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941.
We consider the fractional cointegrated vector autoregressive (CVAR) model of Johansen and Nielsen (2012a) and make two distinct contributions. First, in their consistency proof, Johansen and Nielsen (2012a) imposed moment conditions on the errors that depend on the parameter space, such that when the parameter space is larger, stronger moment conditions are required. We show that these moment conditions can be relaxed, and for consistency we require just eight moments regardless of the parameter space. Second, Johansen and Nielsen (2012a) assumed that the cointegrating vectors are stationary, and we extend the analysis to include the possibility that the cointegrating vectors are non‐stationary. Both contributions require new analysis and results for the asymptotic properties of the likelihood function of the fractional CVAR model, which we provide. Finally, our analysis follows recent research and applies a parameter space large enough that the usual (non‐fractional) CVAR model constitutes an interior point and hence can be tested against the fractional model using a Chi‐squared‐test. 相似文献
942.
G.C.Pedersen J.E.Eldridge 《硫酸工业》2009,(4):21-26
介绍Kimre公司的SXF^TM半错流洗涤器的结构、优点和应用。该洗涤器采用卧式并流气液接触方式,可根据需要分隔成不同操作段,在由交织单丝构成的纤维介质上完成气体的冷却、净化和除沫。与传统立式逆流填料塔相比,该洗涤器的优点为:高度低,泵、阀门、控制器等可在地面安装,容易操作和维修;液气比范围宽;可进行多级操作,包括在一台设备内完成多个化学过程。如用于冶炼烟气净化,所有步骤可在一台设备内完成。列举了化肥厂造粒塔气体净化、磷酸厂气体除氟和硫酸厂干燥塔除沫等应用实例。 相似文献
943.
R. Ranjan C. Pantano P. Fischer 《International Journal of Heat and Mass Transfer》2011,54(21-22):4636-4654
We investigate heat transfer characteristics of a turbulent swept flow in a channel with a wire placed over one of its walls using direct numerical simulation. This geometry is a model of the flow through the wire-wrapped fuel pins, the heat exchanger, typical of many civil nuclear reactor designs. The swept flow configuration generates a recirculation bubble with net mean axial flow. A constant inward heat flux from the walls of the channel is applied. A key aspect of this flow is the presence of a high temperature region at the contact line between the wire and the channel wall, due to thermal confinement (stagnation). We analyze the variation of the temperature in the recirculation bubble at Reynolds number based on the bulk velocity along the wire-axis direction and the channel half height of 5400. Four cases are simulated with different flowrates transverse to the wire-axis direction. This configuration is topologically similar to backward-facing steps or slots with swept flow, except that the dominant flow is along the obstacle axis in the present study and the crossflow is smaller than the axial flow, i.e., the sweep angle is large. The temperature field is simulated at three different Prandtl numbers: 10?2, 10?1 and 1. The lower value of Prandtl number is characteristic of experimental high-temperature reactors that use a molten salt as coolant while the high value is typical of gas (or water vapor) heat exchangers. In addition, mean temperature, turbulence statistics, instantaneous wall temperature distribution and Nusselt number variation are investigated. The peak Nusselt number occurs close to the reattachment location, on the lee side of the wire, and is about 50–60% higher compared to the case without crossflow. The high temperature region follows the growth of the recirculation bubble which increases by about 65% from the lowest to highest amount of crossflow. Particular attention is devoted to the temperature distribution on the walls of the channel and the surface of the wire. The behavior of the heat-flux across the mean dividing streamline of the recirculation bubble is investigated to quantify the local heat transfer rates occurring in this region. 相似文献
944.
Adina L. Ghirişan Simion Drǎgan Alexandru Pop Marinela Simihǎian Vasile Miclǎuş 《加拿大化工杂志》2007,85(6):900-905
The influence of the apatite on the efficiency of neutralization and on heavy metal removal of acid mine waste water has been studied. The analysis of the treated waste water samples with apatite has shown an advanced purification, the concentration of the heavy metals after the treatment of the waste water with apatite being 25 to 1000 times less than the Maximum Concentration Limits admitted by European Norms (NTPA 001/2005). In order to establish the macro‐kinetic mechanism in the neutralization process, the activation energy, Ea, and the kinetic parameters, rate coefficient of reaction, kr, and kt were determined from the experimental results obtained in “ceramic ball‐mill” reactor. The obtained values of the activation energy Ea >> 42 kJ mol?1 (e.g. Ea = 115.50 ± 7.50 kJ mol?1 for a conversion of sulphuric acid ηH2SO4 = 0.05, Ea = 60.90 ± 9.50 kJ mol?1 for η H2SO4 = 0.10 and Ea = 55.75 ± 10.45 kJ mol‐1 for η H2SO4 = 0.15) suggest that up to a conversion of H2SO4 equal 0.15 the global process is controlled by the transformation process, adsorption followed by reaction, which means surface‐controlled reactions. At a conversion of sulphuric acid η H2SO4 > 0.15, the obtained values of activation energy Ea < 42 kJ mol‐1 (e.g. Ea = 37.55 ± 4.05 kJ mol‐1 for η H2SO4 = 0.2, Ea = 37.54 ± 2.54 kJ mol‐1 for η H2SO4 = 0.3 and Ea = 37.44 ± 2.90 kJ mol‐1 for η H2SO4 = 0.4) indicate diffusion‐controlled processes. This means a combined process model, which involves the transfer in the liquid phase followed by the chemical reaction at the surface of the solid. Kinetic parameters as rate coefficient of reaction, kr with values ranging from (5.02 ± 1.62) 10‐4 to (8.00 ± 1.55) 10‐4 (s‐1) and transfer coefficient, kt, ranging from (8.40 ± 0.50) 10‐5 to (10.42 ± 0.65) 10‐5 (m s‐1) were determined. 相似文献
945.
Peptide Bioconjugates of Electron‐Poor Metallocenes: Synthesis,Characterization, and Anti‐Proliferative Activity 下载免费PDF全文
Marcus Maschke Jens Grohmann Claudia Nierhaus Dr. Max Lieb Prof. Dr. Nils Metzler‐Nolte 《Chembiochem : a European journal of chemical biology》2015,16(9):1333-1342
We report the synthesis of metallocene compounds Cp2M with two different electron‐withdrawing substituents on both cyclopentadienyl rings (hexafluoroacetone (HFA) and chlorobenzoyl ( 1 – 5 ); HFA and COOH ( 6 and 7 ), M=Fe or Ru). The COOH‐containing derivatives were used to synthesize peptide bioconjugates with enkephalin ( 8 and 9 ) and neurotensin ( 10 and 11 ) as well as fluorescein‐labeled neurotensin ( 12 ). All the molecules were fully characterized, including X‐ray structures for 6 and 7 . The physicochemical properties (lipophilicity and electrochemistry) and cytotoxicity on MCF‐7, HT‐29, and PT‐45 cancer cells were evaluated for selected compounds. Electrochemical investigation by cyclic voltammetry revealed that all bis‐substituted metallocenes are up to 300 mV harder to oxidize compared to the monosubstituted 2‐ferrocenylhexafluoropropan‐2‐ol (FcHFA: Δ${E{{{\rm f}\hfill \atop 0\hfill}}}$ =214 mV; disubstituted derivatives: up to Δ${E{{{\rm f}\hfill \atop 0\hfill}}}$ =512 mV; both vs. FcH0/+). For the bis‐substituted compounds, log P determinations by RP‐HPLC showed increased lipophilicity in comparison to the monosubstituted FcHFA and RcHFA. Cellular uptake was investigated by fluorescence microcopy, and this revealed endosomal entrapment for 12 . 相似文献
946.
Matthias Engleder Dr. Tea Pavkov‐Keller Dr. Anita Emmerstorfer Altijana Hromic Sabine Schrempf Dr. Georg Steinkellner Dr. Tamara Wriessnegger Prof. Erich Leitner Dr. Gernot A. Strohmeier Dr. Iwona Kaluzna Dr. Daniel Mink Dr. Martin Schürmann Dr. Silvia Wallner Prof. Peter Macheroux Prof. Karl Gruber Dr. Harald Pichler 《Chembiochem : a European journal of chemical biology》2015,16(12):1730-1734
Hydratases provide access to secondary and tertiary alcohols by regio‐ and/or stereospecifically adding water to carbon‐carbon double bonds. Thereby, hydroxy groups are introduced without the need for costly cofactor recycling, and that makes this approach highly interesting on an industrial scale. Here we present the first crystal structure of a recombinant oleate hydratase originating from Elizabethkingia meningoseptica in the presence of flavin adenine dinucleotide (FAD). A structure‐based mutagenesis study targeting active site residues identified E122 and Y241 as crucial for the activation of a water molecule and for protonation of the double bond, respectively. Moreover, we also observed that two‐electron reduction of FAD results in a sevenfold increase in the substrate hydration rate. We propose the first reaction mechanism for this enzyme class that explains the requirement for the flavin cofactor and the involvement of conserved amino acid residues in this regio‐ and stereoselective hydration. 相似文献
947.
An Amphiphilic BODIPY‐Porphyrin Conjugate: Intense Two‐Photon Absorption and Rapid Cellular Uptake for Two‐Photon‐Induced Imaging and Photodynamic Therapy 下载免费PDF全文
Dr. Tao Zhang Dr. Rongfeng Lan Longlong Gong Dr. Baoyan Wu Yuzhi Wang Dr. Daniel W. J. Kwong Prof. Wai‐Kwok Wong Dr. Ka‐Leung Wong Prof. Da Xing 《Chembiochem : a European journal of chemical biology》2015,16(16):2357-2364
The new amphiphilic BODPY‐porphyrin conjugate BZnPP and its precursor BZnPH were synthesised, and their linear and two‐photon photophysical properties, together with their cellular uptake and photo‐cytotoxicity, were studied. This amphiphilic conjugate consists of a hydrophobic BODIPY moiety and a hydrophilic tetra(ethylene glycol) chain bridging a cationic triphenylphosphonium group to an amphiphilic porphyrin ZnP through acetylide linkers at its meso positions. A large two‐photon absorption cross‐section (σ=1725 GM) and a high singlet oxygen quantum yield (0.52) were recorded. Intense linear‐ and two‐photon‐induced red emissions were also observed for both BZnPP and BZnPH. Further in vitro studies showed that BZnPP exhibited very efficient cellular uptake and strong photocytotoxic but weak dark cytotoxic properties towards human breast carcinoma MCF‐7 cells. In summary, the two‐photon‐induced emission and the potent photo‐cytotoxicity of BZnPP make it an efficacious dual‐purpose tumour‐imaging and photodynamic therapeutic agent in the tissue‐transparent spectral windows. 相似文献
948.
Phenylalanine Ammonia‐Lyase‐Catalyzed Deamination of an Acyclic Amino Acid: Enzyme Mechanistic Studies Aided by a Novel Microreactor Filled with Magnetic Nanoparticles 下载免费PDF全文
Diána Weiser Dr. László Csaba Bencze Gergely Bánóczi Ferenc Ender Dr. Róbert Kiss Eszter Kókai Dr. András Szilágyi Prof. Dr. Beáta G. Vértessy Dr. Ödön Farkas Dr. Csaba Paizs Prof. Dr. László Poppe 《Chembiochem : a European journal of chemical biology》2015,16(16):2283-2288
Phenylalanine ammonia‐lyase (PAL), found in many organisms, catalyzes the deamination of l ‐phenylalanine (Phe) to (E)‐cinnamate by the aid of its MIO prosthetic group. By using PAL immobilized on magnetic nanoparticles and fixed in a microfluidic reactor with an in‐line UV detector, we demonstrated that PAL can catalyze ammonia elimination from the acyclic propargylglycine (PG) to yield (E)‐pent‐2‐ene‐4‐ynoate. This highlights new opportunities to extend MIO enzymes towards acyclic substrates. As PG is acyclic, its deamination cannot involve a Friedel–Crafts‐type attack at an aromatic ring. The reversibility of the PAL reaction, demonstrated by the ammonia addition to (E)‐pent‐2‐ene‐4‐ynoate yielding enantiopure l ‐PG, contradicts the proposed highly exothermic single‐step mechanism. Computations with the QM/MM models of the N‐MIO intermediates from l ‐PG and l ‐Phe in PAL show similar arrangements within the active site, thus supporting a mechanism via the N‐MIO intermediate. 相似文献
949.
A Multiple‐Labeling Strategy for Nonribosomal Peptide Synthetases Using Active‐Site‐Directed Proteomic Probes for Adenylation Domains 下载免费PDF全文
Dr. Fumihiro Ishikawa Dr. Takehiro Suzuki Dr. Naoshi Dohmae Prof. Hideaki Kakeya 《Chembiochem : a European journal of chemical biology》2015,16(18):2590-2594
Genetic approaches have greatly contributed to our understanding of nonribosomal peptide biosynthetic machinery; however, proteomic investigations are limited. Here, we developed a highly sensitive detection strategy for multidomain nonribosomal peptide synthetases (NRPSs) by using a multiple‐labeling technique with active‐site‐directed probes for adenylation domains. When applied to gramicidin S‐producing and ‐nonproducing strains of Aneurinibacillus migulanus (DSM 5759 and DSM 2895, respectively), the multiple technique sensitively detected an active multidomain NRPS (GrsB) in lysates obtained from the organisms. This functional proteomics method revealed an unknown inactive precursor (or other inactive form) of GrsB in the nonproducing strain. This method provides a new option for the direct detection, functional analysis, and high‐resolution identification of low‐abundance active NRPS enzymes in native proteomic environments. 相似文献
950.
Novel Tacrine‐Grafted Ugi Adducts as Multipotent Anti‐Alzheimer Drugs: A Synthetic Renewal in Tacrine–Ferulic Acid Hybrids 下载免费PDF全文
Mohamed Benchekroun Dr. Manuela Bartolini Dr. Javier Egea Dr. Alejandro Romero Dr. Elena Soriano Dr. Marc Pudlo Vincent Luzet Prof. Vincenza Andrisano Dr. María‐Luisa Jimeno Dr. Manuela G. López Sarah Wehle Prof. Tijani Gharbi Prof. Bernard Refouvelet Lucía de Andrés Clara Herrera‐Arozamena Prof. Barbara Monti Prof. Maria Laura Bolognesi Prof. María Isabel Rodríguez‐Franco Prof. Dr. Michael Decker Prof. José Marco‐Contelles Dr. Lhassane Ismaili 《ChemMedChem》2015,10(3):523-539
Herein we describe the design, multicomponent synthesis, and biological, molecular modeling and ADMET studies, as well as in vitro PAMPA‐blood–brain barrier (BBB) analysis of new tacrine–ferulic acid hybrids (TFAHs). We identified (E)‐3‐(hydroxy‐3‐methoxyphenyl)‐N‐{8[(7‐methoxy‐1,2,3,4‐tetrahydroacridin‐9‐yl)amino]octyl}‐N‐[2‐(naphthalen‐2‐ylamino)2‐oxoethyl]acrylamide (TFAH 10 n ) as a particularly interesting multipotent compound that shows moderate and completely selective inhibition of human butyrylcholinesterase (IC50=68.2 nM ), strong antioxidant activity (4.29 equiv trolox in an oxygen radical absorbance capacity (ORAC) assay), and good β‐amyloid (Aβ) anti‐aggregation properties (65.6 % at 1:1 ratio); moreover, it is able to permeate central nervous system (CNS) tissues, as determined by PAMPA‐BBB assay. Notably, even when tested at very high concentrations, TFAH 10 n easily surpasses the other TFAHs in hepatotoxicity profiling (59.4 % cell viability at 1000 μM ), affording good neuroprotection against toxic insults such as Aβ1–40, Aβ1–42, H2O2, and oligomycin A/rotenone on SH‐SY5Y cells, at 1 μM . The results reported herein support the development of new multipotent TFAH derivatives as potential drugs for the treatment of Alzheimer′s disease. 相似文献