Boronate Ligands in Materials: Determining Their Local Environment by Using a Combination of IR/Solid‐State NMR Spectroscopies and DFT Calculations

Boronic acids (R‐B(OH)₂) are a family of molecules that have found a large number of applications in materials science. In contrast, boronate anions (R‐B(OH)₃^?) have hardly been used so far for the preparation of novel materials. Here, a new crystalline phase involving a boronate ligand is described, Ca[C₄H₉‐B(OH)₃]₂, which is then used as a basis for the establishment of the spectroscopic signatures of boronates in the solid state. The phase was characterized by IR and multinuclear solid‐state NMR spectroscopy (¹H, ¹³C, ¹¹B and ⁴³Ca), and then modeled by periodic DFT calculations. Anharmonic OH vibration frequencies were calculated as well as NMR parameters (by using the Gauge Including Projector Augmented Wave—GIPAW—method). These data allow relationships between the geometry around the OH groups in boronates and the IR and ¹H NMR spectroscopic data to be established, which will be key to the future interpretation of the spectra of more complex organic–inorganic materials containing boronate building blocks.     

Photophysics of monodisperse platinum-acetylide oligomers: delocalization in the singlet and triplet excited states

A series of monodisperse Pt-acetylide polymers that contain the [-CC-(p-C6H4)-CC-(t-Pt(PBu3)2)-]n repeat unit has been prepared for n = 1, 2, 3, 4, 5, and 7. The photophysical properties of the series provide information concerning the relationship between the oligomer length and delocalization in the singlet and triplet excited states of the pi-conjugated electron system. The results imply that the singlet excited state is delocalized over approximately 6 repeat units; however, the triplet state is considerably more localized. The triplet energy is almost invariant with oligomer length, but the phosphorescence spectra and triplet nonradiative decay rates indicate that the electron-vibrational coupling in the triplet state decreases with increasing oligomer length.     

Gas-phase halonium metathesis and its competitors. Skeletal rearrangements of cationic adducts of saturated ketones

The methyl cation and CF(3)(+) attack saturated, acyclic ketones to make vibrationally excited adduct ions. Despite their high internal energies and short lifetimes, these adducts undergo deep-seated rearrangements that parallel slower processes in solution. Observed pathways include alkene and alkane expulsions, in addition to (in the case of CF(3)(+)) the precedented loss of CF(2)O + HF. For the vast majority of ketones, the principal charged products are the CF(3)(+) adducts of lighter carbonyl compounds, ions that are not easily prepared by other avenues. Evidence for ion structures comes from collisionally activated unimolecular decomposition and bimolecular ion-molecule reactions. Typical examples are di-n-propyl and diisopropyl ketones (both of which produce CH(3)CH=OCF(3)(+) as the principal ion-molecule reaction product) and pentamethylacetone (which produces (CH(3))(2)C=OCF(3)(+) as virtually the sole ion-molecule reaction product). Isotopic labeling experiments account for mechanisms, and DFT calculations provide a qualitative explanation for the relative abundances of products from unimolecular decompositions of the chemically activated CF(3)(+) adduct ions that are initially formed.     

A novel four-component reaction for the synthesis of functionalised dihydropyrimidines

In a multi-component reaction (MCR) of a phosphonate, nitriles, aldehydes and isocyanates, N3-functionalised dihydropyrimidines can be synthesised efficiently via a Horner-Emmons/aza Diels-Alder pathway.     

Optimal Production of a <Emphasis Type="Italic">Rhodococcus erythropolis</Emphasis> ATCC 4277 Biocatalyst for Biodesulfurization and Biodenitrogenation Applications

Rhodococcus sp. has a broad catabolic diversity and unique enzymatic capabilities, and it is able to adapt under extreme conditions. Thereby, the production of this remarkable bacterium has a great biotechnological and industrial importance. In this sense, we sought to improve the R. erythropolis ATCC 4277 growth through a central composite design, by varying the components of nutrient medium (glucose, malt extract, yeast extract, CaCO₃), temperature, and agitation. It was found that the concentrations of glucose and malt extract are not statistically significant, being reduced of 4.0 and 10.0 g L^-1 to 2.0 and 5.0 g L^?1, respectively. The CaCO₃ concentration and temperature were also diminished of 2.0 to 1.16 g L^?1and 28 to 23.7 °C, respectively. Optimal growth conditions provided a 240% increase in final biomass concentration, an increment in specific growth rate, and a growth yield coefficient about five times greater. Application of the optimal conditions in biodesulfurization and biodenitrogenation processes showed that desulfurization capability is not associated with optimal growth conditions; however, it was achieved a 47% of nitrogen removal in the assay containing 10% (w/w) of heavy gas oil.

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Use of combined mass spectrometry methods for the characterization of a new variant of human hemoglobin: The double mutant hemoglobin villeparisis β77(EF1) His → Tyr, β 80 (EF4) Asn → Ser

Hemoglobin Villeparisis was found during a systematic measurement of glycated hemoglobin. Electrospray mass spectra of the globin indicate an apparently unchanged molecular weight within the error range (0.01%). The tryptic digest of the β chain shows a chromatographically abnormal βT-9 peptide. The mass-to-charge ratio value of its [M+H]⁺ ion, as measured by liquid secondary ionization mass spectrometry, is one mass unit lower than that of the normal βT-9. However, the electrospray mass spectrum of this peptide exhibits mainly a doubly charged ion, whereas the normal βT-9 gives a triply charged ion. None of the allowed single amino acid substitutions for a 1-u shift down (Glu → Gln, Asp → Asn, or Asn → Ile) can explain the suppression of one protonation site. This can be due only to the replacement of the internal histidine by a nonbasic residue. Thus at least two amino acid exchanges occur within the same peptide: one involves the internal histidine, and the sum of the mass shifts is ?1 u. Consideration of the βT-9 sequence and taking account for the genetic code rules, the only possibility was ¹¹His → Tyr (+26 mass shift) associated with ¹⁴Asn → Ser (?27 mass shift). This conclusion was consistent with the tandem mass spectrum of the [M+H]⁺ ion and was further confirmed by chemical microsequencing.     

Multipronged Biomimetic Approach To Create Optically Tunable Nanoparticles

Current biomimetics for medical applications use a single biomimetic approach to imitate natural structures, which can be insufficient for reconstructing structurally complex natural systems. Multipronged efforts may resolve these complexities. To achieve interesting nanostructure‐driven optical properties, a dual‐biomimetic system contained within a single nanoagent was engineered to recapitulate chlorosomes, efficient light‐harvesting organelles that have unique dye assemblies and tunable photonic properties. A series of chlorin dyes was synthesized, and these hydrophobic assemblies were stabilized inside a high‐density lipoprotein, a second biomimetic that enabled in vivo utility. This system resulted in tunable tumor imaging of intact (photoacoustic) and disrupted (activatable fluorescence) nanostructures. The successful demonstration of this multipronged biomimetic approach opens the door for reconstruction of complex natural systems for biomedical applications.     

Cloning of the Orange Light‐Producing Luciferase from Photinus scintillans—A New Proposal on how Bioluminescence Color is Determined

Unlike the enchanting yellow‐green flashes of light produced on warm summer evenings by Photinus pyralis, the most common firefly species in North America, the orange lights of Photinus scintillans are infrequently observed. These Photinus species, and likely all bioluminescent beetles, use the same substrates beetle luciferin, ATP and oxygen to produce light. It is the structure of the particular luciferase enzyme that is the key to determining the color of the emitted light. We report here the molecular cloning of the P. scintillans luc gene and the expression and characterization of the corresponding novel recombinant luciferase enzyme. A comparison of the amino acid sequence with that of the highly similar P. pyralis enzyme and subsequent mutagenesis studies revealed that the single conservative amino acid change tyrosine to phenylalanine at position 255 accounted for the entire emission color difference. Additional mutagenesis and crystallographic studies were performed on a H‐bond network, which includes the position 255 residue and five other stringently conserved beetle luciferase residues, that is proximal to the substrate/emitter binding site. The results are interpreted in the context of a speculative proposal that this network is key to the understanding of bioluminescence color determination.     

Finite sphere packing and sphere covering

A basic problem of finite packing and covering is to determine, for a given number ofk unit balls in Euclideand-spaceE ^d , (1) the minimal volume of all convex bodies into which thek balls can be packed and (2) the maximal volume of all convex bodies which can be covered by thek balls. In the sausage conjectures by L. Fejes Tóth and J. M. Wills it is conjectured that, for alld5, linear arrangements of thek balls are best possible. In the paper several partial results are given to support both conjectures. Furthermore, some relations between finite and infinite (space) packing and covering are investigated.This paper was written while the first named author was visiting the Forschungsinstitut für Geistes- und Sozialwissenschaften at the University of Siegen.