Symmetry versus Minimal Pentagonal Adjacencies in Uranium‐Based Polyoxometalate Fullerene Topologies

C U soon : Clusters containing 60, 44, and 36 uranyl peroxide hydroxide polyhedra (see picture) adopt fullerene topologies of maximum symmetry. The largest of these, denoted U60, is topologically identical to C₆₀ with no pentagonal adjacencies and the highest possible symmetry. U44 adopts the topology with maximum symmetry rather than that with the lowest number of pentagonal adjacencies.

     

Electron transfer and singlet oxygen mechanisms in the photooxygenation of dibutyl sulfide and thioanisole in MeCN sensitized by N-methylquinolinium tetrafluoborate and 9,10-dicyanoanthracene. The probable involvement of a thiadioxirane intermediate in electron transfer photooxygenations

Photooxygenations of PhSMe and Bu2S sensitized by N-methylquinolinium (NMQ+) and 9,10-dicyanoanthracene (DCA) in O2-saturated MeCN have been investigated by laser and steady-state photolysis. Laser photolysis experiments showed that excited NMQ+ promotes the efficient formation of sulfide radical cations with both substrates either in the presence or in absence of a cosensitizer (toluene). In contrast, excited DCA promotes the formation of radical ions with PhSMe, but not with Bu2S. To observe radical ions with the latter substrate, the presence of a cosensitizer (biphenyl) was necessary. With Bu2S, only the dimeric form of the radical cation, (Bu2S)2+*, was observed, while the absorptions of both PhSMe+* and (PhSMe)2+* were present in the PhSMe time-resolved spectra. The decay of the radical cations followed second-order kinetics, which in the presence of O2, was attributed to the reaction of the radical cation (presumably in the monomeric form) with O2-* generated in the reaction between NMQ* or DCA-* and O2. The fluorescence quenching of both NMQ+ and DCA was also investigated, and it was found that the fluorescence of the two sensitizers is efficiently quenched by both sulfides (rates controlled by diffusion) as well by O2 (kq = 5.9 x 10(9) M(-1) s(-1) with NMQ+ and 6.8 x 10(9) M(-1) s(-1) with DCA). It was also found that quenching of 1NMQ* by O2 led to the production of 1O2 in significant yield (PhiDelta = 0.86 in O2-saturated solutions) as already observed for 1DCA*. The steady-state photolysis experiments showed that the NMQ+- and DCA-sensitized photooxygenation of PhSMe afford exclusively the corresponding sulfoxide. A different situation holds for Bu2S: with NMQ+, the formation of Bu2SO was accompanied by that of small amounts of Bu2S2; with DCA, the formation of Bu2SO2 was also observed. It was conclusively shown that with both sensitizers, the photooxygenations of PhSMe occur by an electron transfer (ET) mechanism, as no sulfoxidation was observed in the presence of benzoquinone (BQ), which is a trap for O2-*, NMQ*, and DCA-*. BQ also suppressed the NMQ+-sensitized photooxygenation of Bu2S, but not that sensitized by DCA, indicating that the former is an ET process, whereas the second proceeds via singlet oxygen. In agreement with the latter conclusion, it was also found that the relative rate of the DCA-induced photooxygenation of Bu2S decreases by increasing the initial concentration of the substrate and is slowed by DABCO (an efficient singlet oxygen quencher). To shed light on the actual role of a persulfoxide intermediate also in ET photooxygenations, experiments in the presence of Ph2SO (a trap for the persulfoxide) were carried out. Cooxidation of Ph2SO to form Ph2SO2 was, however, observed only in the DCA-induced photooxygenation of Bu2S, in line with the singlet oxygen mechanism suggested for this reaction. No detectable amounts of Ph2SO2 were formed in the ET photooxygenations of PhSMe with both DCA and NMQ+ and of Bu2S with NMQ+. This finding, coupled with the observation that 1O2 and ET photooxygenations lead to different product distributions, makes it unlikely that, as currently believed, the two processes involve the same intermediate, i.e., a nucleophilic persulfoxide. Furthermore, the cooxidation of Ph2SO observed in the DCA-induced photooxygenation of Bu2S was drastically reduced when the reaction was performed in the presence of 0.5 M biphenyl as a cosensitizer, that is, under conditions where an (indirect) ET mechanism should operate. This observation confirms that a persulfoxide is formed in singlet oxygen but not in ET photosulfoxidations. The latter conclusion was further supported by the observation that also the intermediate formed in the reaction of thianthrene radical cation with KO2, a reaction which mimics step d (Scheme 2) in the ET mechanism of photooxygenation, is an electrophilic species, being able to oxidize Ph2S but not Ph2SO. It is thus proposed that the intermediate involved in ET sulfoxidations is a thiadioxirane, whose properties (it is an electrophilic species) seem more in line with the observed chemistry. Theoretical calculations concerning the reaction of a sulfide radical cation with O2-* provide a rationale for this proposal.     

Probing bacterial interactions: integrated approaches combining atomic force microscopy, electron microscopy and biophysical techniques

Recent developments in the application of Atomic Force Microscopy (AFM) and other biophysical techniques for the study of bacterial interactions and adhesion are discussed in the light of established biological and microscopic approaches. Whereas molecular-biological techniques combined with electron microscopy allow the identification and localization of surface constituents mediating bacterial interactions, with AFM it has become possible to actually measure the forces involved in bacterial interactions. Combined with the flexibility of AFM in probing various types of physical interactions, such as electrostatic interactions, specific ligand-receptor interactions and the elastic forces of deformation and extension of bacterial surface polymers and cell wall, this provides prospects for the elucidation of the biophysical mechanism of bacterial interaction. However, because of the biochemical and a biophysical complexity of the bacterial cell wall, integrated approaches combining AFM with electron microscopy and biophysical techniques are needed to elucidate the mechanism by which a bacterium interacts with a host or material surface. The literature on electron microscopy of the bacterial cell wall is reviewed, with particular emphasis on the staining of specific classes of cell-wall constituents. The application of AFM in the analysis of bacterial surfaces is discussed, including AFM operating modes, sample preparation methods and results obtained on various strains. For various bacterial strains, the integration of EM and AFM data is discussed. Various biophysical aspects of the analysis of bacterial surface structure and interactions are discussed, including the theory of colloidal interactions and Bell's theory of cell-to-cell adhesion. An overview is given of biophysical techniques used in the analysis of the properties of bacterial surfaces and bacterial surface constituents and their integration with AFM. Finally, we discuss recent progress in the understanding of the role of bacterial interactions in medicine within the framework of the techniques and concepts discussed in the paper.     

Multiecho multimoment refocussing of motion in magnetic resonance imaging: MEM-MO-RE

Gradient moment nulling techniques for refocussing of spin dephasing resulting from movement during application of magnetic resonance imaging gradients have gained widespread application. These techniques offer advantages over conventional imaging gradients by reducing motion artifacts due to intraview motion, and by recovering signal lost from spin dephasing. This paper presents a simple technique for designing multiecho imaging gradient waveforms that refocus dephasing from the interaction of imaging gradients and multiple derivatives of position. Multiple moments will be compensated at each echo. The method described relies on the fact that the calculation of time moments for nulled moment gradient waveforms is independent of the time origin chosen. Therefore, waveforms used to generate the second echo image for multiple echo sequences with echo times given by TEn = TE1 + (n - 1) * (TE2 - TE1) may also be used for generation of the third and additional echo images. All echoes will refocus the same derivatives of position. Multiecho, multimoment refocussing (MEM-MO-RE) images through the liver in a patient with ampullary adenocarcinoma metastatic to the liver demonstrate the application of the method in clinical scanning.     

Comprehensive determination of trace elements in human saliva by ETA-AAS

A method is described for the comprehensive determination of a series of trace and ultratrace elements (Fe, Mn, Zn, Cu, Sr, Cr, Al and Si) in human saliva by atomic absorption spectrometry with electrothermal atomization and Zeeman-effect background correction. Procedures for sampling of total mixed saliva and its treatment including centrifugation and mineralization by HNO₃ are described in detail. To avoid the use of matrix modifiers, element standards with an artificial saliva matrix were used to construct calibration curves. Instrumental precision, tested by repeated analyses of natural salivas, is good (error less than 5%) for most elements. Lower precision was obtained for elements like Al and Si present in concentrations close to the detection limit. The analysis of some natural salivas clearly shows the influence of the sampling and treatment procedures on the reliability of the data. An accurate standardization of these procedures is thus recommended.     

A multi-method approach for determination of radionuclide distribution in trinitite

The spatial distribution of radiation within trinitite thin sections have been mapped using alpha track radiography and beta autoradiography in combination with optical microscopy and scanning electron microscopy. Alpha and beta maps have identified areas of higher activity, and these are concentrated predominantly within the surficial glassy component of trinitite. Laser ablation-inductively coupled plasma mass spectrometry (LA-ICP-MS) analyses conducted at high spatial resolution yield weighted average ²³⁵U/²³⁸U and ²⁴⁰Pu/²³⁹Pu ratios of 0.00718 ± 0.00018 (2σ) and 0.0208 ± 0.0012 (2σ), respectively, and also reveal the presence of some fission (¹³⁷Cs) and activation products (^152,154Eu). The LA-ICP-MS results indicate positive correlations between Pu ion signal intensities and abundances of Fe, Ca, U and ¹³⁷Cs. These trends suggest that Pu in trinitite is associated with remnants of certain chemical components from the device and surrounding Trinity test-related structures at ground zero. In contrast, negative correlations between Pu ion signals and SiO₂ and K₂O contents were observed within the glassy matrix of trinitite. This LA-ICP-MS result was corroborated by combined back-scattered electron imaging and alpha radiography, and indicates that Pu was not incorporated into unmelted crystalline grains of precursor minerals (i.e., quartz-SiO₂ and K-feldspar-KAlSi₃O₈) present within the desert sand at the Trinity site. The results from this study indicate that the device-related radionuclides were preferentially incorporated into the glassy matrix in trinitite.     

Antifungal activity of Mongolian medicinal plant extracts

Abstract

The in vitro antifungal activity of extracts obtained from 14 medicinal plants of the mongolian flora were investigated by measuring their minimal inhibitory concentration (MIC) against fungi cause of cutaneous diseases such as Candida species, dermatophytes and Malassezia furfur. Among the species examined, Stellaria dichotoma L., Scutellaria scordifolia L. Aquilegia sibirica Fisch. Et Schrenk. and Hyoscyamus niger L. extracts demonstrated antifungal activity against all studied fungi. In particular, S. scordifolia L. methanol extract, obtained at room temperature, showed the best activity against Candida spp., Malassezia furfur and dermatophytes with GMMIC₅₀ values of 22?µg/mL, 64?µg/mL and 32?µg/mL, respectively. The flavones, luteolin and apigenin, identified in S. scordifolia extracts, and rutin identified in S. dichotoma and Hyoscyamus niger L. extracts, could be responsible of the observed antifungal activity.     

Evaluation of flavonoids and furanocoumarins from Citrus bergamia (Bergamot) juice and identification of new compounds

Bergamot juice (BJ) contains different classes of flavonoids (e.g. flavanones and flavones) that can exert beneficial effects on human health. The aim of this study was to evaluate the qualitative and quantitative composition of a BJ obtained from fruits harvested in Southern Italy (Calabria) at the end of their maturation period. The identity of several flavonoids and furanocoumarins was assessed by co-chromatography, UV spectra and molecular weight comparison. The unknown compounds were dissociated by induced collision (CID-MS) and their identity established through the characteristic ions product. By this approach a complete profile of about twenty compounds (furano-coumarins, flavonoids C- and O-glycosides) present in BJ was obtained. Furthermore, three acylated flavanones, present in amounts of 20.1+/-1.1, 89.3+/-2.2 and 190.1+/-3.1 mg/L, respectively, and which seem to correspond to di-oxalate derivatives of neoeriocitrin, naringin and neohesperidin, were identified for the first time in BJ. The other main flavanones were naringin, neohesperidin and neoeriocitrin, and their content was 167.5+/-1.8, 123.9+/-1.7 and 73.3+/-1.6 mg/L, respectively. Concerning flavones, the total amount in BJ was about 160 mg/L and the main ones were vicenin-2, stellarin-2, rhoifolin and neodiosmin. Bergapten and bergamottin were the primary furanocoumarins in BJ and their amounts were 9.0+/-0.4 and 18.2+/-0.5 mg/L, respectively.     

Accurate quantification of steady and pulsatile flow with segmented k-space magnetic resonance velocimetry

Conventional non-segmented magnetic resonance phase velocity mapping (MRPVM) is an accurate but relatively slow velocimetric technique. Therefore, the aim of this study was to evaluate the accuracy of the much faster segmented k-space MRPVM in quantifying flow. The axial velocity was measured in four straight tubes (inner diameter: 5.6-26.2 mm), using a segmented MRPVM sequence with seven lines of k-space per segment. The flow rate and flow volume were accurately quantified (errors<5%) under steady (r²=0.99) and pulsatile flow (r²=0.98), respectively. The measured velocity profiles and flow rates from the segmented sequence agreed with those from the non-segmented (p>0.05). Changing the slice thickness or the field of view did not affect the accuracy of the measurements. The results of this study suggest that fast, segmented MRPVM can be used for accurate flow quantification.