Simplified method for microlitre deuterium measurements in water and urine by gas chromatography-high-temperature conversion-isotope ratio mass spectrometry

Deuterium (2H) in water and urine can be measured by off-line and, more recently, on-line techniques using isotope ratio mass spectrometry (IRMS). We describe a new simple on-line pyrolysis method for the analysis of 2H/1H in water and urine samples by continuous flow IRMS, normally used for 2H/1H measurements in organic compounds. A deactivated column connected the split injector to a high-temperature conversion reactor (TC HD), and 0.5 microL of sample was injected. Accuracy and precision were determined with Vienna Standard Mean Ocean Water (VSMOW), Standard Light Antarctic Precipitation (SLAP), and Greenland Ice Sheet Precipitation (GISP). The range of linearity was measured with a calibration curve of enriched water from 0 up to 0.1 atom percent excess (APE) (i.e. -72 up to 6323 delta per mil (deltaD per thousand)) with a precision of <5 per thousand and accuracy ranging between 1 and 55 per thousand. Blinded reanalysis of urine samples by an equilibration device (Gas Bench) and by a dedicated pyrolysis system (TC/EA) was performed and results compared by the Bland-Altman test. Enrichments ranged between 600 and 2400 per thousand deltaD(VSMOW) with a precision of +/-5 per thousand. Urine enrichments described by our method were strongly correlated with values obtained by Gas Bench and TC/EA (p < 0.0001). There was a significant memory effect that was reduced by injecting the sample 15 times and discarding the first 10 injections, together with accurate furnace conditioning and appropriate cleaning of the syringe. Data indicate that the method is accurate, and that it can be used for water and urine deuterium determination when a Gas Bench or TC/EA instrument is not available and the amount of sample is limited.     

Peptide Bond Formation in the Protonated Serine Dimer Following Vacuum UV Photon-Induced Excitation

Possible routes for intra-cluster bond formation (ICBF) in protonated serine dimers have been studied. We found no evidence of ICBF following low energy collision-induced dissociation (in correspondence with previous works), however, we do observe clear evidence for ICBF following photon absorption in the 4.6–14 eV range. Moreover, the comparison of photon-induced dissociation measurements of the protonated serine dimer to those of a protonated serine dipeptide provides evidence that ICBF, in this case, involves peptide bond formation (PBF). The experimental results are supported by ab initio molecular dynamics and exploration of several excited state potential energy surfaces, unraveling a pathway for PBF following photon absorption. The combination of experiments and theory provides insight into the PBF mechanisms in clusters of amino acids, and reveals the importance of electronic excited states reached upon UV/VUV light excitation.     

Semiconductor laser with extended cavity and intracavity atomic filter

We report on peculiar dynamic features of laser oscillation in a cavity with a semiconductor junction as the gain medium and an intracavity atomic absorber. The output face of the semiconductor is antireflection coated, and lasing action is achieved by using a diffraction grating to close the laser cavity. The spectral analysis of the laser emission evidences a stable emission with narrow linewidth when the oscillating frequency is resonant with the atomic absorber. We also observe frequency bistability and instability. The change between these regimes is controlled through the bias current in a very reproducible way.     

Electrolytic preparation of nanosized Cu/Ni-Cu multilayered coatings

The electrolytic deposition of nanosized Cu/Ni-Cu multilayer coatings on a paraffin-impregnated graphite substrate was performed from an electrolyte consisting of sulphate salts of the above metals and a complex-forming agent, sodium citrate. The multilayer Cu/Ni-Cu coatings were prepared using the potentiostatic method, in which the potential was alternately pulsed between the reduction potentials of the components. Suitable deposition potentials were selected from the polarisation curves. The presence of the thin films was confirmed by atomic absorption spectroscopy (after dissolution) and by optical microscopy. The resulting images show a layered structure of Cu/Ni-Cu coatings formed by Cu, Ni and/or Ni-Cu layers.     

Extent and mechanism of metal ion incorporation into precipitated ferrites

The ability of many noniron metals to be incorporated into the structure of ferrites is being utilized in numerous industrial and environmental applications. The incorporation of some of these metals during Fe(II) oxidation-induced precipitation at moderate temperatures (80-100°C) appears to be limited, for reasons not fully understood, and to extents not always agreed (e.g., Ni(2+), Cr(3+)). In this paper, the incorporation maxima of six metals into the structure of precipitated ferrites (in terms of x in Me(x)Fe(3-)(x)O(4), Me represents a noniron metal) were concluded to be 1.0, 1.0, 0.78, 0.49, 0.35, and 0.0 for Zn(2+), Co(2+), Ni(2+), Al(3+), Cd(2+) and Cr(3+), respectively. With the exception of the much larger Cd(2+), these values were associated with kinetic considerations controlled by the H(2)O exchange rate between the hydration shells surrounding the dissolved metal ion.     

Poisson thickening

Let × be a Poisson point process of intensity λ on the real line. A thickening of it is a (deterministic) measurable function f such that X∪f(X) is a Poisson point process of intensity λ′ where λ′ > λ. An equivariant thickening is a thickening which commutes with all shifts of the line. We show that a thickening exists but an equivariant thickening does not. We prove similar results for thickenings which commute only with integer shifts and in the discrete and multi-dimensional settings. This answers 3 questions of Holroyd, Lyons and Soo. We briefly consider also a much more general setup in which we ask for the existence of a deterministic coupling satisfying a relation between two probability measures. We present a conjectured sufficient condition for the existence of such couplings.     

Reactivity of long conjugated systems: selectivity of Diels-Alder cycloaddition in oligofurans

Taking advantage of the synthetic availability and solubility of long oligofurans, their reactivity toward dienophiles was studied as a model for the rarely investigated reactivity of long conjugated systems. Unlike oligoacenes, the reactivity of oligofurans decreases or remains constant with increasing chain length. Terminal ring cycloadducts of oligofurans are kinetically and thermodynamically favored, whereas central ring cycloadducts are preferred in oligoacenes, because of the different driving forces in the two reactions: π-conjugation in oligofurans and aromatization/dearomatization in oligoacenes.     

Continuity of the value and optimal strategies when common priors change

We show that the value of a zero-sum Bayesian game is a Lipschitz continuous function of the players?? common prior belief with respect to the total variation metric on beliefs. This is unlike the case of general Bayesian games where lower semi-continuity of Bayesian equilibrium (BE) payoffs rests on the ??almost uniform?? convergence of conditional beliefs. We also show upper semi-continuity (USC) and approximate lower semi-continuity (ALSC) of the optimal strategy correspondence, and discuss ALSC of the BE correspondence in the context of zero-sum games. In particular, the interim BE correspondence is shown to be ALSC for some classes of information structures with highly non-uniform convergence of beliefs, that would not give rise to ALSC of BE in non-zero-sum games.     

Ultrasensitive Detection of Salmonella and Listeria monocytogenes by Small‐Molecule Chemiluminescence Probes

Detection of Salmonella and L. monocytogenes in food samples by current diagnostic methods requires relatively long time to results (2–6 days). Furthermore, the ability to perform environmental monitoring at the factory site for these pathogens is limited due to the need for laboratory facilities. Herein, we report new chemiluminescence probes for the ultrasensitive direct detection of viable pathogenic bacteria. The probes are composed of a bright phenoxy‐dioxetane luminophore masked by triggering group, which is activated by a specific bacterial enzyme, and could detect their corresponding bacteria with an LOD value of about 600‐fold lower than that of fluorescent probes. Moreover, we were able to detect a minimum of 10 Salmonella cells within 6 h incubation. The assay allows for bacterial enrichment and detection in one test tube without further sample preparation. We anticipate that this design strategy will be used to prepare analogous chemiluminescence probes for other enzymes relevant to specific bacteria detection and point‐of‐care diagnostics.     

Beyond Equal-Power Sparse NOMA: Two User Classes and Closed-Form Bounds on the Achievable Region

Non-orthogonal multiple access (NOMA) is a promising technology for future beyond-5G wireless networks, whose fundamental information-theoretic limits are yet to be fully explored. Considering regular sparse code-domain NOMA (with a fixed and finite number of orthogonal resources allocated to any designated user and vice versa), this paper extends previous results by the authors to a setting comprising two classes of users with different power constraints. Explicit rigorous closed-form analytical inner and outer bounds on the achievable rate (total class throughput) region in the large-system limit are derived and comparatively investigated in extreme-SNR regimes. The inner bound is based on the conditional vector entropy power inequality (EPI), while the outer bound relies on a recent strengthened version of the EPI. Valuable insights are provided into the potential performance gains of regular sparse NOMA in practically oriented settings, comprising, e.g., a combination of low-complexity devices and broadband users with higher transmit power capabilities, or combinations of cell-edge and cell-center users. The conditions for superior performance over dense code-domain NOMA (taking the form of randomly spread code-division multiple access), as well as a relatively small gap to the ultimate performance limits, are identified. The proposed bounds are also applicable for the analysis of interference networks, e.g., Wyner-type cellular models.