Tetranuclear manganese(II) complexes of thiacalixarene macrocycles with trigonal prismatic six-coordinate geometries: synthesis, structure, and magnetic properties

Two tetranuclear manganese(II) complexes [Mn(II)4(thiaS)2] (1) and [Mn(II)4(thiaSO)2] (2) have been synthesized under solvothermal conditions in methanol with p-tert-butylthiacalix[4]arene (thiaS) and p-tert-butylsulfinylthiacalix[4]arene (thiaSO). For both complexes, the structure has been established from single-crystal X-ray diffraction. [Mn4(thiaS)2].H2O (1) crystallizes in the orthorhombic Immm (No. 71) space group with the following parameters: a = 18.213 (5) angstroms, b = 19.037 (5) angstroms, c = 29.159 (5) angstroms, V = 10110 (4) angstroms3, and Z = 4. [Mn4(thiaSO)2].H2O (2) crystallizes in the monoclinic C2/m (No. 12) space group with the following parameters: a = 33.046(1) angstroms, b = 19.5363 (8) angstroms, c = 15.7773 (9) angstroms, beta = 115.176 (2) degrees, V = 9218.3 (8) angstroms3, and Z = 4. The two complexes are neutral and are best described as manganese squares sandwiched between two thiacalixarene macrocycles. In both complexes, each manganese center is six-coordinated in a trigonal prismatic geometry with four phenoxo oxygen atoms plus two sulfur atoms for 1 or two oxygen atoms from SO groups for 2. The two tetranuclear complexes exhibit identical magnetic behaviors resulting from antiferromagnetic interactions between the four manganese centers. The simulation of the magnetic susceptibility was done considering a single exchange-coupling constant between the manganese(II) ions, J (H = -J(S1S2 + S2S3 + S3S4 + S1S4)). The best fits give the same result for the two complexes: g = 1.94 and J = -5.57 cm(-1).     

A high-pressure mass spectrometric and density functional theory investigation of the thermochemical properties and structure of protonated dimers and trimers of glycine

A new modification of pulsed-ionization high-pressure mass spectrometry (PHPMS) has been used to perform equilibrium thermochemical studies for relatively nonvolatile biomolecules such as amino acids. Binding enthalpy and entropy changes have been measured for proton-bound clusters of glycine, which are in good agreement with both theoretical (DFT) results of this work and a previous blackbody infrared dissociation experiment. Experimental data indicate that a number of conformers of the proton-bound dimer of glycine may coexist in the explored temperature range (360-460 K). Several new, conceptually different isomers (two of them zwitterionic) have been found by DFT calculations, one of which is 7 kJ mol(-1) lower in energy than the structure previously reported to be the energy minimum.     

Cosmic-muon results from the NUSEX experiment

Summary Muon underground data collected in the NUSEX experiment at Mont Blanc have been analysed concerning the following topics: I) vertical muon intensity, II) prompt muon flux, III) muons from the direction of Cygnus X-3. Preliminary results from the analysis of more than 20 000 muons are presented and discussed.

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Riassunto Gli eventi di muoni rivelati sottoterra nell'esperimento NUSEX al Monte Bianco sono stati analizzati per studiare I) l'intensità verticale dei muoni, II) il flusso di muoni pronti, III) l'eccesso di muoni dalla direzione di Cygnus X-3. In questo lavoro sono presentati c discussi i risultati preliminari ottenuti dal'lanalisi di piú di 20.000 eventi.

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Резюме Был проведен анализ данных, собранных в экспеимемнте NUSEX на Мон Блане. Анализировались следующие вопросы: 1) интенсивность вертикальных мюонов, 2) поток мгновенных (быстрых) мюонов, 3) мюоны, движущиеся в направлении от Лебедь X-3. Приводятся и обсуждаются предварительные результаты анализа для более, чем 20 000 муонов.

     

Asymptotically optimal pointwise and minimax quickest change-point detection for dependent data

We consider the quickest change-point detection problem in pointwise and minimax settings for general dependent data models. Two new classes of sequential detection procedures associated with the maximal “local” probability of a false alarm within a period of some fixed length are introduced. For these classes of detection procedures, we consider two popular risks: the expected positive part of the delay to detection and the conditional delay to detection. Under very general conditions for the observations, we show that the popular Shiryaev–Roberts procedure is asymptotically optimal, as the local probability of false alarm goes to zero, with respect to both these risks pointwise (uniformly for every possible point of change) and in the minimax sense (with respect to maximal over point of change expected detection delays). The conditions are formulated in terms of the rate of convergence in the strong law of large numbers for the log-likelihood ratios between the “change” and “no-change” hypotheses, specifically as a uniform complete convergence of the normalized log-likelihood ratio to a positive and finite number. We also develop tools and a set of sufficient conditions for verification of the uniform complete convergence for a large class of Markov processes. These tools are based on concentration inequalities for functions of Markov processes and the Meyn–Tweedie geometric ergodic theory. Finally, we check these sufficient conditions for a number of challenging examples (time series) frequently arising in applications, such as autoregression, autoregressive GARCH, etc.     

Results of the liquid scintillation detector of the Mont Blanc Laboratory

Summary The Liquid Scintillation Detector (LSD experiment) is running since October 1984 in the Mont Blanc Laboratory, with 90 tons of active mass. We discuss here some of the research aims of the experiment, and report the preliminary results on searching for neutrino bursts from collapsing stars and on cosmic-ray muons.

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Riassunto Nell'ottobre 1984 è entrato in misura l'esperimento LSD (Liquid Scintillation Detector) del Laboratorio del Monte Bianco, costituito di 90 tonnellate di rivelatore. In questo lavoro si discutono alcuni degli argomenti di ricerca dell'esperimento e si riportano i risultati preliminari sui burst di neutrini da collassi stellari e sui muoni della radiazione cosmica.

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Резюме Зидкий сцинтилляционный детектор работает с октября 1984 года в лаборатории на Мон Блане. Детектор имеет 90 тонн активной массы. Мы обсуздаем некоторые цели этого эксперимента. Сообщаются предварительные результаты по поиску нейтринных вспышек от коллапсирующих звезд и мюонов в космических лучах.

     

Limit on monopole flux in the Mont Blanc NUSEX experiment

Summary A trigger dedicated to the search of superheavy monopoles operates since about two years in the NUSEX apparatus, installed in the Mont Blanc tunnel. Monopoles are identified by time of flight and visualization of the pulses involved in a trigger. The present upper limit on monopole flux is 2.3·10⁻¹³ cm⁻² s⁻¹ sr⁻¹ (90% c.l.).

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Riassunto Da circa due anni è operativo sull'apparato NUSEX, installato nel tunnel del Monte Bianco, un trigger dedicato alla ricerca dei monopoli previsti dalle teorie di grande unificazione. L'identificazione dei monopoli è basata sul tempo di volo e sulla localizzazione nello spazio degli impulsi coinvolti nel trigger. Il limite superiore fino ad oggi raggiunto per il flusso di monopoli è 2.3·10⁻¹³ cm⁻²s⁻¹ sr⁻¹ (90% c.l.).

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Резюме Триггерная схема, предназначенная для поиска сверхтяжелых монополей, действует в течение почти двух лет в установке NUSEX, расположенной в туннеле под Мон Бланом. Идентификация монополей основана на времени пролета, а локализация в пространстве осуществляется с помощью импульсов в триггерной схеме. Настоящий верхний предел на поток монополей составляет 2.3· ·10⁻¹³ см⁻² с⁻¹ ср⁻¹ (к 90% вероятностью).

     

Unbounded Jacobi Matrices with a Few Gaps in the Essential Spectrum: Constructive Examples

We give explicit examples of unbounded Jacobi operators with a few gaps in their essential spectrum. More precisely a class of Jacobi matrices whose absolutely continuous spectrum fills any finite number of bounded intervals is considered. Their point spectrum accumulates to +?? and ???. The asymptotics of large eigenvalues is also found.     

Fast folding of RNA pseudoknots initiated by laser temperature-jump

RNA pseudoknots are examples of minimal structural motifs in RNA with tertiary interactions that stabilize the structures of many ribozymes. They also play an essential role in a variety of biological functions that are modulated by their structure, stability, and dynamics. Therefore, understanding the global principles that determine the thermodynamics and folding pathways of RNA pseudoknots is an important problem in biology, both for elucidating the folding mechanisms of larger ribozymes as well as addressing issues of possible kinetic control of the biological functions of pseudoknots. We report on the folding/unfolding kinetics of a hairpin-type pseudoknot obtained with microsecond time-resolution in response to a laser temperature-jump perturbation. The kinetics are monitored using UV absorbance as well as fluorescence of extrinsically attached labels as spectroscopic probes of the transiently populated RNA conformations. We measure folding times of 1-6 ms at 37 °C, which are at least 100-fold faster than previous observations of very slow folding pseudoknots that were trapped in misfolded conformations. The measured relaxation times are remarkably similar to predictions of a computational study by Thirumalai and co-workers (Cho, S. S.; Pincus, D.L.; Thirumalai, D. Proc. Natl. Acad. Sci. U. S. A. 2009, 106, 17349-17354). Thus, these studies provide the first observation of a fast-folding pseudoknot and present a benchmark against which computational models can be refined.     

Comparison of Two Bovine Commercial Xenografts in the Regeneration of Critical Cranial Defects

Autologous bone is the gold standard in regeneration processes. However, there is an endless search for alternative materials in bone regeneration. Xenografts can act as bone substitutes given the difficulty of obtaining bone tissue from patients and before the limitations in the availability of homologous tissue donors. Bone neoformation was studied in critical-size defects created in the parietal bone of 40 adult male Wistar rats, implanted with xenografts composed of particulate bovine hydroxyapatite (HA) and with blocks of bovine hydroxyapatite (HA) and Collagen, which introduces crystallinity to the materials. The Fourier-transform infrared spectroscopy (FTIR) analysis demonstrated the carbonate and phosphate groups of the hydroxyapatite and the amide groups of the collagen structure, while the thermal transitions for HA and HA/collagen composites established mainly dehydration endothermal processes, which increased (from 79 °C to 83 °C) for F2 due to the collagen presence. The xenograft’s X-ray powder diffraction (XRD) analysis also revealed the bovine HA crystalline structure, with a prominent peak centered at 32°. We observed macroporosity and mesoporosity in the xenografts from the morphology studies with heterogeneous distribution. The two xenografts induced neoformation in defects of critical size. Histological, histochemical, and scanning electron microscopy (SEM) analyses were performed 30, 60, and 90 days after implantation. The empty defects showed signs of neoformation lower than 30% in the three periods, while the defects implanted with the material showed partial regeneration. InterOss Collagen material temporarily induced osteon formation during the healing process. The results presented here are promising for bone regeneration, demonstrating a beneficial impact in the biomedical field.     

Observations of vacuum spark dynamics from its X-ray emission

The behavior of a medium energy (~1 kJ) pulse-power-driven vacuum spark is shown to depend on the electrode material and form of the anode in otherwise similar conditions of operation. The dynamical evolution of the discharge is followed from its soft X-ray emission. The electrode materials compared are titanium and aluminum with a form of anode that is tubular or conical. The use of a tubular anode favors a more uniform sheath and a better formation of a dense Z-pinch and the ensuing hot spots are found to be at least twice as bright. The position of the brightest spots differs according to the material and the electrode shape, and is found to coincide with the shape of the sheath. The energy output is measured and the density of the plasma in the hot spots may be calculated