Planar 2‐Pyridyl‐1,2,3‐triazole Derived Metallo‐ligands: Self‐assembly with PdCl2 and Photocatalysis

Self‐assembled metallosupramolecular architectures (MSAs) with built‐in functionalities such as light‐harvesting metal centers are a promising approach for developing emergent properties within discrete molecular systems. Herein we describe the synthesis of two new but simple “click” ligands featuring a bidentate 2‐pyridyl‐1,2,3‐triazole chelate pocket linked to a monodentate pyridyl (either 3‐ or 4‐substituted, L1 and L2 ) unit. The ligands and the corresponding four Pd^IIand Pt^IImetallo‐ligands ( Pd1 , Pd2 , Pt1 and Pt2 ) were synthesized and characterized using nuclear magnetic resonance (NMR) spectroscopy, electrospray ionization mass spectrometry (ESI‐MS), and X‐ray crystallography. Solid‐state characterization of the series of ligands and metallo‐ligands revealed that these compounds display a co‐planar conformation of all the aryl units. The Pt^IIcontaining metallo‐ligands ( Pt1 and Pt2 ) were found to assemble into square ( Sqr ) and triangular ( Tri ) shaped architectures when combined with neutral PdCl₂ linker units. Additionally, the ability of the Pt^IImetallo‐ligands and Tri to photocatalyze the cycloaddition of singlet oxygen to anthracene was investigated.     

MNDO calculations on boron–nitrogen derivatives of nonbenzenoid aromatics: I. The two fully boron–nitrogen-alternating isomers of “inorganic azulene”

Modified neglect of diatomic overlap (MNDO) calculations have been used to investigate the ground state properties of the two fully boron-nitrogen-alternating isomers of “inorganic azulene”: 1,3,4,6,8-pentaaza-2,3a, 5,7, 8a-pentaboraazulene ( 1 , 1,3,4,6,8-PAPBAZ) and 2,3a,5,7,8a-pentaaza-1,3,4,6,8-pentaboraazulene ( 2 , 2,3a,5,7,8a-PAPBAZ). Both molecules optimize to planar structures, have exothermic heats of formation (−194.4 kcal/mol and −161.4 kcal/mol, respectively), and exhibit some bond delocalization. The relationship of these two PAPBAZ isomers to their organic parent molecule, azulene, is discussed.     

Highly charged ions in a new era of high resolution X-ray astrophysics

X-ray astronomy and ground-based atomic physics have a long history of fruitful collaboration: Sound understanding of the underlying atomic physics is the key to reliable interpretation of the spectra from celestial sources; conversely, astronomical spectra have been used to benchmark and advance atomic physics. This interplay is about to become even more important as we enter a new era of high-resolution X-ray astrophysics with large effective collection area. Although high-resolution observations with the gratings on the Chandra and XMM-Newton observatories continue to drive new science, upcoming planned and proposed missions will open up new discovery space in the near future that is currently challenging to access: high-resolution spectroscopy on extended sources, in the Fe K band, and on short time scales. This review summarizes open questions in these areas and the design parameters for the Hitomi, XRISM, Athena, and Arcus observatories. The expected high quality of spectra taken with these observatories puts new constraints on the accuracy of atomic reference data required to take full advantage of the diagnostic potential of these spectra.     

Nanosized aerosols from consumer sprays: experimental analysis and exposure modeling for four commercial products

Consumer spray products are already on the market in the cosmetics and household sector, which suggest by their label that they contain engineered nanoparticles (ENP). Sprays are considered critical for human health, because the lungs represent a major route for the uptake of ENP into the human body. To contribute to the exposure assessment of ENP in consumer spray products, we analyzed ENP in four commercially available sprays: one antiperspirant, two shoe impregnation sprays, and one plant-strengthening agent. The spray dispersions were analyzed by inductively coupled plasma mass spectrometry (ICPMS) and (scanning-) transmission electron microscopy ((S)TEM). Aerosols were generated by using the original vessels, and analyzed by scanning mobility particle sizer (SMPS) and (S)TEM. On the basis of SMPS results, the nanosized aerosol depositing in the respiratory tract was modeled for female and male consumers. The derived exposure levels reflect a single spray application. We identified ENP in the dispersions of two products (shoe impregnation and plant spray). Nanosized aerosols were observed in three products that contained propellant gas. The aerosol number concentration increased linearly with the sprayed amount, with the highest concentration resulting from the antiperspirant. Modeled aerosol exposure levels were in the range of 10¹⁰ nanosized aerosol components per person and application event for the antiperspirant and the impregnation sprays, with the largest fraction of nanosized aerosol depositing in the alveolar region. Negligible exposure from the application of the plant spray (pump spray) was observed.     

Numbers,scale and symbols: the public understanding of nanotechnology

Nanotechnology will be an increasing part of the everyday lives of most people in the world. There is a general recognition that few people understand the implications of the technology, the technology itself or even the definition of the word. This lack of understanding stems from a lack of knowledge about science in general but more specifically difficulty in grasping the size scale and symbolism of nanotechnology. A potential key to informing the general public is establishing the ability to comprehend the scale of nanotechnology. Transitioning from the macro to the nanoscale seems to require an ability to comprehend scales of one-billion. Scaling is a skill not common in most individuals and tests of their ability to extrapolate size based upon scaling a common object demonstrates that most individuals cannot scale to the extent needed to make the transition to nanoscale. Symbolism is another important vehicle to providing the general public with a basis to understand the concepts of nanotechnology. With increasing age, individuals are able to draw representations of atomic scale objects, but these tend to be iconic and the different representations not easily translated. Ball and stick models are most recognized by the public, which provides an opportunity to present not only useful symbolism but also a reference point for the atomic scale.     

Glycosylation sites of hemocyanins of Helix pomatia and Sepia officinalis

Glycopeptides were isolated from functional units of two molluscan hemocyanins (Hcs). They were analyzed and localized in the sequences. A comparison with potential N-glycosylation sites of two other molluscan Hcs was made. An immunological cross-reactivity was observed between the beta-Hc and the alpha-macroglobulin of Helix pomotia. ELISA experiments with glycopeptide fractions indicated a competition.     

Preparation and characterization of titania based nanowires

A new method for preparation of titania nanowires with diameter around 10 nm and length up to 2–3 μm is described. The precursor was prepared from sodium titanate by adding ethylene glycole (EG) and heating at temperature of 198°C for 6 h under reflux. The sodium titanate glycolate formed by this way aggregated into 1D nanostructures and was subsequently transformed into titania glycolate during a chemical treatment with 98% sulfuric acid. Titania nanowires with variable amount of anatase and rutile were prepared by heating to temperatures in the range 350–1000°C. The precursor as well as titania based samples were characterized by X-ray diffraction, Infrared spectroscopy, Scanning electron microscopy, High resolution transmission microscopy, Thermogravimetry, Differential thermal analysis, Evolved gas analysis and Emanation thermal analysis. The nitrogen adsorption/desorption was used for surface area and porosity determination. The photoactivity of the prepared titania samples was assessed by the photocatalytic decomposition of 4-chlorophenol in an aqueous slurry under UV irradiation of 365 nm wavelength.     

A primer of substitution tilings of the Euclidean plane

This paper is intended to provide an introduction to the theory of substitution tilings. For our purposes, tiling substitution rules are divided into two broad classes: geometric and combinatorial. Geometric substitution tilings include self-similar tilings such as the well-known Penrose tilings; for this class there is a substantial body of research in the literature. Combinatorial substitutions are just beginning to be examined, and some of what we present here is new. We give numerous examples, mention selected major results, discuss connections between the two classes of substitutions, include current research perspectives and questions, and provide an extensive bibliography. Although the author attempts to represent the field as a whole, the paper is not an exhaustive survey, and she apologizes for any important omissions.