Oligodeoxyfluorosides: Strong Sequence Dependence of Fluorescence Emission

We describe the properties of a series of oligomeric polyfluorophores assembled on the DNA backbone. The 11 oligomers (oligodeoxyfluorosides, ODFs), 4-7 monomers in length, were composed of only two fluorescent monomers and a spacer in varied sequences, and were designed to test how fluorescent nucleobases can interact electronically to yield complexity in fluorescence emission. The monomer fluorophores were deoxyribosides of pyrene and perylene, which emit light in violet and blue wavelengths, respectively. The experiments show that simple variation in sequence and spacing can dramatically change fluorescence, yielding emission maxima ranging from 380 to 557 nm and visible colors from violet to orange-red. Fluorescence lifetime data, excitation spectra, and absorption data point to a number of multi-fluorophore electronic interactions, including pyrene-pyrene and perylene-perylene excimers, pyrene-perylene exciplexes, as well as monomer dye emissions, contributing to the final spectral outcomes. Thus, two simple fluorophores can be readily combined to give emissions over much of the visible spectrum, all requiring only a single excitation. The results demonstrate that fluorescent nucleobases in oligomeric form can act cooperatively as electronic units, and that fluorophore sequence in such oligomers is as important as fluorophore composition in determining fluorescence properties.     

Importance of REP values when comparing the CALUX bioassay results with chemoanalyses results Example with spiked vegetable oils

Differences between chemical activated luciferase gene expression (CALUX) bioassay and chemoanalyses results are observed.This paper shows that calculations of the TEQ values using REP values instead of WHO TEF values give different results. The REP values do affect the results obtained by the CALUX technique. These differences are more marked for the dioxin like PCB compounds (CALUX TEQ values are lower than WHO TEQ values) than for the dioxin compounds (CALUX TEQ values are higher than WHO TEQ values).The CALUX results were compared with the concentrations of the congeners’ spiked into the oil.     

Use of NIRS technology with a remote reflectance fibre-optic probe for predicting major components in bee pollen

In the present work, we study the use of near infra-red spectroscopy (NIRS) technology together with a remote reflectance fibre-optic probe for determination of the major components in bee pollen. The method allows immediate control of the bee pollen without prior sample treatment or destruction through direct application of the fibre-optic probe to the sample.The regression method employed was modified partial least squares (MPLS). The calibration results obtained using 45 samples of bee pollen allowed the measurement of protein, moisture, ash, reducing sugars, and pH with multiple correlation coefficients (RSQ) and prediction corrected standard errors (SEPC) of 0.91, 0.56% for protein, of 0.78 and 0.49% for moisture; 0.92 and 0.049% for ash; 0.81 and 1.32 g of glucose/100 g of bee pollen; 0.84 and 0.15 for pH, respectively.The prediction capacity of the pattern was checked by applying it to samples of unknown pollen in external validation.     

Calculation of vertical ionization potentials of difluoramine by perturbation corrections to koopmans' theorem

The vertical ionization potentials of difluoramine are calculated by perturbation corrections to Koopmans' theorem. The calculation shows that difluoraimine has three overlapping bands between 15 and 16 eV. The calculated results compare well with the experimental values. The photoelectron spectrum of difluoramine is compared with that of OF₂ and CH₂F₂.     

103Rh-NMR-spektroskopischer Nachweis der gemischten Nonahalogenodirhodate(III), [Rh2ClnBr9–n]3−, n = 0–9

¹⁰³Rh NMR Spectroscopic Evidence of Mixed Nonahalogenodirhodates(III), [Rh₂Cl_nBr_9–n]^3?, n = 0–9 On heating a mixture of the tetrabutylammonium salts (TBA)₃[Rh₂Cl₉] and (TBA)₃[Rh₂Br₉] at 60°C in propylenecarbonate the complete system of the mixed nonahalogenodirhodates(III) [Rh₂Cl_nBr_9–n]^3?, n = 0–9 is formed. In the ¹⁰³Rh nmr spectra 40 different species have been detected, 16 with two equivalent ¹⁰³Rh atoms each resulting in one singlet and 24 with inequivalent ¹⁰³Rh atoms each pair giving two resonances. The signals of the geometric isomeres are not resolved. All 64 expected resonances are really observed. By additional measuring of the ¹⁰³Rh nmr spectra of the fractions n = 0–4 separable by ion exchange chromatography on DEAE cellulose, and utilizing characteristic increments of chemical shifts the complete and unambiguous assignment of all signals is achieved.     

Cellulose microfibrils from banana farming residues: isolation and characterization

Cellulose microfibrils have been prepared from banana rachis using a combination of chemical and mechanical treatments. The morphology and structure of the samples were characterized using transmission electron microscopy, atomic force microscopy, and X-ray diffraction. Fourier-transformed infrared spectroscopy (FTIR) was used to characterize the chemical modifications of the samples after each treatment. Suspensions of bundled or individualized 5-nm-wide microfibrils were obtained after homogenization (PH) whereas an organosolv (PO) treatment resulted in shorter aggregates of parallel cellulose microcrystallites. The sharper rings in the X-ray diffraction pattern of the PO-treated sample suggest a higher crystallinity due to a more efficient removal of hemicelluloses and dissolution of amorphous zones by the acid treatment. Both microfibrils and microcrystals prepared by both methods can be used as reinforcing filler in nanocomposite materials.     

Combined application of 2D NMR correlation methods and ab initio chemical shift calculations to the structure determination of new heterocyclic compounds

The combined use of 2D NMR correlation methods and ab initio chemical shift calculations is efficient and, in some cases, virtually the only way to determine the structures of new organic compounds. This approach enabled us to establish the structure of the major unusual product of the three-component reaction of imidazo[1,5-a]quinoxalin-4-one, bis(2-chloroethyl)amine hydrochloride, and potassium carbonate in DMF. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2172–2179, December, 2006. Dedicated to Professor A. V. Il’yasov on the occasion of his 70th birthday.     

低温反应制备高纯度纳米BN包覆Al2O3和ZrO2粉体

硼酸和尿素在氮气中于650℃反应,生成t-BN-Al2O3和t-BN-ZrO2纳米包覆粉.IR分析表明,反应产物中含CH2和CN基团的杂质属尿素缩聚的复杂产物,经450℃煅烧即可除去.硼酸和尿素完全反应,得到纯净的纳米复合粉体.BN产率大于99%,在复合粉中的含量与计算值吻合.     

Chemical and thermal analysis of the biopolymers in thyme (Thymus vulgaris)

Thyme (Thymus vulgaris) has been known, long time ago, for its aromatic properties. It contains essential oils and polymers such as cellulose (mixture of hemicellulose and cellulose) and lignin. The thyme, studied in this work, was gathered from the same place, in the period from November 1999 to October 2000. The chemical analysis (water, total ash, essential oils, extractive substances, cellulose, holocellulose and lignin) can be used roughly in the characterisation of the four periods that correspond to the four seasons of the year. The cellulose level was found to be more than lignin level in the wet periods (growth of the plant). The opposite was found in the dry periods. The total ash and essential oil levels were found to be high during the period of high pluviometry. The thermal decomposition of cellulose and holocellulose was found to fit well with the first-order kinetics. The activation energy, under air flow, was 185 and 196 kJ mol⁻¹ for cellulose and holocellulose, respectively. The maximum decomposition rate and thermal analysis heating rate of lignin were found to have a direct linear relationship.     

Strategies for measurements of pseudocontact shifts in protein NMR spectroscopy.

Paramagnetic metal ions bound to proteins generate a dipolar field that can be accurately probed by pseudocontact shifts (PCS) displayed by the protein's nuclear spins. PCS are highly useful for determining the coordinates of individual spins in the molecule and for rapid structure determinations of entire protein-protein and protein-ligand complexes. However, PCS measurements require reliable resonance assignments for the molecule in its paramagnetic state and in a diamagnetic reference state. This article discusses different approaches for pairwise resonance assignments, with emphasis on a strategy which exploits chemical exchange between the two states.