bluuebunny/crossref_metadata_2025 huggingface dataset:
Flow‐cytometric analysis of peripheral blood neutrophils: A simple, objective, independent and potentially clinically useful assay to facilitate the diagnosis of myelodysplastic syndromes
Authors: Cherian Sindhu , Moore Jonni , Bantly Andrew , Vergilio Jo‐Anne , Klein Peter , Luger Selina , Bagg Adam
Published: June 2005

The diagnosis of myelodysplastic syndromes (MDS) is based upon cytopenias, morphologic dysplasia, and cytogenetic abnormalities. Because morphologic dyspoiesis may be subtle, and many cases have normal cytogenetics, additional objective diagnostic tools are needed. We previously developed a novel peripheral blood neutrophil flow‐cytometric (FCM) scoring system to identify patients with MDS. Here, in an analysis of 25 patients, we demonstrate that FCM abnormalities are independent of currently measured parameters in MDS, including cytopenias, marrow blast percent, and IPSS score. Importantly, FCM abnormalities were seen in 9/16 MDS patients with normal cytogenetics, suggesting that this simple, non‐invasive assay could play a central role in the diagnosis of MDS. Am. J. Hematol. 79:243–245, 2005. © 2005 Wiley‐Liss, Inc.
Evaluation of single‐tube osmotic fragility as a screening test for thalassemia
Authors: Chow Jason , Phelan Lorraine , Bain Barbara J.
Published: June 2005

A single‐tube osmotic fragility test has been proposed for thalassemia screening with a range of different concentrations of saline having been employed. We have compared the sensitivity and specificity of 0.32%, 0.34%, and 0.36% buffered saline, and on the basis of our findings, recommend the use of 0.36% saline. This gave definitely positive or equivocal results in 81 of 85 patients with β thalassemia trait and in 4 of 4 with α0 thalassemia trait. There were 14% false positive results in hematologically normal patients and 81% of the samples from patients with various variant hemoglobins gave positive results. The sensitivity was 95% and specificity 86%. The single‐tube osmotic fragility test is potentially useful in under‐resourced laboratories although it cannot replace automated red cell indices using electronic counters. Am. J. Hematol. 79:198–201, 2005. © 2005 Wiley‐Liss, Inc.
Titelbild: Supramolecular Coordination Assemblies of Dinuclear FeIII Complexes (Angew. Chem. 27/2005)
Authors: Schmitt Wolfgang , Hill Jonathan P. , Juanico M. Paula , Caneschi Andrea , Costantino Ferdinando , Anson Christopher E. , Powell Annie K.
Published: June 2005

Fleißigen Bienen könnten die im Titelbild gezeigten Honigwaben‐Netzwerke auch gefallen. Die Netzwerke beruhen auf zweikernigen FeIII‐Einheiten, Aminocarbonsäure‐Liganden und Kalium‐Gegenionen. Die Eigenschaften der hydrophoben organischen Liganden haben einen großen Einfluss auf die Struktur der hydrophilen anorganischen Zone, die wiederum die Gesamtstruktur der supramolekularen Gebilde prägt. Mehr über diese Untersuchungen findet sich in der Zuschrift von W. Schmitt, A. K. Powell et al. auf S. 4259 ff.
Cover Picture: Supramolecular Coordination Assemblies of Dinuclear FeIII Complexes (Angew. Chem. Int. Ed. 27/2005)
Authors: Schmitt Wolfgang , Hill Jonathan P. , Juanico M. Paula , Caneschi Andrea , Costantino Ferdinando , Anson Christopher E. , Powell Annie K.
Published: June 2005

Busy bees may also find the honeycomb networks shown in the cover picture attractive. The networks are based on dinuclear FeIII subunits, aminocarboxylic acid ligands, and potassium counterions. The properties of the hydrophobic organic ligands strongly influence the structure of the hydrophilic inorganic zone which in turn affects the overall structure of the supramolecular assemblies. For more information on this approach see the Communication by W. Schmitt, A. K. Powell, and co‐workers on page 4187 ff.
Structural changes during the thermal stabilization of modified and original polyacrylonitrile precursors
Authors: Jie Liu , Wangxi Zhang
Published: June 2005

A polyacrylonitrile (PAN) precursor fiber of a special grade for preparing carbon fibers was modified by the impregnation of an aqueous KMnO4 solution. The effects of the modification on the lateral and morphology structure, related to the crystalline properties of both the precursors and preoxidized fibers, such as the orientation index, crystal size, and crystallinity index, were measured by wide‐angle X‐ray diffraction. For both modified and original PAN fibers, a comparative study of the changes of the elemental content during the process of preoxidation, the relations between the thermal stress and heat‐treatment temperature, and the effect of the modification on the skin/core structure of a preoxidized fiber were also introduced by the use of elemental analysis, optical microscopy, and so on. The modification of KMnO4 was demonstrated to increase the density, increase the crystallinity index, increase the preferred orientation index, and decrease the crystal size for a modified precursor fiber and for a preoxidized fiber developed from a modified precursor fiber after a different heat‐treatment temperature. KMnO4 also showed a catalytic action, accelerating the rate of preoxidation and reducing the time of thermal stabilization; this improved the homogenization of the cross‐section structure and led to an improvement in the tensile strength of 15–20% and an improvement in the elongation of 20–30% in the resulting carbon fibers. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 2047–2053, 2005
Normal distribution of melanocytes in the mouse heart
Authors: Mjaatvedt Corey H. , Kern Christine B. , Norris Russel A. , Fairey Sarah , Cave Courtney L.
Published: June 2005

We report the consistent distribution of a population of pigmented trp‐1‐positive cells in several important septal and valvular structures of the normal mouse (C57BL/6) heart. The pigmented cell population was first apparent by E16.5 p.c. in the right atrial wall and extended into the atrium along the interatrial septum. By E17.5, these cells were found along the apical membranous interventricular septum near or below the surface of the endocardium. The most striking distribution of dark pigmented cells was found in the tricuspid and mitral valvular leaflets and chordae tendineae. The normal distribution of pigmented cells in the valvuloseptal apparatus of C57BL/6 adult heart suggests that a premelanocytic lineage may participate in the earlier morphogenesis of the valve leaflets and chordae tendineae. The origin of the premelanocyte lineage is currently unknown. The most likely candidate populations include the neural crest and the epicardially derived cells. The only cell type in the heart previously shown to form melanocytes is the neural crest. The presence of neural crest cells, but not melanocytes, in some of the regions we describe has been reported by others. However, previous reports have not shown a contribution of melanocytes or neural crest derivatives to the atrioventricular valve leaflets or chordae tendineae in mouse hearts. If these cells are of neural crest origin, it would suggest a possibly greater contribution and persistence of neural crest cells to the valvuloseptal apparatus than has been previously understood. © 2005 Wiley‐Liss, Inc.
Internal luminal pressure during early chick embryonic brain growth: Descriptive and empirical observations
Authors: Desmond Mary E. , Levitan Michael L. , Haas Andrew R.
Published: June 2005

If the intraluminal pressure of the brain is decreased for 24 hr, the brain and neuroepithelium volumes are both reduced in half. The current study measured the intraluminal pressure throughout the period of rapid brain growth using a servo‐null micropressure monitoring system. From 613 measurements made on 55 embryos, we show that the intraluminal pressure over this time period is appropriately described by a linear model with correlation coefficient of 0.752. To assess whether sustained hyperpressure would increase mitosis, elevated intraluminal pressure was induced in 10 embryos for 1‐hr duration via a gravity‐fed drip. The mitotic density and index of the mesencephalon were measured for the 10 embryos. Those embryos, in which the colchicine solution was added to the intraluminal cerebrospinal fluid creating a sustained hyperpressure, exhibited at least a 2.5‐fold increase in both the mitotic density and index compared with control embryos. Based on the small sample size, we cautiously conclude that sustained hyper‐intraluminal pressure does stimulate mitosis. © 2005 Wiley‐Liss, Inc.
Regional cardiac ganglia projections in the guinea pig heart studied by postmortem DiI tracing
Authors: Harrison Theresa A. , Perry Kristi M. , Hoover Donald B.
Published: June 2005

Our purpose was to identify and localize intrinsic cardiac ganglia innervating distinct regions of the heart using postmortem tracing of nerve projections with DiI, a method not previously used to study the intrinsic cardiac nervous system. We also investigated the possibility of collateral innervation of myocardium and intrinsic ganglia. In isolated paraformaldehyde‐fixed guinea pig hearts, crystals of DiI (1,1′‐dioctadecyl‐3,3,3′,3′‐tetramethylindocarbocyanine perchlorate) were inserted into the posterior ventricular myocardium below the atrioventricular groove, the right atrium, or the left ventricular septum. Hearts were placed in the dark at 37°C for 2–14 weeks to allow DiI diffusion within neuronal membranes. Labeled neurons were observed in intracardiac ganglia after at least 4 weeks of dye exposure. Labeling was restricted to the inferior‐most ganglia (those near the atrioventricular groove) when DiI was inserted into the posterior ventricular myocardium and to ganglia near the sinus node after right atrial DiI placement. Application of DiI to the left ventricular septum resulted in neuron labeling in ganglia primarily in the interatrial septum near the atrioventricular node. After 8 weeks, DiI‐labeled nerve fibers and varicosities were seen surrounding unlabeled neurons in some ganglia, suggesting that axons terminating in or passing through the DiI application site in posterior ventricular tissue had collateral branches innervating these ganglia. These results indicate that intrinsic innervation of major cardiac subdivisions is accomplished by regionally segregated cardiac ganglia. Also, tracing with DiI has provided evidence for collateral nerve projections that could be the substrate for novel intracardiac regulatory circuits. © 2005 Wiley‐Liss, Inc.
Results of the magnetic survey at Deir al‐Barsha, Egypt
Authors: Herbich Tomasz , Peeters Christoph
Published: June 2005

The site of Deir al‐Barsha (Middle Egypt) is well known for its nomarchal rock tombs cut in the cliffs and dating to the Middle Kingdom (2040–1640 BC), but the presence of a necropolis of the same date in the sandy gravel desert plain was seldom mentioned in the past. Part of this necropolis had been investigated at the beginning of the twentieth century, but no plans or detailed accounts were ever published. The tombs were observed then to be structures lined with mud bricks with shafts going down several metres. In 2002, when archaeologists returned to this burial ground, few of the archaeological remains were still visible on the surface, the area being pitted with deep craters left over from the earlier excavations. The objective of the research, which was to gain insight into the overall organization and social stratification of the cemetery, required the use of the magnetic surveying method. A series of anomalies was registered in effect and interpreted as the images of shafts and accompanying ground structures (circuit walls). Several of these features have already been verified in excavations. The magnetic study has also led to the discovery of a previously unrecognized dirt road cutting across the necropolis from the nomarchal tombs to the Nile valley. The research has also attested later post‐burial human activity: the magnetic maps have provided a record of several hundred of pits dug by grave robbers and not visible presently on the surface. Copyright © 2005 John Wiley & Sons, Ltd.
Detection of archaeological crop marks on declassified CORONA KH‐4B intelligence satellite photography of Southern England
Authors: Fowler Martin J. F. , Fowler Yvonne M.
Published: June 2005

Recently declassified intelligence satellite photographs acquired in the 1960s and early 1970s by the CORONA programme have been found to be an important source of low‐cost, relatively high resolution, overhead photography that can be used in the prospection for archaeological features. Hitherto, the material has been used primarily to detect archaeological features in the arid regions of Asia Minor and the Middle East either in relief or through changes in soil tone resulting from the presence of former human habitation. In this paper the authors describe, for the first time, the detection of archaeological crop marks on CORONA KH‐4B photography of southern England indicating that there could be a wider utility of the CORONA archive for archaeological prospection in temperate regions. Copyright © 2005 John Wiley & Sons, Ltd.
Synthesis and Properties of Electrophosphorescent Chelating Polymers with Iridium Complexes in the Conjugated Backbone
Authors: Zhen Hongyu , Jiang Changyun , Yang Wei , Jiang Jiaxing , Huang Fei , Cao Yong
Published: June 2005

The synthesis of electrophosphorescent chelating polymers by Suzuki polycondensation of A‐A‐ and B‐B‐type monomers is described, in which the fluorene‐alt‐carbazole (PFCz) segment is used as polymer backbone. By using alkyl‐substituted ligands of iridium complex monomers, chelating copolymers with higher contents of iridium complex can be synthesized. Chemical and photophysical characterization confirm that the Ir complex is incorporated into the polymer backbone as one of the monomer repeat units by means of two 5‐bromotolylpyridine ligands. Chelating polymers with Ir complexes in the conjugated polymer backbone show highly efficient energy transfer of excitons from the PFCz host segment to the Ir complex by an intramolecular trapping mechanism. The external quantum and luminous efficiencies of a device made with PFCzMppyIrhm4 copolymer reach 4.1 % ph/el (photons/electron) and 5.4 cd A−1, respectively, at a current density of 32.2 mA cm−2, an emission peak of 577 nm, and a luminance of 1730 cd cm−2. Most important, the devices made from the chelating copolymers show no notable efficiency decay with increasing current density due to reduced concentration quenching and triplet–triplet (T–T) annihilation. This indicates that incorporation of the phosphorescent complex into the rigid conjugated polymer main chain is a new way to simultaneously realize high efficiency, long‐term stability, and simple processing of phosphorescent polymer light‐emitting diodes.
Nonlinear Optical Properties in Calix[n]arenes: Orientation Effects of Monomers
Authors: Datta Ayan , Pati Swapan K.
Published: June 2005

We investigate the nonlinear optical (NLO) polarizations for various geometric arrangements of the dipolar chromophores in a calix[n]arene geometry. The interactions were studied by using (HF)3as model compounds both in parallel and frustrated orientations. The interdipolar angle between the monomer molecules is varied so that many different arrangements of the dipoles can be realized which is associated with the opening up of the calix[n]arene rings. Quantum‐chemical calculations at both ab initio and semiempirical levels, show that the all‐parallel arrangement of the dipoles exhibit the maximum magnitude for the nonlinear optical coefficients at small interdipolar angles for all interdipolar distances. In the frustrated orientations however, the NLO response is maximum at large interdipolar angles corresponding to the flattened calix[n]arene rings. The role of hydrogen bonding in stabilizing these assemblies in various conformations has been investigated. Crystallographic database analysis for calix[3]arenes shows that optical properties in real molecular systems can be modeled based on our simple interaction theory.
IPy2BF4‐Mediated Rearrangements of 1,2‐Difunctionalized Compounds and Olefins
Authors: Fañanás Francisco J. , Álvarez‐Pérez Mónica , Rodríguez Félix
Published: June 2005

Acetal derivatives are easily obtained from 1,2‐difunctionalized compounds by a new reaction mediated by IPy2BF4 with a mechanism based on a 1,2‐migration of aryl or alkyl groups. A new oxidative rearrangement reaction of olefins is also described. Moreover, when this metal‐free protocol is applied to cyclic olefins, interesting ring‐contraction reactions are observed. The new methodologies described here are a clean and efficient alternative to known strategies that make use of potentially toxic metallic complexes.
Intramolecular Hydrogen‐Bond‐Assisted Planarization of Asymmetrically Functionalized Alternating Phenylene–Pyridinylene Copolymers
Authors: Vetrichelvan Muthalagu , Valiyaveettil Suresh
Published: June 2005

We report on the synthesis and characterization of a series of asymmetrically functionalized amphiphilic polymers with alternating π‐donor units (e.g., substituted benzene) and π‐acceptor units (e.g., pyridine) along the polymer backbone. The purpose of our present work involves incorporation of functional groups along the main chain to form intrachain hydrogen bonds, which promote planarization of the polymer backbone, and to fine‐tune the optical properties. The structure–property relationship of polymers P 1–P 6 was investigated by means of analytical methods, such as FTIR spectroscopy, 1H and 13C NMR spectroscopy, UV/Vis spectroscopy, fluorescence spectroscopy, gel permeation chromatography, thermogravimetric analysis, cyclic voltammetry, and X‐ray powder diffraction. All polymers were soluble in common organic solvents, and the optical and fluorescence spectra of the polymers showed significant changes according to the formation (P 4, P 5) or absence (P 6) of intramolecular hydrogen bonding along the polymer backbone. Moreover, the 2,6‐ or 3,5‐linkage of the pyridine rings in P 5 and P 6, respectively, reduced the conjugation along the polymer backbone and this is reflected in their optical properties. The optical properties of the polymers were influenced by the addition of acid (P 1–P 6), base (P 4–P 6), and metal ions (e.g., Cu2+, Fe3+, Ag+, Ni2+, Pd2+, Mn2+, Zn2+, Mg2+, and Pr3+). Such polymers could be used in various applications, including sensors and stimuli‐responsive displays.
Synthesis, Crystal Structures, and Properties of Oxovanadium(IV)–Lanthanide(III) Heteronuclear Complexes
Authors: Shi Wei , Chen Xiao‐Yan , Zhao Yan‐Nan , Zhao Bin , Cheng Peng , Yu Ao , Song Hai‐Bin , Wang Hong‐Gen , Liao Dai‐Zheng , Yan Shi‐Ping , Jiang Zong‐Hui
Published: June 2005

A new series of oxovanadium(IV)–lanthanide(III) heteronuclear complexes [Yb(H2O)8]2[(VO)2(TTHA)]3⋅21 H2O (1), {[Ho(H2O)7(VO)2(TTHA)][(VO)2(TTHA)]0.5}⋅ 8.5 H2O (2), {[Gd(H2O)7(VO)2(TTHA)][(VO)2(TTHA)]0.5}⋅8.5 H2O (3), {[Eu(H2O)7][(VO)2(TTHA)]1.5}⋅ 10.5 H2O (4), and [Pr2(H2O)6(SO4)2][(VO)2(TTHA)] (5) (H6TTHA=triethylenetetraaminehexaacetic acid) were prepared by using the bulky flexible organic acid H6TTHA as structure‐directing agent. X‐ray crystallographic studies reveal that they contain the same [(VO)2(TTHA)]2− unit as building block, but the Ln3+ ion lies in different coordination environments. Although the lanthanide ions always exhibit similar chemical behavior, the structures of the complexes are not homologous. Compound 1 is composed of a [Yb(H2O)8]3+ ion and a [(VO)2(TTHA)]2− ion. Compounds 2 and 3 are isomorphous; both contain a trinuclear [Ln(H2O)7(VO)2(TTHA)]+ (Ln=Ho for 2 and Gd for 3) ion and a [(VO)2(TTHA)]2− ion. Compound 4 is an extended one‐dimensional chain, in which each Eu3+ ion links two [(VO)2(TTHA)]2− ions. For 5, the structure is further assembled into a three‐dimensional network with an interesting framework topology comprising V2Pr2 and V4Pr2 heterometallic lattices. Moreover, 4 and 5 are the first oxovanadium(IV)–lanthanide(III) coordination polymers and thus enlarge the realm of 3d–4f complexes. The IR, UV/Vis, and EPR spectra and the magnetic properties of the heterometallic complexes were studied. Notably, 2 shows unusual ferromagnetic interactions between the VO2+ and Ho3+ ions.
Deformed Phthalocyanines: Synthesis and Characterization of Zinc Phthalocyanines Bearing Phenyl Substituents at the 1‐, 4‐, 8‐, 11‐, 15‐, 18‐, 22‐, and/or 25‐Positions
Authors: Fukuda Takamitsu , Homma Shigetsugu , Kobayashi Nagao
Published: June 2005

The synthesis of a series of zinc phthalocyanines partially phenyl‐substituted at the 1‐, 4‐, 8‐, 11‐, 15‐, 18‐, 22‐, and/or 25‐positions (the so‐called α‐positions) is reported. Macrocycle formation based on 3,6‐diphenylphthalonitrile, o‐phthalonitrile, and zinc acetate predominantly yielded the near‐planar disubstituted complex and opposite tetrasubstituted isomer, while the lithium method yielded the sterically hindered hexasubstituted complex and adjacent tetrasubstituted isomer. All compounds have been characterized by 1H NMR, MALDI‐TOF‐MS, and elemental analysis methods. In addition, crystal structures have been solved for the di‐, hexa‐, and octasubstituted complexes and the adjacent tetrasubstituted isomer. DFT geometry optimization calculations predict more highly deformed structures than those observed in the crystals. The packing force of the crystals cannot therefore be ignored, particularly for the less phenyl‐substituted derivatives. The crystal structures have revealed that overlap of the phenyl groups causes substantial deformation of the phthalocyanine (Pc) ligands within the crystals, while strong π–π stacking in the remainder of the Pc moiety lacking phenyl substituents can suppress the impact of the deformation. Absorption spectra show sizable red shifts of the Q‐band with increasing number of phenyl groups. Analysis of the results of absorption spectra and electrochemical measurements reveals that a substantial portion of the red shift is attributable to the ring deformations. Molecular orbital calculations lend further support to this conclusion. A moderately intense absorption band emerging at around 430 nm for highly deformed octaphenyl‐substituted zinc Pc can be assigned to the HOMO→LUMO+3 transition, which is parity‐forbidden for planar Pcs, but becomes allowed since the ring deformations remove the center of symmetry.
Efficient CF and CC Activation by a Novel N‐Heterocyclic Carbene–Nickel(0) Complex
Authors: Schaub Thomas , Radius Udo
Published: June 2005

The NHC‐stabilized complex [Ni2(iPr2Im)4(cod)] (1) was isolated in good yield from the reaction of [Ni(cod)2] with 1,3‐diisopropylimidazole‐2‐ylidene (iPr2Im). Compound1is a source of the [Ni(iPr2Im)2] complex fragment in stoichiometric and catalytic transformations. The reactions of1with ethylene and CO under atmospheric pressure or with equimolar amounts of diphenylacetylene lead to the compounds [Ni(iPr2Im)2(η2‐C2H4)] (2), [Ni(iPr2Im)2(η2‐C2Ph2)] (3), and [Ni(iPr2Im)2(CO)2] (4) in good yields. In all cases the [Ni(iPr2Im)2] complex fragment is readily transferred without decomposition or fragmentation. In the infrared spectrum of carbonyl complex4, the CO stretching frequencies are observed at 1847 and 1921 cm−1, and are significantly shifted to lower wavenumbers compared with other nickel(0) carbonyl complexes of the type [NiL2(CO)2]. Complex1activates the CF bond of hexafluorobenzene very efficiently to give [Ni(iPr2Im)2(F)(C6F5)] (5). Furthermore, [Ni2(iPr2Im)4(cod)] (1) is also an excellent catalyst for the catalytic insertion of diphenylacetylene into the 2,2′ bond of biphenylene. The reaction of1with equimolar amounts of biphenylene at low temperature leads to [Ni(iPr2Im)2(2,2′‐biphenyl)] (6), which is formed by insertion into the strained 2,2′ bond. The reaction of diphenylacetylene and biphenylene at 80 °C in the presence of 2 mol % of1as catalyst yields diphenylphenanthrene quantitatively and is complete within 30 minutes.
Synthesis and Optical Resolution of a Series of Inherently Chiral Calix[4]crowns with Cone and Partial Cone Conformations
Authors: Luo Jun , Zheng Qi‐Yu , Chen Chuan‐Feng , Huang Zhi‐Tang
Published: June 2005

A series of inherently chiral calix[4]arenes with cone and partial cone conformations and with crown ether moieties of variable size have been readily synthesized. By taking advantage of the carboxy appendage on the lower rim, these were condensed with the chiral auxiliary (S)‐BINOL to form diastereomers which, in most cases, could be separated by preparative TLC, or more desirably, by column chromatography on silica gel (diastereomeric excess >99 % based on HPLC analysis). Seven enantiopure antipodes of inherently chiral calix[4]crowns were obtained after hydrolysis. It has been found that both the size of the crown moiety and alkylation of the last phenolic hydroxy group (accompanied with or without a change in the conformation) affect the separation of the diastereomers.
Selective Guest Encapsulation by a Cobalt‐Assembled Cage Molecule
Authors: Harrison Roger G. , Burrows Jessica L. , Hansen Lee D.
Published: June 2005

Metal‐assembled resorcinarene‐based cages enclose space and entrap organic molecules from water. Addition of cobalt(II) ions to a neutral, aqueous solution of a resorcinarene that has iminodiacetic acids attached to its upper rim results in the formation of cages. These cages not only entrap organic molecules, but they do so in a selective manner. Guests with optimum size, shape, and polarity are preferentially entrapped. For example, selection of p‐xylene is twenty thousand times more favorable than that of m‐xylene. The enthalpy of resorcinarene deprotonation and cage formation was calculated by performing calorimetry studies and ranged from −305 to −348 kJ mol−1. The change in enthalpy of guest encapsulation varied by as much as 43 kJ mol−1. The differences in change in free energy of guest encapsulation varied by −16 kJ mol−1. The changes in enthalpy and free energy of guest encapsulation were used to calculate the changes in entropy, which ranged from −97 to +37 J mol−1 K−1. An enthalpy–entropy compensation of guest encapsulation was observed.
Rigid Nanoscopic Containers for Highly Dispersed, Stable Metal and Bimetal Nanoparticles with Both Size and Site Control
Authors: Wang Chunlei , Zhu Guangshan , Li Jian , Cai Xiaohui , Wei Yuhong , Zhang Daliang , Qiu Shilun
Published: June 2005

We demonstrate a novel strategy for the preparation of mesoporous silica‐supported, highly dispersed, stable metal and bimetal nanoparticles with both size and site control. The supporting mesoporous silica, functionalized by polyaminoamine (PAMAM) dendrimers, is prepared by repeated Michael addition with methyl acrylates (MA) and amidation reaction with ethylenediamine (EDA), by using aminopropyl‐functionalized mesoporous silica as the starting material. The encapsulation of metal nanoparticles within the dendrimer‐propagated mesoporous silica is achieved by the chemical reduction of metal‐salt‐impregnated dendrimer–mesoporous silica by using aqueous hydrazine. The site control of the metal or bimetal nanoparticles is accomplished by the localization of inter‐ or intradendrimeric nanoparticles within the mesoporous silica tunnels. The size of the encapsulated nanoparticles is controlled by their confinement to the nanocavity of the dendrimer and the mesopore. For Cu and Pd, particles locate at the lining of mesoporous tunnels, and have diameters of less than 2.0 nm. For Pd/Pt, particles locate at the middle of mesoporous tunnels and have diameters in the range of 2.0–4.2 nm. The Pd and Pd/Pt nanoparticles are very stable in air, whereas the Cu nanoparticles are stable only in an inert atmosphere.
Wiederaufladbare Batterien
Authors: Winter Martin , Besenhard Jürgen O.
Published: June 2005

As a matter of fact, most of our technical electrochemical energy storage systems operate outside the limitations of thermodynamics. As in the case of rechargeable batteries with aqueous electrolytes (part I of this article), kinetics control the operation and safety also in batteries with nonaqueous electrolytes (this second and final part).A striking example is the lithium ion battery which possesses an operating voltage of >3,5 V and a very high energy density. From a thermodynamic viewpoint such a cell is impossible because the used organic electrolyte is in contact with two lithium insertion electrodes that operate at extreme reducing and oxidizing potentials, respectively. However, a unique mechanism kinetically prevents the decomposition of the electrolyte due to the formation of electronically insulating interphases between electrode and electrolyte that are still permeable to the electrochemically active Li+ cations. Lithium ion batteries have already made their breakthrough into the market as small format systems for portable electronics. The only „kinetically shielded”︁ high energy density, however, might be a safety complication for large format batteries, which are assembled for electric vehicle (EV) propulsion. Safety concerns are also valid for high temperature (300°C) batteries such as the sodium‐sulfur and sodium‐nickel chloride systems. These systems are still in the stage of „experimental batteries”︁, which may find future application in large units for EV's or uninterruptible power systems. The paper is concluded by a performance comparison of various rechargeable battery systems with aqueous and nonaqueous electrolytes. (Possible) applications in consumer electronics and EV's are discussed in more detail.
Kupfer — Die biochemische Bedeutung eines Metalls
Authors: Pascaly Matthis , Jolk Ingo , Krebs Bernt
Published: June 2005

The essential trace element copper plays a key role in living systems. Its metalloproteins are involved in various reactions. The IT ononuclear blue copper type‐1 proteins take, part in electron transfer processes. Type‐2 proteins can either act as oxidases, oxygenases, dioxygenases, or superoxide dismutases, containing one copper core. Dinuclear copper centers of Type‐3 proteins are the oxygen transport system hemocyanin, oxidases and oxygenases. Due to this variety of functions copper deficiency and also abundance can cause severe damage of any life form.
Sandwich‐artige Cyclopentadienylkomplexe von Hauptgruppenelementen
Authors: Jutzi Peter
Published: June 2005

Cyclopentadienyl (Cp) complexes of maingroup elements are classified and compared in terms of structural types, bonding features, and characteristic reactions. Halfsandwich, sandwich and multidecker sandwich arrangements of different type are observed including cluster species with weak or strong metal‐metal bonds. The Cp‐El bonding ranges from mainly covalent to purely ionic with important structure‐determining intermolecular contacts in the latter. π‐Complexation allows the stabilisation of compounds with low‐valent elements such as AI(I), Ga(I), and Si(I1). Important reaction principles and applications are shortly described.
Chemische Biologie
Authors: Splittgerber Ute
Published: June 2005

Chemische Biologie ist eine junge Forschungsrichtung im Grenzgebiet zwischen Organischer Cherme und Zellbiologie, welche aus einem Bedarf nach neuen Techniken zur Untersuchung zellbiologischer Mechanismen entstanden ist. Chemische Methoden werden mit biochemischen und molekularbiologischen Methoden kombiniert, um neuartige Möglichkeiten für die biologische Grundlagenforschung zu schaffen. So werden synthetische Oligosaccharide kovalent an die Oberfläche lebender Zellen gebunden, die Konzentration von Calciumionen im Zytosol künstlich reguliert und Rezeptoren künstlich aktiviert.
Fritz Haber, Carl Bosch und Friedrich Bergius — Protagonisten der Hochdrucksynthese
Authors: Stoltzenberg Dietrich
Published: June 2005

It is tried to fix the limits between the notions high pressure synthesis and high temperature chemistry. The work of Fritz Haber to apply high pressure to synthetise ammonia and of Friedrich Bergius to liquify coal to synthetise petrol is described. Special attention is given to the merits of Carl Bosch and his coworkers at BASF for applying the high pressure synthesis into industrial scale. The consequences of thc work of Haber, Bergius und Bosch on chemistry, social and political life and their importance for the present are considered.
Elektrosynthesen. Strom doppelt genutzt: Erste technische „Paired Electrosynthesis”︁
Authors: Hannebaum Heinz , Pütter Hermann
Published: June 2005

Eine neue Elektrosynthese erfüllt erstmals den Traum der Elektrochemiker, gleichzeitig Anoden‐ und Kathodenreaktion für organische Synthesen technisch zu nutzen.
Vorbereitungen für die Jahrtausend‐Party
Authors: Magin Rudolf
Published: June 2005

Around the world, BASF has been preparing for Y2K since 1996. The Information services and the Process Control Technology divisions, as well as embedded systems and logistics, not to mention the company's customers and suppliers have all been systenmatically tested for Y2K capability. In addition, special precautionary measures in particular, at large Verbund sites – will be in place during the switchover period.
Successful carboplatin desensitization in patients with proven carboplatin allergy
Authors: Confino‐Cohen Ronit , Fishman Amiram , Altaras Marco , Goldberg Arnon
Published: June 2005

BACKGROUND

Carboplatin is one of the most useful and well tolerated cytotoxic drugs for gynecologic malignancies. Hypersensitivity to carboplatin is not rare among patients receiving multiple recurrent treatments with this drug. The aim of the current study was to offer a safe and convenient carboplatin desensitization strategy to patients with a proven allergic reaction to this drug.

METHODS

Patients with an immediate objective allergic reaction to carboplatin were skin tested with the drug. A 6‐hour carboplatin desensitization protocol was administered to the patients with a carboplatin‐positive skin test on each of the following treatment courses.

RESULTS

Twenty‐three patients with an allergic reaction to carboplatin and a positive skin test were included in the current study. Twenty patients (86.9%) were desensitized. One patient developed a mild urticarial rash. Nineteen patients tolerated 80 desensitization courses uneventfully.

CONCLUSIONS

The data presented a successful desensitization protocol for individuals with a proven allergic reaction to carboplatin. The protocol was safe and convenient and offered an effective therapeutic strategy to patients who required this drug. Cancer 2005. © 2005 American Cancer Society.
2‐Chlorodeoxyadenosine and cytarabine combination therapy for idiopathic hypereosinophilic syndrome
Authors: Jabbour Elias , Verstovsek Srdan , Giles Francis , Gandhi Varsha , Cortes Jorge , O'Brien Susan , Plunkett William , Garcia‐Manero Guillermo , Ellen Jackson C. , Kantarjian Hagop , Andreeff Michael
Published: June 2005

BACKGROUND

Hypereosinophilic syndrome (HES) is a rare, disabling, and incurable disease. In this study, a combination of 2‐chlorodeoxyadenosine (2‐CdA) and cytosine arabinoside (ara‐C) chemotherapy was evaluated in patients with HES.

METHODS

Nine patients with HES were treated with ara‐C (1 g/m2) given intravenously over 2 hours at 0 hours, 48 hours, 72 hours, 96 hours, and 120 hours; and 2‐CdA (12 mg/m2 per day) was given as a continuous intravenous infusion over 5 days starting at 24 hours. A second course of the same therapy was administered in patients who had a response.

RESULTS

All patients had signs and symptoms of end‐organ involvement. The median time from diagnosis to therapy was 25 months. Seven patients had received prior therapies. Five patients (55%) achieved a complete remission (CR), 1 after receiving 2 courses of therapy. Elimination of eosinophilia was accompanied by the resolution of symptoms. The median disease‐free survival and overall survival after the diagnosis for patients who achieved CR was 26 months and 44 months, respectively. Treatment was tolerated well. Febrile neutropenia occurred in 28% of the 14 courses that were given. The median time to recovery from neutropenia and thrombocytopenia was 17 days and 39 days, respectively.

CONCLUSIONS

The combined 2‐CdA and ara‐C chemotherapy regimen had activity in patients with HES. Cancer 2005. © 2005 American Cancer Society.
Inefficacy of F‐18 fluorodeoxy‐D‐glucose‐positron emission tomography scans for initial evaluation in early‐stage cutaneous melanoma
Authors: Wagner Jeffrey D. , Schauwecker Donald , Davidson Darrell , Logan Theodore , Coleman John J. , Hutchins Gary , Love Charlene , Wenck Stacie , Daggy Joanne
Published: June 2005

BACKGROUND

The purpose of the current study was to determine the sensitivity and specificity of initial F‐18 fluorodeoxy‐D‐glucose‐positron emission tomography (FDG‐PET) scanning for detection of occult lymph node and distant metastases in patients with early‐stage cutaneous melanoma.

METHODS

The authors conducted a prospective nonrandomized clinical trial. Inclusion criteria were patients with cutaneous melanoma tumors > 1.0 mm Breslow thickness, local disease recurrence, or solitary intransit metastases without regional lymph or distant metastases by standard clinical evaluation. All patients underwent whole‐body FDG‐PET scanning before surgical therapy. Abnormal PET findings were studied by targeted conventional imaging and/or biopsy. FDG‐PET scans were interpreted in a blinded fashion. Regional lymph node basins were staged by sentinel lymph node biopsy (SLNB). PET scan findings in regional lymph nodes were compared with histology of SLNB specimens. Abnormal distant PET scan findings were studied with repeat conventional scan imaging at 3–6 months and were correlated with the first site(s) of clinical disease recurrence. Blinded PET scan findings were correlated with all information to determine sensitivity and specificity.

RESULTS

There were 144 assessable patients with a mean tumor depth of 2.8 mm. The median follow‐up for these patients was 41.4 months. Blinded interpretations of FDG‐PET scan images showed that 31 patients (21%) had signs of metastatic disease, 13 patients had probable regional lymph node metastases, and 18 patients had 23 sites of possible distant metastases. SLNB and/or follow‐up demonstrated regional lymph node metastases in 43 of 184 lymph node basins in 40 patients (27.8%). Compared with all clinical information, FDG‐PET scan sensitivity for detection of regional lymph node metastases was 0.21 (95% confidence [CI], 0.10–0.36) and specificity was 0.97 (95% CI, 0.93–0.99). No distant sites were confirmed to be true positive by targeted conventional imaging/biopsy at the time of presentation. Thirty‐four patients (23.6%) presented with 54 foci of metastatic disease at initial disease recurrence. FDG‐PET scan sensitivity for prediction of the first site(s) of clinical disease recurrence was 0.11 (95% CI, 0.04–0.23). Excluding patients with brain metastases, FDG‐PET scan sensitivity for detection of occult Stage IV disease in patients was 0.04 (95% CI, 0.001–0.20) and specificity was 0.86 (95% CI, 0.79–0.92).

CONCLUSIONS

FDG‐PET scanning did not impact the care of patients with early‐stage melanoma already staged by standard techniques. Routine FDG‐PET scanning was not recommended for the initial staging evaluation in this population. Cancer 2005. © 2005 American Cancer Society.
Epidemiology and outcomes of serious influenza‐related infections in the cancer population
Authors: Cooksley Catherine D. , Avritscher Elenir B. C. , Bekele Benjamin N. , Rolston Kenneth V. , Geraci Jane M. , Elting Linda S.
Published: June 2005

BACKGROUND

Although patients with cancer generally respond favorably to vaccination, they may not receive annual influenza vaccinations. The current population‐based study described the epidemiology and outcomes of potentially preventable, serious influenza‐related infections in patients with cancer.

METHODS

From the Nationwide Inpatient Sample, the authors created a subsample that included discharges with any International Classification of Diseases, ninth revision, diagnosis code for cancer and principal diagnosis code for influenza, bronchopneumonia, or pneumonia caused by an unspecified organism. From the latter two diagnosis codes, the authors estimated excess cases during the influenza season for each year and stratum, then selected a random sample from fall and winter discharges. Subset analyses included weighted sample means, frequencies, and analysis of variance values. The authors converted charges to costs using cost‐to‐charge ratios and inflated these to 2003 U.S. dollars. Hospitalization and mortality rates were calculated using 5‐year cancer prevalence estimates.

RESULTS

The estimated mean annual hospital discharges of patients with cancer with potentially preventable, serious influenza‐related infections numbered 16,000. The average length and cost per stay were 6 days and > $6300, respectively. Approximately 9% of patients died in the hospital and 31% needed further skilled care. The estimated age‐specific rates for hospitalization and death per 100,000 in the prevalent cancer population were 219 and 17.4, respectively, for patients age < 65 years and 623 and 59.4, respectively, for those age ≥ 65 years. Hospitalization costs averaged $1300 more for patients age < 65 years.

CONCLUSIONS

Death from influenza‐related infections occurred in an estimated 9% of patients with cancer hospitalized for such. Using recommended vaccination schedules for patients with cancer and their contacts reduced hospitalizations, treatment delays, and deaths in this highly susceptible population. Cancer 2005. © 2005 American Cancer Society.
Analysis and experimental verification of the linear correlation of the operation condition among the bifurcation points of current‐mode‐controlled buck–boost converter
Authors: Cheng K. W. Eric , Liu M.
Published: June 2005

The operation parameter of the buck–boost converter is examined for its boundary of the first flip bifurcation. It is found that the parameters exhibit a linear relation for the same parameter at another bifurcation point. The bifurcation parameters also have a linear correlation between them. Theoretical analysis is presented to explain how this can occur. Simulation and experimental results at 20 kHz are used to present these novel results. Copyright © 2005 John Wiley & Sons, Ltd.
Wavelet‐AI equalization and detection for indoor diffuse infrared wireless systems
Authors: Dickenson R. J. , Ghassemlooy Z.
Published: June 2005

This paper briefly reviews motivators for indoor diffuse infrared wireless communications and discusses the difficulties in realizing high data rate implementations. We consider a sub‐set of traditional performance enhancing techniques and compare them with the proposed novel wavelet and artificial intelligence (AI) detection mechanism. Results of computer simulations for both the minimum mean square error (MMSE) equalizer and wavelet–AI receivers are presented that indicate the performance of the wavelet–AI receiver is almost indistinguishable from that of the match filter MMSE receiver. Copyright © 2005 John Wiley & Sons, Ltd.
Intercellular growth factor signaling and the development of mouse tracheal submucosal glands
Authors: Rawlins Emma L. , Hogan Brigid L.M.
Published: June 2005

To provide a genetic framework for investigating changes in airway submucosal gland function in human respiratory disease, we have investigated their counterparts in normal and mutant mice. We describe their morphogenesis in relation to the expression of genes encoding conserved intercellular signaling pathways. Submucosal glands are severely reduced in number and size in mice heterozygous for Fgf10. Glands are completely absent in mice lacking Ectodysplasin (Eda) and Edaradd (Eda receptor adaptor protein), members of the tumor necrosis (TNF) superfamily of signaling factors. Furthermore, components of the Eda and closely related pathways are transcribed throughout the respiratory system in the adult mouse. Finally, the temporal and spatial pattern of Bmp4 expression suggests that it may control submucosal gland development and homeostasis. Taken together, our observations have important implications for the better understanding of the submucosal gland remodeling that occurs in human respiratory disease. Developmental Dynamics 233:1378–1385, 2005. © 2005 Wiley‐Liss, Inc.
Cells of all somitic compartments are determined with respect to segmental identity
Authors: Fomenou Marlyse Dieuguie , Scaal Martin , Stockdale Frank E. , Christ Bodo , Huang Ruijin
Published: June 2005

Development of somite cells is orchestrated by two regulatory processes. Differentiation of cells from the various somitic compartments into different anlagen and tissues is regulated by extrinsic signals from neighboring structures such as the notochord, neural tube, and surface ectoderm. Morphogenesis of these anlagen to form specific structures according to the segmental identity of each somite is specified by segment‐specific positional information, based on the Hox‐code. It has been shown that following experimental rotation of presomitic mesoderm or newly formed somites, paraxial mesodermal cells adapt to the altered signaling environment and differentiate according to their new orientation. In contrast, presomitic mesoderm or newly formed somites transplanted to different segmental levels keep their primordial segmental identity and form ectopic structures according to their original position. To determine whether all cells of a segment, including the dorsal and ventral compartment, share the same segmental identity, presomitic mesoderm or newly formed somites were rotated and transplanted from thoracic to cervical level. These experiments show that cells from all compartments of a segment are able to interpret extrinsic local signals correctly, but form structures according to their original positional information and maintain their original Hox expression in the new environment. Developmental Dynamics 233:1386–1393, 2005. © 2005 Wiley‐Liss, Inc.
An automated in situ hybridization screen in the medaka to identify unknown neural genes
Authors: Deyts Carole , Candal Eva , Joly Jean‐Stephane , Bourrat Franck
Published: June 2005

Despite the fact that a large body of factors that play important roles in development are known, there are still large gaps in understanding the genetic pathways that govern these processes. To find previously unknown genes that are expressed during embryonic development, we optimized and performed an automated whole‐mount in situ hybridization screen on medaka embryos at the end of somitogenesis. Partial cDNA sequences were compared against public databases and identified according to similarities found to other genes and gene products. Among 321 isolated genes showing specific expression in the central nervous system in at least one of five stages of development, 55.14% represented genes whose functions are already documented (in fish or other model organisms). Additionally, 16.51% were identified as conserved unknown genes or genes with unknown function. We provide new data on eight of these genes that presented a restricted expression pattern that allowed for formulating testable hypotheses on their developmental roles, and that were homologous to mammalian molecules of unknown function. Thus, gene expression screening in medaka is an efficient tool for isolating new regulators of embryonic development, and can complement genome‐sequencing projects that are producing a high number of genes without ascribed functions. Developmental Dynamics 234:698–708, 2005. © 2005 Wiley‐Liss, Inc.