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High-performance large-scale graph analytics are essential to timely analyze relationships in big datasets. Conventional processor architectures suffer from inefficient resource usage and bad scaling on those workloads. To enable efficient and scalable graph analysis, Intel developed the Programmable Integrated Unified Memory Architecture (PIUMA) as a part of the DARPA Hierarchical Identify Verify Exploit (HIVE) program. PIUMA consists of many multithreaded cores, fine-grained memory and network accesses, a globally shared address space, powerful offload engines, and a tightly integrated optical interconnection network. This article presents the PIUMA architecture and documents our experience in designing and building a prototype chip and its bring-up process. PIUMA silicon has successfully powered on demonstrating key aspects of the architecture, some of which will be incorporated into future Intel products.

Reaction of Ni(NCS)2with 4-(Boc-amino)pyridine in acetonitrile leads to the formation of a new coordination polymer with the composition Ni(NCS)2(4-(Boc-amino)pyridine)2·MeCN (1-MeCN). In the crystal structure the Ni(II) cations are linked by the anionic ligands into chains that are further connected into layers by intermolecular N–H···O hydrogen bonding. These layers are stacked and channels are formed, in which acetonitrile molecules are located. Solvent removal leads to the ansolvate 1, which shows microporosity as proven by sorption measurements. Single crystal X-ray investigations reveal that the solvent removal leads to a change in symmetry from primitive to C-centered, which is reversible and which proceeds via a topotactic reaction leaving the network intact. The magnetic properties of 1-MeCN and 1are governed by the ferromagnetic exchange between spins of Ni(II) forming chains. The susceptibility and specific heat for such a quantum Heisenberg chain of S= 1 spins with zero-field splitting are calculated using the DMRG method and compared with the experimental results.

Backward induction (BI) was one of the earliest methods developed for solving finite sequential games with perfect information. It proved to be especially useful in the context of Tom Schelling’s ideas of credible versus incredible threats. BI can be also extended to solve complex games that include an infinite number of actions or an infinite number of periods. However, some more complex empirical or experimental predictions remain dramatically at odds with theoretical predictions obtained by BI. The primary example of such a troublesome game is Centipede. The problems appear in other long games with sufficiently complex structure. BI also shares the problems of subgame perfect equilibrium and fails to eliminate certain unreasonable Nash equilibria.

Accurate predictions of net ecosystem productivity (NEPc) of forest ecosystems are essential for climate change decisions and requirements in the context of national forest growth and greenhouse gas inventories. However, drivers and underlying mechanisms determining NEPc(e.g., climate and nutrients) are not entirely understood yet, particularly when considering the influence of past periods. Here we explored the explanatory power of the compensation day (cDOY)—defined as the day of year when winter net carbon losses are compensated by spring assimilation—for NEPcin 26 forests in Europe, North America, and Australia, using different NEPcintegration methods. We found cDOY to be a particularly powerful predictor for NEPcof temperate evergreen needleleaf forests (R2= 0.58) and deciduous broadleaf forests (R2= 0.68). In general, the latest cDOY correlated with the lowest NEPc. The explanatory power of cDOY depended on the integration method for NEPc, forest type, and whether the site had a distinct winter net respiratory carbon loss or not. The integration methods starting in autumn led to better predictions of NEPcfrom cDOY then the classical calendar method starting 1 January. Limited explanatory power of cDOY for NEPcwas found for warmer sites with no distinct winter respiratory loss period. Our findings highlight the importance of the influence of winter processes and the delayed responses of previous seasons' climatic conditions on current year's NEPc. Such carry‐over effects may contain information from climatic conditions, carbon storage levels, and hydraulic traits of several years back in time. Compensation day (cDOY) is the day of year when net C losses during winter are compensated by net C uptake in springcDOY largely explains annual net ecosystem productivity NEPcof forests when the site has a distinct winter respiratory loss periodcDOY and its explanatory power depends on the integration method for annual NEPcand on the forest type

Cyclic AMP (cAMP) signaling is localized to multiple spatially distinct microdomains, but the role of cAMP microdomains in cancer cell biology is poorly understood. Here, we present a tunable genetic system that allows us to activate cAMP signaling in specific microdomains. We uncover a nuclear cAMP microdomain that activates a tumor-suppressive pathway in a broad range of cancers by inhibiting YAP, a key effector protein of the Hippo pathway, inside the nucleus. We show that nuclear cAMP induces a LATS-dependent pathway leading to phosphorylation of nuclear YAP solely at serine 397 and export of YAP from the nucleus with no change in YAP protein stability. Thus, nuclear cAMP inhibition of nuclear YAP is distinct from other known mechanisms of Hippo regulation. Pharmacologic targeting of specific cAMP microdomains remains an untapped therapeutic approach for cancer; thus, drugs directed at the nuclear cAMP microdomain may provide avenues for the treatment of cancer.

To facilitate discovery of compounds modulating sphingosine-1-phosphate (S1P) signaling, the authors used high-throughput mass spectrometry technology to measure S1P formation in human whole blood. Since blood contains endogenous sphingosine (SPH) and S1P, mass spectrometry was chosen to detect the conversion of an exogenously added 17-carbon-long variant of sphingosine, C17SPH, into C17S1P. The authors developed procedures to achieve homogeneous mixing of whole blood in 384-well plates and for a method requiring minimal manipulations to extract S1P from blood in 96- and 384-well plates prior to analyses using the RapidFire® mass spectrometry system.

The synthesis and spectroscopic characterization of [Cp*2Mo2P2Se3] (1; Cp* = C5Me5) and its use as a molecular building block in the formation of copper(I) halide polymers is described. The reaction of 1in CH2Cl2with 2 equiv. of CuBr and CuI in CH3CN under diffusion conditions gave [(Cp*2Mo2P2Se3)2(CuBr)2] (2) and [(Cp*2Mo2P2Se3)(CuX)3(CH3CN)]n(X = I; 3/4), respectively. The structure of 2is distinguished by a central Cu2Br2ring coordinated on each side by a tripledecker complex through one of its P atoms. A 2D network is formed by weak interactions between Se atoms of neighboring molecules. Compound [(Cp*2Mo2P2Se3)(CuI)3(CH3CN)]nexists in two isomeric forms 3and 4. The crystal structure of 3can be described as a two‐dimensional polymer that is formed by ribbons containing looped chains of three Cu2I2rings and attached [Cp*2Mo2P2Se3] molecules. The structure of 4contains a ribbon in which tripledecker molecules are linked through their P atoms to (CuI)6clusters. The ribbons are connected by weak Se···Se interactions. The reaction of a mixture of 1and P4Se3with CuI gave [(Cp*2Mo2P2Se3)(P4Se3)(CuI)2]n. The crystal structure analysis of 5reveals a new type of organometallic–inorganic framework in which 1and P4Se3are linked by Cu2I2rings.

ABSTRACTBy using a detergent-washed membrane preparation, the interaction of the fungal natural product inhibitor aureobasidin A (AbA) with inositol phosphorylceramide synthase (IPC synthase) was studied by kinetic analysis of wild-type and mutant enzyme-catalyzed reactions. AbA inhibited the wild-type enzyme from both Candida albicansand Saccharomyces cerevisiaein an irreversible, time-dependent manner, with apparent Kivalues of 183 and 234 pM, respectively. Three synthetic chemistry-derived AbA derivatives, PHA-533179, PHA-556655, and PHA-556656, had affinities 4 to 5 orders of magnitude lower and were reversible inhibitors that competed with the donor substrate phosphatidylinositol (PI). AbA was a reversible, apparently noncompetitive inhibitor, with a Kiof 1.4 μM, of the IPC synthase from an AbA-resistant S. cerevisiaemutant. The Kmvalues for both substrates (ceramide and PI) were similar when they interacted with the mutant and the wild-type enzymes. By contrast, the Vmaxfor the mutant enzyme was less than 10% of that for the wild-type enzyme. A comparison of the results obtained with AbA with those obtained with two other natural products inhibitors, rustmicin and khafrefungin, revealed that while rustmicin appeared to be a reversible, noncompetitive inhibitor of the wild-type enzyme, with a Kiof 16.0 nM, khafrefungin had the kinetic properties of a time-dependent inhibitor and an apparent Kiof 0.43 nM. An evaluation of the efficiencies of these compounds as inhibitors of the mutant enzyme revealed for both a drop in the apparent affinity for the enzyme of more than 2 orders of magnitude.

The article offers a report about the combat operational stress control program of the U.S. Marine Corps. The author discusses the significance of the program to the marines and how it can prevent stress injuries. According to the report, the program intends to avoid the temporary stress injuries and to quickly identify and treat stress illnesses.

The oxidative addition of (2,2-dibromovinyl)ferrocene [Br2C=C(H)–Fc] (1) to [Pd(PPh3)4] yields the heterodinuclear σ-alkenyl complex trans-[{Pd(Br)(PPh3)2}–C(Br)=C(H)–Fc] (2). Nucleophilic attack of sodium thiolates on 1 unexpectedly affords the vinyl thioether derivatives (Z)-[(RS)(H)C=C(H)–Fc] (4a: R = Ph; 4b: R = tBu; 4c: R = Et). Complexes 4a and 4c can also be prepared by addition of NaSR across the triple bond of Fc–C≡C–H (3). Addition of an excess of NaSR to 1 affords the dithioether derivatives (Z)-[(RS)(H)C=C(SR)–Fc] (5a: R = Ph; 5b: R = p-tolyl; 5c: R = Et). An addition/elimination sequence is suggested to account for this surprising result. The yield of 5c is very low due to a competing formation of ethynylferrocene (3). Reaction of 5b with [Re(thf)(CO)3(μ-Br)]2 and [PtCl2(PhCN)2] leads to the heterodinuclear chelate complexes [Fc{C(S–p-tolyl)=C(H)(S–p-tolyl)}Re(Br)(CO)3] (6) and [Fc{C(S–p-tolyl)=C(H)(S–p-tolyl)}PtCl2] (7a), respectively. Metathesis of the fluxional compound 7a in the presence of NaI affords [Fc{C(S–p-tolyl)=C(H)(S–p-tolyl)}PtI2] (7b). The electrochemical properties of some of these complexes have been studied by means of cyclic voltammetry, and the molecular structures of 1, 2, 3, 4b, 4c and 6 have been determined by X-ray diffraction. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)

The reaction of [Ni(COD)2] with [Cp*2NbTe2H] (1; Cp* = η-C5Me5) in the presence of Ph2PCH2PPh2 (dppm) in boiling toluene gives black-violet [(Cp*2Nb)2NiTe4] (3). If [Cp′2NbTe2H] (2; Cp′ = tBuC5H4) is used under similar conditions dark-brown [(Cp′Nb)2Ni5Te7(dppm)2] (4) is formed. The structures of 3 and 4 have been determined crystallographically. Complex 3 contains a severely distorted NiTe4 tetrahedron to which two niobocene groups are coordinated. Density functional analysis of the electronic structure of the NiTe4 building block shows that it is best described as an [Ni(η2-Te2)2]2– fragment. The structure of 4 reveals the presence of two Ni5 and Te5 tetragonal pyramids stacked into each other in an opposite way. Six of the Te bridges form two triangular faces, each of which is capped by a Cp′Nb fragment. Additionally, two dppm ligands bridge the long Ni–Ni edges of the Ni4 bases. Oxidation of 3 with [(C5H5)2Fe]BPh4 gives paramagnetic [(Cp*2Nb)2NiTe4]BPh4 (6), whereas oxidation with [(C5H5)2Fe]PF6 proceeds with fluoride transfer to give [Cp*2NbF2]PF6 (5). Electrochemical studies of 3 reveal the existence of the redox couples [3]2+/[3]+/[3]0/[3]–/[3]2–. Density functional calculations carried out on the different oxidation states of 3 reveal the following main features: the persistent presence of Nb–Ni bonds and the retention of Te–Te bonds in cationic and neutral species and their breaking off in reduced forms. Irrespective of the initial site of electrochemical attack, the Te atoms and Cp rings are principally affected in the final products.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)

The heritability of structural properties of the high-carbon steel 1 CS67 during laboratory casting, hot and cold strip rolling, soft annealing, as well as the impact of processing conditions on the final mechanical properties of the strip were studied. Ferrite grain size seems to be more intensively affected by the casting's cooling rate and subsequent heating time than by the phase transformations before conventional rolling. Owing to higher ferrite content resulting from finer austenite grain size, samples obtained after laboratory remelting and casting are characterised by lower yield stress and strength, in combination with higher ductility. A simple model of mean equivalent stress values dependent on temperature, strain and strain rate was developed using the results of hot flat-rolling tests.

Calamagrostis arundinaceaL. (Roth.) and C. villosa(Chaix.) J.F. Gmel are two grass species substituting forest communities on deforested areas in Central Europe. They were exposed to enhanced ultraviolet-B (UV-B, λ = 290–320 nm) radiation during 22 weeks. A system of modulated lamps operating under field conditions was used to simulate a 25 % increase of incident UV-B radiation. CO2assimilation seemed to be limited by a decrease of stomatal conductance (gs) in C. arundinacea, whereas carboxylation activity of ribulose-1,5-bisphosphate carboxylase/oxygenase (RuBPCO) was not affected. On the contrary, gsand RuBPCO activity decreased in C. villosa. These physiological adjustments resulted in growth changes; above-ground biomass decreased in C. villosa(prevailing negative effect) and significantly increased in C. arundinacea(prevailing positive effect) in response to enhanced UV-B radiation.

Treatment of 4,4-dichloro-1,1-diphenyl-2-azabuta-1,3-diene [Cl2C=C(H)-N=CPh2] (1) with excess sodium isopropylthiolate or sodium thiophenolate in DMF yielded the 2-azabutadiene derivatives (RS)2C=C(H)–N=CPh2 (2) (2a R = iPr; 2b R = Ph). Nucleophilic attack of the sodium salt of ethyl thioglycolate on 1 afforded as the sole product the six-membered heterocyclic compound ethyl 2-ethoxycarbonylmethylthio-5,5-diphenyl-5,6-dihydro-4H-1,4-thiazine-6-carboxylate (5). The reaction is initiated by substitution of the two vinyl-bound chloro substituents to give {EtO(O=)CCH2S}2C=C(H)–N=CPh2 (2c) as intermediate. A mechanism that accounts for the subsequent cyclisation reaction is proposed. The 2-azabutadiene derivative (PhO)2C=C(H)–N=CPh2 (7) was obtained by the reaction of 1 with sodium phenolate. The regioselectivity of the incoming nucleophile is roughly correlated with its hardness/softness in accord with Pearson’s HSAB principle. The molecular structures of 2a,b, 5 and 7 were determined by single-crystal X-ray diffraction. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)

Reactions between the metal(ii) salts [M(CH3CN)n](BF4)2(M = Fe, n= 6; M = Mn, n= 4) and some organic anionic polynitriles were studied. With the pentacyanopropenide anion pcp−[pcp−= (NC)2CC(CN)C(CN)2−], were obtained, according to the experimental conditions, the new complexes [M(pcp)2(H2O)4] (1, M = Fe; 2, M = Mn) and [M(pcp)2] (3, M = Fe; 4= Mn). Use of the hexacyano-3,4-diazahexadienediide anion [(NC)2CC(CN)NNC(CN)C(CN)22−] instead of pcp−did not afford polynitrile metal complexes but led to a new organic derivative 5, of formula C10N8H2. Crystallographic studies indicated that the isostructural compounds 1and 2involve discrete monomeric units with pcp ligands acting with a monodentate coordination mode and having the metal in a pseudooctahedral trans-MN2O4environment; however, a rich hydrogen bond system gives rise to a 3D array. Complex 3, which presents metal in a pseudooctahedral MN6environment, has a 3D structure arising from pcp ligands having an unprecedented μ3-coordination mode. Compound 5is a bicyclic derivative with a pyrazolo[1,5-a]pyrimidine skeleton. In all derivatives, the organic part is essentially planar and involves a strongly delocalized π system. The magnetic properties of the inorganic complexes have been studied in the 2–300 K range. Fit of the magnetic data indicates high spin complexes with weak antiferromagnetic interactions in 2, 3and 4and the presence of a significant zero field splitting of the Fe(ii) ion in 1.

A mathematical model of a catalytic converter for automobile diesel engines that contains zeolites for adsorption of hydrocarbons has been developed. The model includes a description of mass- and heat-transfer resistance at the external surface of the monolith washcoat and internal diffusion within the catalytic washcoat layer. Kinetic parameters for adsorption and oxidation of hydrocarbons [propene (C3H6), decane (C10H22), and toluene (C6H5CH3)], CO oxidation, and NOx adsorption and reduction were evaluated on the basis of dynamic experiments. Model simulations of dynamic operation regimes illustrate the effects of the inlet flow rate, temperature and adsorption capacity on the light-off, integral conversions, and spatiotemporal concentration patterns in the monolith. The effects of varying the transport properties of the washcoat layer (effective diffusion coefficient) and washcoat thickness are also investigated.

Total in vitroactivity of RuBPCO (ribulose-1,5-bisphosphate carboxylase/oxygenase) enzyme was assayed spectrophotometrically by the continuous measurement of 3-phosphoglycerate-dependent NADH oxidation in a coupled enzyme system. RuBPCO activities were found in the ranges 1.01–2.76 and 1.23–3.10 µmol(CO2) m−2s− 1in current Norway spruce needles growing in ambient (AC) and elevated (EC) CO2concentration, respectively. RuBPCO activity in AC needles from the upper layer (U) was 11–15 % higher compared to those from the middle (M) layer, and even 44–56 % higher compared to the lower (L) layer of spruce crown. Over the vegetation season, we observed a highly significant decrease of RuBPCO activity in the EC-U needles from 3.10 (July) to 1.60 (October) µmol(CO2) m−2s−1as a consequence of downward feedback regulation. Moreover, this down-regulation was not caused by a non-specific decrease in total leaf nitrogen content.Total in vitroactivity of RuBPCO (ribulose-1,5-bisphosphate carboxylase/oxygenase) enzyme was assayed spectrophotometrically by the continuous measurement of 3-phosphoglycerate-dependent NADH oxidation in a coupled enzyme system. RuBPCO activities were found in the ranges 1.01–2.76 and 1.23–3.10 µmol(CO2) m−2s− 1in current Norway spruce needles growing in ambient (AC) and elevated (EC) CO2concentration, respectively. RuBPCO activity in AC needles from the upper layer (U) was 11–15 % higher compared to those from the middle (M) layer, and even 44–56 % higher compared to the lower (L) layer of spruce crown. Over the vegetation season, we observed a highly significant decrease of RuBPCO activity in the EC-U needles from 3.10 (July) to 1.60 (October) µmol(CO2) m−2s−1as a consequence of downward feedback regulation. Moreover, this down-regulation was not caused by a non-specific decrease in total leaf nitrogen content.

Four deuterium‐labelled ABA catabolites of high isotopic purity were prepared for hormone profiling studies using HPLC‐ESI‐MS‐MS. The catabolites, namely [7′,7′,7′‐d3]‐PA, [7′,7′,7′‐d3]‐DPA, [5,8′,8′,8′‐d4]‐7′‐hydroxyABA and [4,5,8′,8′,8′‐d5]‐ABA glucose ester were prepared either by biotransformation or chemical synthesis starting with labelled ABA. The labelled compounds are employed as internal standards for plant hormone profiling by liquid chromatography–electrospray–tandem mass spectrometry. Copyright © 2005 John Wiley & Sons, Ltd.

In a previous paper (Grof, Z.; Kosek, J.; Marek, M. Morphogenesis model of growing polyolefin particles. AIChE J., accepted), we have introduced the model of the morphological evolution of polyolefin particles in catalytic polymerization reactors. The model considers the polyolefin particle to consist of a large number of microelements with viscoelastic interactions acting among them. Here we present the results of the systematic mapping from the parametric space of catalyst activity, reaction conditions, mass transport resistance, and viscoelastic properties of polyolefins into the space of possible morphological developments, such as the formation of hollow particles, particles with macrocavities, regular or irregular replication of particle shape during its growth, highly porous or compact particles, the formation of fine particles, etc. The predicted particle morphologies are compared with experimental findings. We focus on the effect of temperature on the morphogenesis of polyolefin particles and identify the reaction conditions leading to the disintegration of the growing particle into fine particles, which is the unwanted phenomenon observed in industrial reactors. The causes of different pore space morphologies of Ziegler−Natta and metallocene-born polyolefin particles are also investigated.