An infrared investigation of the catalyst formation in the system Ni(acac)2, C3H4, (iBu)3AL for propadiene polymerization

The catalyst formation in the system Ni(acac)2, C3H4, (iBu)3Al was investigated by means of infrared spectroscopy. It was found that the Al(acac)3 and (iBu)2Al(acac) formed are both by-products of catalyst formation without a catalytic activity. Ni(acac)2 loses its acac groups forming the unstable (iBu)2Ni compound; without C3H4 being present, this compound disproportionates to Ni metal and isobutane and isobutene. In the presence of C3H4 an allyl-nickel complex is formed, which reacts with (iBu)3Al to give the actual catalyst, possibly a bimetallic allyl—nickel-aluminium complex. Catalysts such as Ni(acac)2, C3H4, (iBu)3Al and (πC3H5)2Ni with or without (iBu)3Al all selectively give 1, 2, 1, 2-polypropadiene. A Lewis base like pyridine not only decreases the polymerization rate but also changes the selectivity towards the formation of 1, 2, 2, 1-polymer

On the origin of vanillyl alcohol oxidases

Vanillyl alcohol oxidase (VAO) is a fungal flavoenzyme that converts a wide range of para-substituted phenols. The products of these conversions, e.g. vanillin, coniferyl alcohol and chiral aryl alcohols, are of interest for several industries. VAO is the only known fungal member of the 4-phenol oxidising (4PO) subgroup of the VAO/PCMH flavoprotein family. While the enzyme has been biochemically characterised in great detail, little is known about its physiological role and distribution in fungi. We have identified and analysed novel, fungal candidate VAOs and found them to be mostly present in Pezizomycotina and Agaricomycotina. The VAOs group into three clades, of which two clades do not have any characterised member. Interestingly, bacterial relatives of VAO do not form a single outgroup, but rather split up into two separate clades. We have analysed the distribution of candidate VAOs in fungi, as well as their genomic environment. VAOs are present in low frequency in species of varying degrees of relatedness and in regions of low synteny. These findings suggest that fungal VAOs may have originated from bacterial ancestors, obtained by fungi through horizontal gene transfer. Because the overall conservation of fungal VAOs varies between 60 and 30% sequence identity, we argue for a more reliable functional prediction using critical amino acid residues. We have defined a sequence motif P-x-x-x-x-S-x-G-[RK]-N-x-G-Y-G-[GS] that specifically recognizes 4PO enzymes of the VAO/PCMH family, as well as additional motifs that can help to further narrow down putative functions. We also provide an overview of fingerprint residues that are specific to VAOs

System and method for synchronising a data processing network

A data processing system according to the invention comprising a group of at least a first and a second module, wherein each module has a data processing facility, a clock for timing data transmissions from the module to another module, a time-slot counter for counting a number of time slots which are available for transmission of data. The modules have a first operational state wherein the counted number of time slots is less than or equal to a predetermined number, in which operational state data transmission is enabled, and a second operational state wherein the number is in excess of the predetermined number, in which second operational state data transmission is disabled, Each module has a notifying facility for notifying when it is in the second operational state. The data processing system has at least one detecting facility that detects whether the other modules have notified that they are in the second operational state and the modules each have an initialization facility for resetting the time-slot counter when the module is in the second operational state and each of the other modules has notified that it is in the second operational state

Age of high-grade gneisses south of Grand Lake, Newfoundland

Crystalline rocks of the Steel Mountain Subzone of the Humber Zone in southwest Newfoundland give an age for granulite-grade metamorphism of 1498+9/-8 Ma, similar to ages from the Long Range inlier and northwestern Cape Breton Island. Peralkaline leucogranite was emplaced at 608 ± 4 Ma. The emplacement of anorthosite-gabbro complexes and amphibolite-grade metamorphism took place between these dates. The southern part of the Dunnage Zone (Central Gneiss Subzone), in contact with the Steel Mountain Subzone at the Long Range Fault, lacks Precambrian crystalline rocks, but was intruded by charnockitic plutons and metamorphosed to granulite facies at 460 ±10 Ma. This subzone was exhumed before 435 Ma. In the Meelpaeg Subzone of the Gander Zone, which is in contact with the Central Gneiss Subzone along the Victoria River Fault, the oldest intrusive component of a granoblastic migmatitic gneiss was emplaced at 418 ± 4 Ma. These data demonstrate that both the Long Range and Victoria River faults form major tectonic boundaries. Subzones appear to have been thrust westward in Silurian or later time. RÉSUMÉ Les roches cristallines de la sous-zone du mont Steel, dans la zone de Humber du sud-ouest de Terre-Neuve, ont donné des âges de 1498+9/-8 Ma pour le métamorphisme de haul grade, similaires à ceux de la boutonnière de Long Range et du nord de l'ile-du-Cap-Breton. Un leucogranite peralcalin s'est mis en place à 608 ± 4 Ma. L'intrusion des complexes à anorthosite-gabbro et le métamorphisme au faciès amphibolite se sont produits entre ces deux évènements. La partie sud de la zone de Dunnage (sous-zone de gneiss centrale), en contact avec la sous-zone du mont Steel a la faille de Long Range, ne contient pas de roches cristallines précambriennes mais à 616 recouped par des plutons charnockitiques et à 616 métamorphisée au faciès granulite à 460 ± 10 Ma. Cette sous-zone a été exhumge avant 435 Ma. Dans la sous-zone Mulpaeg de la zone de Gander, qui est mise en contact avec la sous-zone de gneiss centrale par la faille de la rivière Victoria, la phase intrusive la plus ancienne d'un gneiss migmatitique et granoblastique s'est mise en place à 418 ± 4 Ma. Ces données démontrent que les failles de Long Range et de la rivière Victoria sont des frontières tectoniques majeures. Les sous-zones semblent avoir subi un chevauchement vers l'ouest au plus tard au Silurien. [Traduit par le journal

LPMLE3 : a novel 1-D approach to study water flow in streambeds using heat as a tracer

We introduce LPMLE3, a new 1-D approach to quantify vertical water flow components at streambeds using temperature data collected in different depths. LPMLE3 solves the partial differential equation for coupled water flow and heat transport in the frequency domain. Unlike other 1-D approaches it does not assume a semi-infinite halfspace with the location of the lower boundary condition approaching infinity. Instead, it uses local upper and lower boundary conditions. As such, the streambed can be divided into finite subdomains bound at the top and bottom by a temperature-time series. Information from a third temperature sensor within each subdomain is then used for parameter estimation. LPMLE3 applies a low order local polynomial to separate periodic and transient parts (including the noise contributions) of a temperature-time series and calculates the frequency response of each subdomain to a known temperature input at the streambed top. A maximum-likelihood estimator is used to estimate the vertical component of water flow, thermal diffusivity, and their uncertainties for each streambed subdomain and provides information regarding model quality. We tested the method on synthetic temperature data generated with the numerical model STRIVE and demonstrate how the vertical flow component can be quantified for field data collected in a Belgian stream. We show that by using the results in additional analyses, nonvertical flow components could be identified and by making certain assumptions they could be quantified for each subdomain. LPMLE3 performed well on both simulated and field data and can be considered a valuable addition to the existing 1-D methods

Shigellosis and AIDS : Report of a case and brief review of the literature

Contains fulltext : 4491.pdf (publisher's version ) (Open Access

Automating Agential Reasoning: Proof-Calculi and Syntactic Decidability for STIT Logics

This work provides proof-search algorithms and automated counter-model extraction for a class of STIT logics. With this, we answer an open problem concerning syntactic decision procedures and cut-free calculi for STIT logics. A new class of cut-free complete labelled sequent calculi G3LdmL^m_n, for multi-agent STIT with at most n-many choices, is introduced. We refine the calculi G3LdmL^m_n through the use of propagation rules and demonstrate the admissibility of their structural rules, resulting in auxiliary calculi Ldm^m_nL. In the single-agent case, we show that the refined calculi Ldm^m_nL derive theorems within a restricted class of (forestlike) sequents, allowing us to provide proof-search algorithms that decide single-agent STIT logics. We prove that the proof-search algorithms are correct and terminate

Cut-free Calculi and Relational Semantics for Temporal STIT Logics

We present cut-free labelled sequent calculi for a central formalism in logics of agency: STIT logics with temporal operators. These include sequent systems for Ldm , Tstit and Xstit. All calculi presented possess essential structural properties such as contraction- and cut-admissibility. The labelled calculi G3Ldm and G3Tstit are shown sound and complete relative to irreflexive temporal frames. Additionally, we extend current results by showing that also Xstit can be characterized through relational frames, omitting the use of BT+AC frames

Mixed-Integer MPC Strategies for Fueling and Density Control in Fusion Tokamaks

Model predictive control (MPC) is promising for fueling and core density feedback control in nuclear fusion tokamaks, where the primary actuators, frozen hydrogen fuel pellets fired into the plasma, are discrete. Previous density feedback control approaches have only approximated pellet injection as a continuous input due to the complexity that it introduces. In this letter, we model plasma density and pellet injection as a hybrid system and propose two MPC strategies for density control: mixed-integer (MI) MPC using a conventional mixed-integer programming (MIP) solver and MPC utilizing our novel modification of the penalty term homotopy (PTH) algorithm. By relaxing the integer requirements, the PTH algorithm transforms the MIP problem into a series of continuous optimization problems, reducing computational complexity. Our novel modification to the PTH algorithm ensures that it can handle path constraints, making it viable for constrained hybrid MPC in general. Both strategies perform well with regards to reference tracking without violating path constraints and satisfy the computation time limit for real-time control of the pellet injection system. However, the computation time of the PTH-based MPC strategy consistently outpaces the conventional MI-MPC strategy