bluuebunny/crossref_metadata_2025 huggingface dataset:
Mapping the Isoprenoid Binding Pocket of PDEδ by a Semisynthetic, Photoactivatable N‐Ras Lipoprotein
Authors: Alexander Michael , Gerauer Marc , Pechlivanis Markos , Popkirova Boriana , Dvorsky Radovan , Brunsveld Luc , Waldmann Herbert , Kuhlmann Jürgen
Published: October 2008

Biologically functional Ras isoforms undergo post‐translational modifications starting with farnesylation of the most C‐terminal cysteine. Combined with further processing steps, this isoprenylation allows for the anchoring of these proteins in endomembranes, where signal transduction events take place. The specific localization is subject to dynamic regulation and assumed to modulate the activity of Ras proteins by governing their spatiotemporal distribution. The δ subunit of phosphodiesterase (PDEδ) has attracted attention as a solubilization factor of isoprenylated Ras. In this study, we demonstrate that critical residues in the putative isoprenoid pocket of PDEδ can be mapped by coupling with a semisynthetic N‐Ras lipoprotein in which the native farnesyl group of the processed protein was replaced by a photoactivatable geranyl benzophenone moiety. The crosslinked product included parts of β‐sheet 9 of PDEδ, which contains the highly conserved amino acids V145 and L147. Modeling of the PDEδ–geranyl benzophenone (GerBP) complex supports the conclusion that the photolabeled sequence is embedded in the putative isoprenoid pocket of PDEδ.
Ancillary Ligands and Spectator Cations as Controlling Factors in the Construction of Coordination and Hydrogen‐Bonded Networks with the tert‐Bu‐CC⊃Agn (n=4, 5) Supramolecular Synthon
Authors: Zhao Liang , Wan Chong‐Qing , Han Jie , Chen Xu‐Dong , Mak Thomas C. W.
Published: October 2008

Supramolecular networks constructed with the tBuCC⊃Agn (n=4 or 5) metal–ligand synthon and trifluoroacetate have been transformed through the introduction of ancillary terminal nitrile ligands, from acetonitrile through propionitrile to tert‐butyronitrile, giving rise to a 2D coordination network in AgCCtBu⋅3 AgCF3CO2⋅H2O (1), a 2D hydrogen‐bonded network in AgCCtBu⋅5 AgCF3CO2⋅4 CH3CN⋅H2O (2), a 2D hybrid coordination/hydrogen‐bonded network in AgCCtBu⋅3 AgCF3CO2⋅CH3CH2CN⋅2 H2O (3), and another 2D coordination network in AgCCtBu⋅4 AgCF3CO2⋅ (CH3)3CCN⋅2 H2O (4). Concomitantly, the linkage modes between adjacent ethynide‐bound Agn aggregates in these compounds are also changed. A layer‐type hydrogen‐bonded host lattice in isostructural AgCCtBu⋅4 AgCF3CO2⋅(R4N)(CF3CO2)⋅ 2 H2O (R4=BnMe3, 5; R4=Et4, 6; R4=nPr4, 7) is obtained by introducing quaternary ammonium cations as guest templates, which occupy the interstices and thereby mediate the interlayer separation. Use of the bulky nBu4N+ cation leads to disruption of the host network in AgCCtBu⋅4 AgCF3CO2⋅3[(nBu4N)(CF3CO2)]⋅H2O (8) with generation of a discrete dense nido‐Ag5 cluster.
Polysulfurated Pyrene‐Cored Dendrimers: Luminescent and Electrochromic Properties
Authors: Gingras Marc , Placide Virginie , Raimundo Jean‐Manuel , Bergamini Giacomo , Ceroni Paola , Balzani Vincenzo
Published: October 2008

We have synthesized a novel class of dendrimers, consisting of a polysulfurated pyrene core with appended poly(thiophenylene) dendrons (PyG0, PyG1, and PyG2, see Scheme 1), which exhibit remarkable photophysical and redox properties. In dichloromethane or cyclohexane solution they show a strong, dendron‐localized absorption band with a maximum at around 260 nm and a band in the visible region with a maximum at 435 nm, which can be assigned to the pyrene core strongly perturbed by the four sulfur substituents. The dendrimers exhibit a strong (Φ=0.6), short‐lived (τ=2.5 ns) core‐localized fluorescence band with maximum at approximately 460 nm in cyclohexane solution at 293 K. A strong fluorescence is also observed in dichloromethane solution at 293 K, in dichloromethane/chloroform rigid matrix at 77 K, and in the solid state (powder) at room temperature. The dendrimers undergo reversible chemical and electrochemical one‐electron oxidation with formation of a strongly colored deep blue radical cation. A second, reversible one‐electron oxidation is observed at more positive potential values. The photophysical and redox properties of the three dendrimers are finely tuned by the length of their branches. The strong blue fluorescence and the yellow to deep blue color change upon reversible one‐electron oxidation can be exploited for optoelectronic devices.
Size‐Specific, Colorimetric Detection of Counteranions by Using Helical Poly(phenylacetylene) Conjugated to L‐Leucine Groups through Urea Acceptors
Authors: Kakuchi Ryohei , Nagata Sachiko , Sakai Ryosuke , Otsuka Issei , Nakade Hiroshi , Satoh Toshifumi , Kakuchi Toyoji
Published: October 2008

A colorimetric detection susceptible to the dimensions of guest counteranions has been demonstrated by using poly(phenylacetylene) with L‐leucine and urea functionalities (poly‐PA‐Leu). Poly‐PA‐Leu was prepared from N‐(4‐ethynylphenylcarbamoyl)‐L‐leucine ethyl ester (PA‐Leu) by using [Rh+{η6‐C6H5)B−(C6H5)3}(2,5‐norbornadiene)] as a catalyst. The biased helical conformation of poly‐PA‐Leu was demonstrated through Cotton effects in the circular dichroism (CD) spectra. The addition of ammonium salts, including tetra‐n‐butylammonium acetate, tetra‐n‐butylammonium chloride, and tetra‐n‐butylammonium bromide anions (CH3COO−, Cl−, and Br−), into the poly‐PA‐Leu solution intensified the CD responses of poly‐PA‐Leu, which is indicative of the chiral adjustability of anion recognition by using urea groups. In addition, the combination of poly‐PA‐Leu with the CH3COO−, Cl−, and Br− anions promoted large redshifts in the absorption spectra, thus providing dramatic color changes from pale yellow to red. Guest dependency in the CD and UV/Vis spectra was clearly correlated with the size of the counteranions. Fundamentally, the addition of tetra‐n‐butylammonium nitrate, tetra‐n‐butylammonium hydrogen sulfate, tetra‐n‐butylammonium perchlorate, tetra‐n‐butylammonium azide, tetra‐n‐butylammonium fluoride, and tetra‐n‐butylammonium iodide anions (NO3−, HSO4−, ClO4−, N3−, F−, and I−) has no effect on either the CD or UV/Vis profiles of poly‐PA‐Leu. The guest specificity observed in the CD and UV/Vis spectra clearly demonstrated the guest‐dimension selectivity of poly‐PA‐Leu in counteranion recognition.
Interaction of Dinuclear Ruthenium(II) Supramolecular Cylinders with DNA: Sequence‐Specific Binding, Unwinding, and Photocleavage
Authors: Malina Jaroslav , Hannon Michael J. , Brabec Viktor
Published: October 2008

Metallosupramolecular chemistry was used to design a new class of synthetic agents, namely, tetracationic supramolecular cylinders, that bind strongly and noncovalently in the major groove of DNA. To gain additional information on interactions of the cylinders with DNA we explored DNA unwinding and sequence‐specific binding properties, as well as DNA photonuclease activity of ruthenium(II) metallosupramolecular cylinder [Ru2L3]4+, where L is a bis‐pyridylimine ligand. We found that [Ru2L3]4+ unwinds negatively supercoiled plasmid DNA and exhibits binding preference to regular alternating purine–pyrimidine sequences in a similar way to the [Fe2L3]4+ analogue. Photocleavage studies showed that, unlike [Fe2L3]4+, [Ru2L3]4+ induces single‐strand breaks on irradiation by visible and UVA light and cleaves DNA mainly at guanine residues contained preferentially in regularly alternating purine–pyrimidine nucleotides. As [Ru2L3]4+ binds and cleaves DNA in a sequence‐dependent manner, it may provide a useful tool for basic and applied biology, such as for controlled manipulation of the genome.
Biocatalytic Enantioselective Synthesis of N‐Substituted Aspartic Acids by Aspartate Ammonia Lyase
Authors: Weiner Barbara , Poelarends Gerrit J. , Janssen Dick B. , Feringa Ben L.
Published: October 2008

The gene encoding aspartate ammonia lyase (aspB) from Bacillus sp. YM55‐1 has been cloned and overexpressed, and the recombinant enzyme containing a C‐terminal His6 tag has been purified to homogeneity and subjected to kinetic characterization. Kinetic studies have shown that the His6 tag does not affect AspB activity. The enzyme processes L‐aspartic acid, but not D‐aspartic acid, with a Km of ≈15 mM and a kcat of ≈40 s−1. By using this recombinant enzyme in the reverse reaction, a set of four N‐substituted aspartic acids were prepared by the Michael addition of hydroxylamine, hydrazine, methoxylamine, and methylamine to fumarate. Both hydroxylamine and hydrazine were found to be excellent substrates for AspB. The kcat values are comparable to those observed for the AspB‐catalyzed addition of ammonia to fumarate (≈90 s−1), whereas the Km values are only slightly higher. The products of the enzyme‐catalyzed addition of hydrazine, methoxylamine, and methylamine to fumarate were isolated and characterized by NMR spectroscopy and HPLC analysis, which revealed that AspB catalyzes all the additions with excellent enantioselectivity (>97 % ee). Its broad nucleophile specificity and high catalytic activity make AspB an attractive enzyme for the enantioselective synthesis of N‐substituted aspartic acids, which are interesting building blocks for peptide and pharmaceutical synthesis as well as for peptidomimetics.
Mechanism of the Intramolecular Hydroamination of Alkenes Catalyzed by Neutral Indenyltitanium Complexes: A DFT Study
Authors: Müller Carsten , Koch Rainer , Doye Sven
Published: October 2008

Three mechanistic pathways for the [Ind2TiMe2]‐catalyzed intramolecular hydroamination of alkenes have been investigated by employing density functional theory calculations on the possible intermediates and transition states. The results indicate that the reaction cycle proceeds via a Ti–imido–amido complex as the catalytically active species. However, at the moment, the question as to whether this imido–amido complex is involved in a [2+2]‐cycloaddition with the alkene or a newly proposed insertion of the alkene into a TiN single bond cannot be answered; the calculated barriers of both the insertion mechanism and the [2+2]‐cycloaddition mechanism are similar (143 vs. 136 kJ mol−1), and both pathways are in accordance with the experimentally observed rate law (first‐order dependence on the aminoalkene concentration). Interestingly, the newly proposed insertion mechanism that takes place by an insertion of the alkene moiety into the TiN single bond of an imido–amido complex seems to be much more likely than a mechanism that involves an alkene insertion into a TiN single bond of a corresponding trisamide. The latter mechanism, which has been proposed in analogy to rare‐earth‐metal‐catalyzed hydroamination reactions, can be ruled out for two reasons: a surprisingly high activation barrier (164 kJ mol−1) and the fact that the rate‐limiting insertion step is independent of the aminoalkene concentration. This is in sharp contrast to the experimental findings for indenyltitanium catalysts.
Exploring the Reactivity of C(sp3)‐Cyclometalated IrIII Compounds in Hydrogen Transfer Reactions
Authors: Azerraf Clarite , Gelman Dmitri
Published: October 2008

The manuscript describes the synthesis and full characterization of a new PC(sp3)P‐based cyclometalated IrIII complex that manifests an exceptional thermal stability, as well as outstanding reactivity in hydrogen transfer reactions. The described compound represents the first example of a new family of stable C(sp3)‐metalated compounds.
Physical Vapor Deposition of [EMIM][Tf2N]: A New Approach to the Modification of Surface Properties with Ultrathin Ionic Liquid Films
Authors: Cremer Till , Killian Manuela , Gottfried J. Michael , Paape Natalia , Wasserscheid Peter , Maier Florian , Steinrück Hans‐Peter
Published: October 2008

Ultrathin films of the ionic liquid (IL) 1‐ethyl‐3‐methylimidazolium bis(trifluoromethylsulfonyl)imide, [EMIM][Tf2N], are prepared on a glass substrate by means of an in situ thermal‐evaporation/condensation process under ultrahigh‐vacuum conditions. By using X‐ray photoelectron spectroscopy (XPS), it is demonstrated that the first layer of the IL film grows two dimensionally, followed by the three‐dimensional growth of successive layers. The first molecular layer consists of a bilayer, with the [EMIM]+ cations in contact to the surface and the [Tf2N]− anions at the vacuum side. The ultrathin IL films are found to be stable under ambient conditions.
Charge Transport through Molecular Rods with Reduced π‐Conjugation
Authors: Lörtscher Emanuel , Elbing Mark , Tschudy Meinrad , von Hänisch Carsten , Weber Heiko B. , Mayor Marcel , Riel Heike
Published: October 2008

A series of oligophenylene rods of increasing lengths is synthesized to investigate the charge‐transport mechanisms. Methyl groups are attached to the phenyl rings to weaken the electronic overlap of the π‐subsystems along the molecular backbones. Out‐of‐plane rotation of the phenyl rings is confirmed in the solid state by means of X‐ray analysis and in solution by using UV/Vis spectroscopy. The influence of the reduced π‐conjugation on the resonant charge transport is studied at the single‐molecule level by using the mechanically controllable break‐junction technique. Experiments are performed under ultra‐high‐vacuum conditions at low temperature (50 K). A linear increase of the conductance gap with increasing number of phenyl rings (from 260 meV for one ring to 580 meV for four rings) is revealed. In addition, the absolute conductance of the first resonant peaks does not depend on the length of the molecular wire. Resonant transport through the first molecular orbital is found to be dominated by charge‐carrier injection into the molecule, rather than by the intrinsic resistance of the molecular wire length.
Interaction of NO2 with Model NSR Catalysts: Metal–Oxide Interaction Controls Initial NOx Storage Mechanism
Authors: Desikusumastuti Aine , Staudt Thorsten , Qin Zhihui , Happel Markus , Laurin Mathias , Lykhach Yaroslava , Shaikhutdinov Shamil , Rohr Friedemann , Libuda Jörg
Published: October 2008

Using scanning tunneling microscopy (STM), molecular‐beam (MB) methods and time‐resolved infrared reflection absorption spectroscopy (TR‐IRAS), we investigate the mechanism of initial NOx uptake on a model nitrogen storage and reduction (NSR) catalyst. The model system is prepared by co‐deposition of Pd metal particles and Ba‐containing oxide particles onto an ordered alumina film on NiAl(110). We show that the metal–oxide interaction between the active noble metal particles and the NOx storage compound in NSR model catalysts plays an important role in the reaction mechanism. We suggest that strong interaction facilitates reverse spillover of activated oxygen species from the NOx storage compound to the metal. This process leads to partial oxidation of the metal nanoparticles and simultaneous stabilization of the surface nitrite intermediate.
Efficient Catalytic Decomposition of Formic Acid for the Selective Generation of H2 and H/D Exchange with a Water‐Soluble Rhodium Complex in Aqueous Solution
Authors: Fukuzumi Shunichi , Kobayashi Takeshi , Suenobu Tomoyoshi
Published: October 2008

Formic acid (HCOOH) decomposes efficiently to afford H2 and CO2 selectively in the presence of a catalytic amount of a water‐soluble rhodium aqua complex, [RhIII(Cp*)(bpy)(H2O)]2+ (Cp*=pentamethylcyclopentadienyl, bpy=2,2′‐bipyridine) in aqueous solution at 298 K. No CO was produced in this catalytic decomposition of HCOOH. The decomposition rate reached a maximum value at pH 3.8. No deterioration of the catalyst was observed during the catalytic decomposition of HCOOH, and the catalytic activity remained the same for the repeated addition of HCOOH. The rhodium‐hydride complex was detected as the catalytic active species that undergoes efficient H/D exchange with water. When the catalytic decomposition of HCOOH was performed in D2O, D2 was produced selectively. Such an efficient H/D exchange and the observation of a deuterium kinetic isotope effect in the catalytic decomposition of DCOOH in H2O provide valuable mechanistic insight into this efficient and selective decomposition process.
Preparing for the ‘real’ market: national patterns of institutional learning and company behaviour in the European Emissions Trading Scheme (EU ETS)
Authors: Engels Anita , Knoll Lisa , Huth Martin
Published: October 2008

European companies have reacted in different ways to the European Emissions Trading Scheme (EU ETS), Phase I. While some companies engaged in an active trading behaviour focused on additional revenues, others adopted a strategy orientated to mere compliance with the scheme and aimed for balanced accounts only. This article provides the outcomes of a survey on company behaviour under the EU ETS in Germany, the United Kingdom, the Netherlands and Denmark from 2005 to 2006, in which cross‐national differences in trading behaviour are linked to national patterns of policy implementation and the political economies in which companies operate. Thus, specific country patterns of institutional preparation and institutional learning for the ‘real’ CO2 allowance market in Phase II of the EU ETS (2008–2012) are sketched. Whereas Phase I is distinguished by a net over‐allocation of allowances, Phase II is expected to entail some level of scarcity of allowances. We argue that companies are prepared differently to meet the challenges of the future EU ETS. Copyright © 2008 John Wiley & Sons, Ltd and ERP Environment.
A European Perspective on recent trends in US climate policy
Authors: Moslener Ulf , Sturm Bodo
Published: October 2008

Without the participation of the United States, for many years the world's largest emitter of greenhouse gases, mitigation of global climate change seems hardly conceivable. Despite the US rejection of the Kyoto Protocol and the reluctance of the Bush administration to engage in post‐Kyoto negotiations, recent developments suggest that the US position towards climate policy might change in the medium run. This study provides an overview on current trends in US climate policy. We outline the main elements of national climate policy proposals and state‐level initiatives. Based on this overview, recent trends in US climate policy are related to the European approach to combat climate change. Furthermore, we elaborate on the aspects that may be important for Europe to design its own domestic and international climate policy in order to achieve the long‐term global goal of stabilizing greenhouse gas concentrations. While it seems likely that the US will take a leading role in international climate policy, it can also be expected to challenge the European position in many respects rather than to simply support any Kyoto‐type process. Copyright © 2008 John Wiley & Sons, Ltd and ERP Environment.
Cognitive load, trigger salience, and the facilitation of triggered displaced aggression
Authors: Vasquez Eduardo Antonio
Published: October 2008

Researchers hypothesize that a state of limited cognitive processing capacity increases aggression. In the context of the triggered displaced aggression (TDA) paradigm, a 2 (Salience of triggering event: high/low) × 2 (Cognitive load at trigger: yes/no) × 2 (Cognitive load at aggression: yes/no) between participants experiment tested this hypothesis. Results showed that inducing cognitive load in previously provoked participants while they received a triggering provocation augmented aggression toward the target when the latter was highly salient. Affective reactions to the trigger partially mediated this effect. In contrast to expectation, however, inducing cognitive load while participants aggressed against their target did not affect aggression levels. Copyright © 2008 John Wiley & Sons, Ltd.
Shoes influence lower limb muscle activity and may predispose the wearer to lateral ankle ligament injury
Authors: Kerr Robin , Arnold Graham P. , Drew Tim S. , Cochrane Lynda A. , Abboud Rami J.
Published: October 2008

Lateral ankle ligaments are injured by hyperinversion of the foot. Foot position is controlled by the lower limb muscles. Awareness of foot position is impaired by wearing shoes. We aimed to determine the influence of wearing shoes upon muscle activity. Sixty‐two healthy subjects underwent the same measurements, barefoot and with standardized shoes in a random order. Electromyography (EMG) was recorded from the peroneus longus muscle in response to sudden and unanticipated inversion of the ipsilateral foot. Following foot inversion, the EMG signal showed an initial peak muscle contraction followed by a sustained smaller contraction. Both changes were significantly greater in shoes compared to the barefoot condition for all tested degrees of inversion. Muscle contraction following sudden inversion of the foot was significantly greater when wearing shoes. This greater muscular contraction may be an intrinsic mechanism to oppose the increased moment created by the inverted foot/shoe condition, and hence, may counter balance the increased tendency to injure the lateral ankle ligaments created by wearing shoes. © 2008 Orthopaedic Research Society. Published by Wiley Periodicals, Inc. J Orthop Res 27:318–324, 2009
Posterior tibial artery‐based multilobar combined flap free transfer for repair of complex soft tissue defects
Authors: Zhang Xu , Wang Xiaohua , Wen Sumin , Zhu Hongwei , Ning Zhiwen , Mi Xu , Li Chenglin , Yu Ruxia
Published: October 2008

In this report, the posterior tibial artery (PTA) based multilobar combined flap is introduced for the repair of complex soft tissue defects. The flap was designed based on the perforatoring branches of PTA in the anterior soleus muscle septum, which supply the skin over the medial side of the calf and the entire soleus muscle. The saphenous nerve was included in one perforator flap of the combined flap for reinnervation. The tibial artery was repaired with a vein graft after harvest of flap. From October 2005 to February 2007, eight patients (6 males, 2 females) underwent PTA‐based multilobar combined flap transfer for coverage of soft tissue defects involving the foot (three cases), hand (two cases), and calf (three cases). Each combined flap composed of two to three perforator flaps, and the size of the perforator flaps ranged from 4 × 2 cm to 10 × 8 cm. With an average follow‐up of 6 months, all flaps survived without complications and injured extremities showed a good functional recovery with restoration of the partial protective sensation on the flap with reinnervation. This clinical report has shown that a reliable multilobar combined flap can be designed based on the perforators of the posterior tibial artery and used for coverage of the complex wound. © 2008 Wiley‐Liss, Inc. Microsurgery, 2008.
Early surgical exploration of radial nerve injury associated with fracture shaft humerus
Authors: Noaman Hassan , Khalifa Abdel Rahman , El‐Deen Mohamed Alam , Shiha Anis
Published: October 2008

The series included 36 patients, predominantly male, mean age 30.3 years. The most common cause of injury was motor car accident in 20 patients. Postreduction radial nerve injury occurred in nine cases. Open fracture humerus with radial nerve injury in seven cases. The fractures were situated in the middle or distal third of the humeral shaft. Most were transverse fractures. Twelve patients had surgery on the day of injury and the other 24 at a mean of 8 days later (3–14). Narrow dynamic compression plate was generally used for fixation. Exploration of the radial nerve demonstrated compression at the lateral intermuscular septum in 19 cases, entrapment in the fracture site in nine cases, and loss of its continuity in eight cases. Neurolysis was required in 20 cases, epineurorrhaphy in nine cases, interfascicular nerve grafts in five, and first‐intention tendon transfer in two. Results of nerve surgery were assessed with the MRC (Medical Research Council) at a mean follow‐up of 8.2 years. Outcome was rated good to excellent in 28 patients, fair in 1, and poor (failure) in 3. First‐intention tendon transfers were performed in 2 patients and 2 patients were lost to follow‐up. Mean delay to recovery was 7 months after neurolysis and nerve repair and 15 months after nerve grafts. The fracture was united in all cases. The mean time of union was 5 months. © 2008 Wiley‐Liss, Inc. Microsurgery, 2008.
Microvascularly augmented transverse rectus abdominis myocutaneous flap for breast reconstruction—Reappraisal of its value through clinical outcome assessment and intraoperative blood gas analysis
Authors: Lee Jing‐Wei , Lee Yao‐Chou , Chang Tsai‐Wang
Published: October 2008

Our experience with 73 transverse rectus abdominis myocutaneous (TRAM) flap transfers was reviewed to see the variance in the incidence of complications among three groups of patients undergoing different types of surgical techniques. The TRAM flap was transferred as a free flap in 26 patients, a unipedicled flap in 25 patients, and a microvascularly augmented pedicled flap in 22 patients. Our data demonstrated that the incidence of partial flap loss and fat necrosis in the microvascularly augmented group was significantly lower than that in the unipedicled flap group (P < 0.01), and also lower than that in the free flap group with a statistically marginal significance (P = 0.055). Supplemental surgery is less often required in the microvascularly augmented group than in the conventional TRAM group (P = 0.002). Substantial increase in venous O2 concentration (P = 0.03), O2 saturation level (P = 0.007), and pH value (P = 0.002) was noticed following supercharge, and this very fact testifies to the perfusion‐promoting effect of the microvascular augmentation maneuver. © 2008 Wiley‐Liss, Inc. Microsurgery, 2008.
Peroneal artery perforator‐based propeller flap reconstruction of the lateral distal lower extremity after tumor extirpation: Case report and literature review
Authors: Rad Ariel N. , Singh Navin K. , Rosson Gedge D.
Published: October 2008

Background: Soft tissue defects in the distal lower extremity present a formidable challenge due to the lack of reliable local flap options. Pedicled adipofasciocutaneous flaps provide the closest match to local tissues, but random pattern flaps are limited in reliability, size, reach, and arc‐of‐rotation. One hundred and eighty degree perforator‐based propeller flaps are an innovative option because they provide robust axial perfusion to flaps with significantly greater surface area and ease of transposition versus that provided by their random pattern counterparts in these anatomic regions traditionally addressed with free tissue transfer. Case: We present a rare case of aggressive digital papillary carcinoma of the posteriolateral ankle and Achilles region. Wide local excision resulted in a defect with Achilles tendon exposure and denudation. A fasciocutaneous propeller flap based on a dominant peroneal artery perforator was raised and rotated 180° to resurface the wound, providing a gliding surface for Achilles tendon function. The reconstruction was successful with no complications, excellent contour, and esthetic appearance. Conclusions: Peroneal perforator‐based propeller flaps in the ankle region are useful local options providing unparalleled form and function, with excellent surface area and mobility, for dynamic areas of the lower extremity, without sacrificing any major vessels or nerves. This technique adds to the reconstructive microsurgeon's armamentarium for complex coverage of the ankle region. © 2008 Wiley‐Liss, Inc. Microsurgery, 2008.
Microvascular augmented pedicled jejunum transfer for vaginal reconstruction using a laparoscopy‐assisted technique
Authors: Özkan Ömer , Akar Münire Erman , Özkan Özlenen , Mesci Ayhan , Çolak Taner
Published: October 2008

Although there is no distinct, absolute, and ideal method for vaginal reconstruction, intestinal transfers are preferable to the other described techniques in the main clinics. In this report, we describe the transfer of a jejunal segment for vaginal reconstruction in a 20‐year‐old female patient, harvesting the flap based on its vascular pedicle by means of a laparoscopic technique that obviates the use of midline laparotomy. To prevent any vascular compromise, two different vascular supply sources were provided for the flap performing additional arterial and venous microvascular anastomosis. The results have confirmed the feasibility of the technique. The functional, structural, and esthetic advantages of the jejunal flap and the lower donor site morbidity of the laparoscopy‐assisted technique that were rather encouraging are described and discussed. © 2008 Wiley‐Liss, Inc. Microsurgery, 2008.
Partial muscle harvest: Our first 100 cases attempting to preserve form and function at the donor site
Authors: Brooks Darrell , Buntic Rudolf F.
Published: October 2008

The authors report their first 100 partial muscle flaps as a strategy to preserve form and function of the donor site in muscle transplantation. Between 2003 and 2007, 62 partial superior latissimus (PSL) flaps and 38 partial medial rectus (PMR) flaps were transplanted for head and neck, upper and lower extremity, and chest wall reconstruction. All flaps survived. There were hematomas at the donor sites in two PMR cases. Form and function were preserved at the donor site in all cases. The PSL provided comparable muscle volume and pedicle length to the entire rectus abdominis muscle. An additional benefit was its use as a functional muscle. The PMR flap provided comparable muscle volume to the gracilis muscle. An additional benefit was a much longer vascular pedicle. Small to moderate sized flaps can be harvested from the fabric of the latissimus dorsi and rectus abdomenis muscles and be reliably transplanted. When positioned at the superior edge of the latissimus or medial edge of the rectus muscle, adequate blood flow and innervation to the residual muscle result in preservation of form and function at the donor site. The benefits of muscle transplantation can be realized without the associated morbidity of muscle harvest. © 2008 Wiley‐Liss, Inc. Microsurgery, 2008.
Albert lautman et le souci brisé du mouvement
Authors: Alunni Charles
Published: October 2008

Nous posons l'oeuvre d'Albert Lautman comme une sorte d'opérateur de brisure de symétrie dans le cadre de l'opposition traditionnelle de la philosophie spéculative et des sciences physico-mathématiques. L'enjeu pour la philosophie en est, à de très rares exceptions près, encore très mal perçu. Sur ce plan, nous reprenons la question du « platonisme » supposé de Lautman, et nous le confrontons à sa lecture fondamentale de Martin Heidegger. Les conséquences de cette inscription dans le sillon heideggérien sont fondamentales pour une juste restitution de cette pensée et de cette philosophie dans ce qu'elles conservent de plus actuel. Sur l'autre versant, celui des percées lautmaniennes dans le champ de la physique mathématique, nous insistons sur l'extrême alacrité prospectiviste de son regard, sa puissance philosophique venant renforcer cette singulière sensibilité à ce qui fit l'essentiel des mathématiques et de la physique théorique de son temps. En ce sens, sa position occupe bel et bien l'un des points nodaux du site « surrationaliste ».
Einstein et « Zweistein »
Authors: Stachel John
Published: October 2008

Comme le suggère le sobriquet « Zweistein », Wolfgang Pauli fut considéré par la communauté des théoriciens de la physique comme son membre le plus éminent après Albert Einstein. Durant plus de trente-cinq ans, les deux hommes entretinrent des relations intellectuelles et personnelles. Cet article analyse les relations entre quatre thèmes récurrents de leurs discussions. 1) La théorie de la relativité: à l'âge de 20 ans, Pauli préparait un manuel qui fera autorité sur la relativité, manuel qu'il révisera vers la fin de sa vie et qui demeure incomparable aux yeux des physiciens et des historiens de la physique. 2) La théorie du champ unifié: même s'il éprouvait de la sympathie, à l'origine, pour les recherches d'Einstein en vue d'une unification des théories de l'électromagnétisme et de la gravitation, à laquelle il apporta plusieurs contributions majeures, Pauli en vint à considérer une telle entreprise comme stérile. 3) Les fondements de la mécanique quantique: le jugement négatif porté par Pauli sur le programme de recherche d'Einstein s'accentua en raison de leur profond désaccord sur le rôle que la mécanique quantique était appelée à jouer dans les développements futurs de la physique théorique. 4) La gravitation quantique: Pauli reconnaissait toutefois que, tant qu'une réconciliation fructueuse de la mécanique quantique et de la relativité générale ne serait pas accomplie - réconciliation qui nous échappe toujours-, les scientifiques ne pourraient ignorer le défi qu'Einstein adressait à la mécanique quantique.
Anthropologie, psychanalyse et « civilisation » du Brésil dans l'entre-deux-guerres
Authors: Dias Duarte Luis Fernando
Published: October 2008

Ce travail concerne la régulation morale de la Personne dans Je contexte du Brésil des années vingt aux années quarante, à partir de l'analyse des intenses rapports tissés dans cette période entre lanthropologie et la psychanalyse. Il décrit les conditions dans lesquelles s'établit Je dialogue entre ces deux savoirs, dans Je cadre des projets de «civilisation» du pays, entre les initiatives d'éducation et d'hygiénisation de l'État central et les débats médicaux et intellectuels sur les rapports entre l'héritage «africain» et la possibilité de dépasser la condition culturelle « arriérée » du pays.
Objective Evidence for Optimum Knot Configuration
Authors: Lee Alex C. H. , Fahmy Ramy R. R. , Hanna George B.
Published: October 2008

Background

The knot configurations used in clinical practice often are based on tradition and previous training. This study was designed to test the hypothesis that knot quality improves with the addition of a single throw in two‐throw and three‐throw knots. We tested this hypothesis by using commonly used knot configurations and suture materials.

Methods

Three suture materials, SURGIPRO, BIOSYN and POLYSORB, of 3‐0 caliber were used. The break force and integrated force of each material, a single‐hitch throw on each material, and 2160 knots of six configurations were measured by using tensiometry. The knot quality scores (KQS) of the different knot configurations were compared by using nonparametric tests.

Results

A single‐hitch throw on the suture material reduced the break force by up to 40%. The addition of an extra throw improved KQS in 2 × 1 × 1, 2 × 2, and 2 × 2 × 1 knots. The four‐throw knot configurations resulted in high KQS and low slippage rates. The 2 × 2 knots were most likely to slip and had the lowest KQS.

Conclusions

If a double‐hitch throw is used in the first throw, two to three further throws are recommended. The four‐throw knot configurations have the best knot qualities and should generally be used.
Surgical Outcome and Prognostic Factors in Intrahepatic Cholangiocarcinoma
Authors: Nakagohri Toshio , Kinoshita Taira , Konishi Masaru , Takahashi Shinichiro , Gotohda Naoto
Published: October 2008

Background

The clinicopathologic features and surgical outcome of intrahepatic cholangiocarcinoma are not fully understood.

Methods

Fifty‐six consecutive patients with intrahepatic cholangiocarcinoma who underwent surgical resection at the National Cancer Center Hospital East between October 1992 and July 2007 were retrospectively analyzed. Intrahepatic cholangiocarcinomas were subdivided into solitary tumors and tumors with intrahepatic metastasis.

Results

Complete tumor removal (R0 resection) was performed in 42 patients (75%). The 5‐year survival rate for patients with intrahepatic cholangiocarcinoma (n = 56), patients with a solitary tumor (n = 46), and patients with intrahepatic metastasis (n = 10) were 32, 38, and 0%, respectively. There was a significant difference in survival between patients with a solitary tumor and those with intrahepatic metastasis (p < 0.0001). The 5‐year survival rate for patients with stage I (n = 3), II (n = 9), III (n = 15), and IV disease (n = 26) was 100, 67, 37, and 0%, respectively. There was a significant difference in survival between stage I and stage IV (p = 0.011), between stage II and stage IV (p = 0.0002), and between stage III and stage IV (p = 0.0015). The most frequent site of recurrence was the liver. Univariate analysis showed that intrahepatic metastasis, portal vein invasion, hepatic duct invasion, lymph node metastasis, perineural invasion, and positive surgical margin (R1) were significantly associated with poor survival. Multivariate analysis confirmed that intrahepatic metastasis was a significant and independent prognostic indicator after surgical resection for intrahepatic cholangiocarcinoma (p = 0.001). No patient with intrahepatic metastasis survived more than 10 months in this study.

Conclusions

Intrahepatic metastasis was the strongest predictor of poor survival in intrahepatic cholangiocarcinoma.
Mycobacterium Chelonae Infection Following Silicone Arthroplasty of the Metacarpophalngeal Joints: A Case Report
Authors: Iordache Sorin Daniel , Daneman Nick , Axelrod Terry S.
Published: October 2008

We present a case of infection caused by an uncommon pathogen, Mycobacterium chelonae, in a patient that underwent Swanson silicone arthroplasty of the metacarpophalangeal joints for rheumathoid arthritis. This is the first report of an infection caused by nontuberculous Mycobacteria in flexible silicone implants in the hand. The patient was successfully treated with implant removal, debridement, and antimicrobials tailored to the results of in vitro susceptibility testing.
The normal form of the Navier–Stokes equations in suitable normed spaces
Authors: Olson Eric , Ziane Mohammed , Foias Ciprian , Hoang Luan
Published: October 2008

We consider solutions to the incompressible Navier–Stokes equations on the periodic domain

\Omega = [0,2\pi ]^{3}

with potential body forces. Let

\mathcal{R} \subseteq H^{1}(\Omega )^{3}

denote the set of all initial data that lead to regular solutions. Our main result is to construct a suitable Banach space

S_{A}^{ \star }

such that the normalization map

W:\mathcal{R}\rightarrow S_{A}^{ \star }

is continuous, and such that the normal form of the Navier–Stokes equations is a well-posed system in all of

S_{A}^{ \star }

. We also show that

S_{A}^{ \star }

may be seen as a subset of a larger Banach space

V^{ \star }

and that the extended Navier–Stokes equations, which are known to have global solutions, are well-posed in

V^{ \star }

.
Effect of amino acids on cell proliferation and protein p53 expression in organotypic culture of lymphoid tissue from neonatal rats
Authors: Chalisova N.I. , Zakutskii A.N.
Published: October 2008

The effect of the larger molecular weight l‐amino acids on the development of spleen explants from 1‐ and 21‐day rats in organotypic tissue culture was studied. The amino acids asparagine, lysine, arginine, and glutamic acid inhibited the growth zone of explants of immature tissue from 1‐day animals but had an opposite, stimulating, effect on mature spleen tissue of 21‐day rats. Immunohistochemical analysis revealed a reciprocal correlation between the expression of the proapoptotic protein, p53, and T‐cell proliferation in response to lysine, asparagine, and glutamic acid. Interestingly only arginine reduced the area of p53 expression both in explants of mature and immature spleen tissue. The ability of arginine to reduce p53 expression can be suggested as one of the mechanisms of the tumor growth stimulation.
Secretion from acinar cells of the exocrine pancreas: Role of enteropancreatic reflexes and cholecystokinin
Authors: Singer Manfred V. , Niebergall‐Roth Elke
Published: October 2008

Although the molecular machinery and mechanism of cell secretion in acinar cells of the exocrine pancreas is well documented and clear, only recently has the pharmacophysiology of pancreatic exocrine secretion come to light. Therefore, we focus in this article on the current understanding of the pharmacophysiology of pancreatic exocrine secretion. The pancreatic secretory response to ingestion of a meal is mediated via a complex interplay of neural, humoral and paracrine mediators. A major role in the control of the intestinal phase of pancreatic secretion is attributed to vago‐vagal enteropancreatic reflexes. In the scheme of this control mechanism, afferents originating in the duodenal mucosa, and efferents mediating central input on the pancreatic ganglia, activate intrapancreatic postganglionic neurons. Experiments utilizing specific receptor antagonists demonstrate the involvement of both muscarinic M1 and M3 receptors expressed in pancreatic acinar cells. Cholecystokinin (CCK), originally implicated in the humoral secretion of pancreatic enzymes, through a direct action on acinar CCK receptors, is also essential to the enteropancreatic reflex mechanism. CCK stimulation of the exocrine pancreatic secretion through excitation of sensory afferents of the enteropancreatic reflexes, is a paracrine mode of CCK action, and is probably the only one in humans and the predominant one in rats. In dogs, however, CCK acts on the pancreas via both the humoral and a paracrine route. More recent experiments suggest further possible sites of CCK action. Additionally, at the brain stem, vago‐vagal enteropancreatic reflexes may be modulated by input from higher brain centres, particularly the hypothalamic‐cholinergic system in the tonic stimulation of preganglionic neurons of the dorsal motor nucleus of the vagus projecting into the pancreas.
Experimental reconsideration of the utility of serum starvation as a method for synchronizing mammalian cells
Authors: Cooper Stephen , Gonzalez‐Hernandez Mariam
Published: October 2008

Accurate cell‐size determinations support the prediction that serum starvation and related whole‐culture methods cannot synchronize cells. Theoretical considerations predict that whole‐culture methods of synchronization cannot synchronize cells. Upon serum starvation, the fraction of cells with a G1‐phase amount of DNA increased, but the cell‐size distribution is not narrowed. In true synchronization, the cell‐size distribution should be narrower than the cell‐size distribution of the original culture. In contrast, cells produced by a selective (i.e. non‐whole‐culture) method have a specific DNA content, a narrow size distribution, and divide synchronously. The general theory leading to the conclusion that whole‐culture methods for synchronization do not work implies that one can generalize these serum‐starvation results to other cell lines and other whole‐culture methods, to conclude that these methods do not synchronize cells.
Association with actin mediates the EGTA‐resistant binding of cytosolic phospholipase A2‐α to the plasma membrane of activated platelets
Authors: Hastings Ann D. , Herbert Shane P. , Gawler Debra , Walker John H.
Published: October 2008

The association of cytosolic phospholipase A2‐α (cPLA2α) with intracellular membranes is central to the generation of free arachidonic acid and thromboxane A2 in activated platelets. Despite this, the site and nature of this membrane association has not been fully characterised upon platelet activation. High resolution imaging showed that cPLA2α was distributed in a partly structured manner throughout the resting platelet. Upon glass activation or thrombin stimulation, cPLA2α relocated to a peripheral region corresponding to the platelet plasma membrane. Upon thrombin stimulation of platelets a major pool of cPLA2α was associated with the plasma membrane in an EGTA‐resistant manner. EGTA‐resistant membrane binding was abolished upon de‐polymerisation of actin filaments by DNase I and furthermore, cPLA2α co‐immunoprecipitated with actin upon thrombin stimulation of platelets. Immunofluorescence microscopy studies revealed that, upon platelet activation, cPLA2α and actin co‐localised at the plasma membrane. Thus we have identified a novel mechanism for the interaction of cPLA2α with its membrane substrate via interaction with actin.
Long term exercise capacity in patients with hypertrophic cardiomyopathy treated with percutaneous transluminal septal myocardial ablation
Authors: Malek Lukasz A. , Chojnowska Lidia , Klopotowski Mariusz , Maczynska Renata , Demkow Marcin , Witkowski Adam , Kusmierczyk Beata , Piotrowicz Ewa , Konka Marek , Dabrowski Maciej , Ruzyllo Witold
Published: October 2008

Background:

In hypertrophic obstructive cardiomyopathy, percutaneous transluminal septal myocardial ablation (PTSMA) improves functional capacity in the short term. However, long term functional capacity is unknown.

Aim:

To assess the long term exercise capacity of patients with hypertrophic obstructive cardiomyopathy undergoing PTSMA.

Methods:

Twenty three patients (56.5% male, mean age 44.5±13.6 years) who underwent PTSMA were included. All patients had also undergone a symptom limited cardiopulmonary exercise treadmill test before the procedure, then after 3 months (early follow‐up) and after a mean 7.2±1.0 years (long term follow‐up).

Results:

Before PTSMA, mean maximal pressure gradient in the left outflow tract (LVOTGmax) was 82±29 mmHg, 17 patients had NYHA functional class ≥ III and peak oxygen uptake (pVO2) was 18±4 ml/kg/min. PTSMA led to a reduction in mean LVOTGmax (to 29 ± 19 mmHg. p<.0001), improvement of heart failure symptoms (NYHA≥III in 1 patient, p<.0001) and an increase of pVO2 (to 22±6 ml/kg/min, p =.0002) at short term. LVOTGmax, functional class and pVO2 did not change significantly during long term follow‐up compared to early follow‐up. However, there was a continuous improvement in percentage predicted pVO2 over time.

Conclusions:

In patients with hypertrophic obstructive cardiomyopathy and symptoms of heart failure, PTSMA leads to stable long term improvement of objectively measured exercise capacity.
Circadian expression of FGF21 is induced by PPARα activation in the mouse liver
Authors: Oishi Katsutaka , Uchida Daisuke , Ishida Norio
Published: October 2008

Peroxisome proliferator‐activated receptor α (PPARα) is a nuclear receptor that regulates the expression of genes associated with lipid metabolism. Recent studies have suggested that the expression of PPARα‐dependent fibroblast growth factor 21 (FGF21) plays important roles in adaptation to fasting, such as lipolysis and ketogenesis. We found that a nighttime injection of bezafibrate, a ligand of PPARα, effectively induced FGF21 expression, whereas a daytime injection did not affect it. Furthermore, bezafibrate‐induced circadian FGF21 expression was abolished in PPARα‐deficient mice. These observations suggest that bezafibrate‐induced circadian FGF21 expression is due to circadian variations in the responsiveness of the PPARα system in the liver.
Interaction of fatty acid with myoglobin
Authors: Sriram Renuka , Kreutzer Ulrike , Shih Lifan , Jue Thomas
Published: October 2008

Upon titration with palmitate, the 1H NMR spectra of metmyoglobin cyanide (MbCN) reveal a selective perturbation of the 8 heme methyl, consistent with a specific interaction of myoglobin (Mb) with fatty acid. Other detectable hyperfine shifted resonances of the heme group remain unchanged. Mb also enhances fatty acid solubility, as reflected in a more intense methylene peak of palmitate in Mb solution than in Tris buffer. Ligand binding analysis indicates an apparent palmitate dissociation constant (K
d) of 43 μM. These results suggest that Mb can bind fatty acid and may have a role in facilitating fatty acid transport in the cell.
The peripheral light‐harvesting complexes from purple sulfur bacteria have different ‘ring’ sizes
Authors: Kereïche Sami , Bourinet Laurent , Keegstra Wilko , Arteni Ana A. , Verbavatz Jean-Marc , Boekema Egbert J. , Robert Bruno , Gall Andrew
Published: October 2008

The integral membrane light‐harvesting (LH) proteins from purple photosynthetic bacteria form circular oligomers of an elementary unit that is composed of two very hydrophobic polypeptides, termed α and β. These apoprotein dimers are known to associate into closed circular arrays of 8, 9 and 16 α/β‐mers. We report the existence of peripheral LH proteins purified from Allochromatium vinosum with two intermediate ring sizes and postulate that one is a 13 α/β‐mer. This shows that LH proteins are able to form membrane rings of continuously increasing diameter from 68 to 115 Å. The presence of these new ring sizes warrants further study, as it will help to further validate the structure–function models of LH proteins currently found in the literature.