DSC) is carried out to investigate the glass transition temperature which is used to study the plasticizing effect of the ionic liquid. The highest conducting ionic liquid-based polymer electrolyte is used to fabricate electrical double-layer capacitors (EDLC). The electrochemical potential window is evaluated using linear sweep voltammetry (LSV). The electrochemical capacitance of the EDLC is evaluated through cyclic voltammetry (CV) and galvanostatic charge–discharge (GCD). The electrochemical potential window of ionic liquid-added polymer electrolyte is extended from 1.35 to 2.6 V. Cyclic voltammetry (CV) proves the improvement in specific capacitance of the electrical double-layer capacitors (EDLCs) containing ionic liquid-added polymer electrolyte.     

Switching from linear to cyclic δ‐Polyvalerolactone synthesized via zeolitic imidazolate framework as a catalyst: A promising approach

A series of spray dried zeolitic imidazolate frameworks (ZIFs = ZIF‐8, ZIF‐67, and Zn/Co‐ZIF) are used as a catalyst for the bulk ring‐opening polymerization of δ‐valerolactone without any co‐catalyst to generate polyvalerolactone. Interestingly, using the same catalyst under the same reaction conditions could manipulate the structure of the product polymer, and thus its physical properties. Thus, using a dried substrate leads to the formation of the cyclic polymer while a linear polymer was formed on using the commercially available substrate. An activated monomer mechanism has been suggested where the propagating zinc alkoxide undergoes an intramolecular transesterification to release cyclic or linear polyvalerolactone. The ROP of δ‐VL without drying shows that the polymeric zwitterions have little tendency to cyclize in the presence of moisture. At 140 °C, ZIF‐8 shows a superior catalytic activity resulting in the production of cyclic polyvalerolactone having a high molecular weight as compared to ZIF‐67 or Zn/Co‐ZIF due to the presence of highly active sites. The catalyst could be recycled and reused without any significant loss of catalytic activity.     

Oxidation of Oxazolines and Thiazolines to Oxazoles and Thiazoles. Application of the Kharasch-Sosnovsky Reaction

Using a modification of the Kharasch-Sosnovsky reaction, the oxidation of oxazolines and thiazolines bearing a variety of 2-alkyl substituents (chiral and achiral) were smoothly oxidized to their corresponding oxazoles and thiazoles, respectively. The key feature involved in the successful implementation of this important oxidation was the use of a mixture of Cu(I) and Cu(II) salts to enhance the oxidation of the intermediate captodative radical, 24. The main limitation of this method was shown when the oxidation failed with oxazolines/thiazolines lacking the carboalkoxy group at C-4.