bluuebunny/crossref_metadata_2025 huggingface dataset:
The World Health Organization and the Transition From “International” to “Global” Public Health
Authors: Brown Theodore M. , Cueto Marcos , Fee Elizabeth
Published: December 2005

The term “global health” is rapidly replacing the older terminology of “international health.” We describe the role of the World Health Organization (WHO) in both international and global health and in the transition from one to the other. We suggest that the term “global health” emerged as part of larger political and historical processes, in which WHO found its dominant role challenged and began to reposition itself within a shifting set of power alliances.

Between 1948 and 1998, WHO moved from being the unquestioned leader of international health to being an organization in crisis, facing budget shortfalls and diminished status, especially given the growing influence of new and powerful players. We argue that WHO began to refashion itself as the coordinator, strategic planner, and leader of global health initiatives as a strategy of survival in response to this transformed international political context.
Health Measurement in the Third Era of Health
Authors: Breslow Lester
Published: December 2005

When writing about “the second epidemiologic revolution,” Terris discussed 2 eras in health. The first era—the communicable disease era—began during ancient times and continues today; the second era—the chronic disease era—began during the 20th century, particularly among the industrialized nations.

Although neither revolution against these types of diseases is complete, we have made such considerable progress that substantial and growing segments of the population no longer regard disease as the only, or even the primary, health problem. Increasingly, the goal is a long and fruitful life, not simply the absence of disease. That potential and the effort to achieve it compose the third era of health, and a proposed new measure of health is outlined in this article.
An Unusual Foreign Body Ingestion in a Schizophrenic Patient: Case Report
Authors: Abraham Benjamin , Alao Adekola O.
Published: December 2005

The topic of foreign body ingestion has received extensive coverage in the areas of surgery, emergency medicine, and pediatrics. A subset of this topic, the intentional ingestion of foreign bodies, however, is much less common, and requires special evaluation and management. Here, we report a case of ingestion of a rolled, metal tuna can lid in a male prison inmate previously diagnosed with depression and paranoid schizophrenia. Following evaluation by the surgical team, the foreign body was removed by laparotomy and the patient was discharged back to the prison without complication. In many cases, ingestions of this type involve a command hallucination ordering the patient to swallow the foreign body. Interestingly, the patient in the present case reported auditory hallucinations commanding him not to swallow the can lid. On further investigation, we found that patient had a proclivity toward this swallowing behavior even prior to his incarceration. Early identification of inmates with this proclivity has important implications for treatment and prevention.
Show Me the Money: Cost-Benefit Analysis in the Work Environment
Authors: Levenstein Charles , Dunn Mary Lee
Published: December 2005

During the last several decades, Cost-Benefit Analysis (CBA) has become a widely used technique in public policy-making. This review examines CBA from perspectives of both advocates and critics; it looks at its theory and practice, its purported advantages and shortcomings in application. It also proposes several ways in which the process can be made more accountable.
Covalently Linked Tetraphenylporphyrin Trimers and Tetramers and their
Coordination Behaviour
Authors: VAIJAYANTHIMALA G. , KRISHNAN V.
Published: December 2005

Several covalently linked tetraphenyl porphyrin trimers and tetramers
bearing ethylene oxide bridges originating from the m and p positions of
adjacent and/or opposite meso-aryl groups have been synthesized and
characterized by fast atom bombardment mass spectroscopy,
1 H NMR, optical absorption and emission
spectroscopies. The fully and partially metallated zinc(II) and copper(II)
derivatives have been prepared and their photophysical properties are
outlined. The steady-state and time-resolved fluorescence studies of the
heterotrimers indicate efficient energy transfer from the ZnP to the H
2 P unit. The efficiency and rate of energy
transfer are dependent on the number of free-base units in the
hetero-oligomers and the geometrical position of the porphyrin units. The
heterotrimers consisting of one, two and three zinc(II) centres bind
4,4″-bipyridyl in different modes as revealed by the nature of binding
curves. The bipyridyl ligand functions as a chelate in the complexes of
biszinc(II) porphyrin trimers while two bipyridyls bind to trizinc(II)
porphyrin trimers with one ligand functioning as a chelate and another
exhibiting monodentate coordination behaviour. The folding of two ZnP units
is clearly seen in the complexes of bis and triszinc(II) trimers with
bipyridyl, which is substantiated by molecular mechanics calculations. Axial
ligation studies with trimers show that the preorganization of porphyrin
hosts is necessary for recognition of the guest. The binding of bipyridyl to
the trimers is followed by global conformational changes and this behaviour
is analogous to activated complex binding in induced-fit enzymes.
Resonance Raman Spectra and Crystal Structure of Lithium Phthalocyaninate(1-) Iodine: a Realistic Model for the Starch-Iodine Complex
Authors: LATTE B. , KIENAST A. , BRUHN C. , LOIDL A. , HOMBORG H.
Published: December 2005

The lithium phthalocyaninate(1-) iodine inclusion complex [( Lipc −)· I ], prepared by the reaction of anhydrous lithium iodide with molten 1,2-dicyanobenzene, crystallizes tetragonally in the space group P4/mcc with a = 14.057(3) Å, b = 6.397(1) Å, V = 1264.0(4) Å3, Z = 2. Lithium is in a crystallographically imposed strictly square planar coordination geometry with a Li - N distance of 1.940(7) Å. Linear chains of equidistant iodine atoms are segregated from adjacent metal-over-metal stacks of the planar lithium phthalocyaninate(1-) molecules, which are staggered by 40.2(5)°. Resonance Raman spectra have been studied in comparison with those of the starch-iodine complex [(starch)·I]. The identity of the iodine chromophore in both complexes is essentially the same. It consists of an iodine chain in a hydrophobic environment. Its character is predominately ‘aliphatic’ in [(starch)·I] and ‘aromatic’ in [( Lipc −)· I ].
Interaction of Acenannulated Metallotetraazaporphyrins with the Lewis Acid Aluminum Bromide
Authors: FREYER WOLFGANG , MINH L. Q.
Published: December 2005

Interaction of metal complexes of linearly benzo-annulated tetraazaporphyrins such as tetra-tert-butyltetrabenzoporphyrazine, tetra-tert-butyltetranaphthoporphyrazine, and octaphenyltetraanthra-porphyrazine, with the Lewis acid AlBr 3 in nitrobenzene and ethylbromide has been studied by absorption spectroscopy. The interaction is characterized by stepwise formation of several protonated complexes with the superacid H +[ AlBr 4]−. Mono-, di-, tri- and tetraprotonated species can be formed. The absorption maxima are shifted up to 1300 nm depending on annulation, metal ion and concentration of the Lewis acid.
Electrochemical Reduction of Nitrous Oxide (N2O) Catalysed by Tetraaminophthalocyanatocobalt(II) Adsorbed on a Graphite Electrode in Aqueous Solution
Authors: ZHANG JIUJUN , TSE YU-HONG , LEVER A. B. P. , PIETRO W. J.
Published: December 2005

The surface electrochemical response of the Co II/ Co I redox process of tetraaminophthalocyaninatocobalt(II) ( Co II TAPc ) adsorbed on a graphite electrode, was studied in the pH range of 2–13. In aqueous solution, the Co II TAPc adsorbed graphite electrode displays very strong electrocatalytic activity toward N 2 O reduction to N 2, a process which was examined by cyclic and rotating disk electrode voltammetries. The possible application of this Co II TAPc modified electrode in N 2 O analysis was explored.
The Synthesis and Properties of Some Polyfluoroalkoxy Substituted Phthalocyanines
Authors: KONDRATENKO N. V. , NEMYKIN V. N. , LUKYANETS E. A. , KOSTROMINA N. A. , VOLKOVAN S. V. , YAGUPOLSKII L. M.
Published: December 2005

A series of 4-(polyfluoroalkoxy)phthalonitriles have been prepared in high yield by nucleophilic substitution of the nitro group in 4-nitrophthalonitrile on polyfluoroalkoxy groups at room temperature. These dinitriles have been cyclotetramerized in the presence of cobalt or copper salts into the corresponding phthalocyanine complexes. The spectral properties and coordination chemistry of some of them have been studied.
Sulfonated Phthalocyanines: Photophysical Properties, in vitro Cell Uptake and Structure-activity Relationships
Authors: EDREI R. , GOTTFRIED V. , VAN LIER J. E. , KIMEL S.
Published: December 2005

Aluminium phthalocyanines sulfonated to a different degree ( AlPcS n) and consisting of various isomeric species were studied by spectroscopic techniques to determine their tendencies to form dimers and aggregates. These characteristics were compared with the cell-penetrating properties of the species, using the Ehrlich ascites mouse tumor cell line, to arrive at structure-activity relationships. AlPcS n preparations consisting of the least number of isomeric species exhibited the highest tendency to form dimers and aggregates, whereas the more complex preparations, consisting of many isomeric products, showed more consistent monomeric features in aqueous environments. Uptake in cells was shown to correlate well with the overall hydrophobicity of the preparation and inversely with its degree of aggregation in the extracellular environment. Among the purified, single isomeric AlPcS n the amphiphilic disulfonated AlPcS 2a , enriched in positional isomers featuring sulfonate groups on adjacent phthalic subunits, showed the best membrane-penetrating properties. Even higher cell uptake was observed for the AlPcS 2mix reflecting a combination of optimal lipophilicity and a low degree of aggregation. Similarly, in the case of AlPcS 4, the pure isomeric compound showed less cell uptake than the mixed isomeric preparation of similar hydrophobicity, reflecting the higher degree of aggregation invoked by its symmetrical structure. Our data indicate that mixed sulfonated phthalocyanine preparations may exert higher photodynamic efficacy in biological applications as compared to the pure isomeric constituents.
Synthesis and Crystal Structure of 2,4,6-Triphenylpyrylium Acetonato(C)chlorophthalocyaninato(2–)iridate(III) Monohydrate
Authors: HÜCKSTÄDT HEINER , HOMBORG HEINER
Published: December 2005

Phthalocyaninato(2–)iridate(I) is oxidized by air in acetone to form acetonato(C)chlorophthalocyaninato(2–)iridate(III) in the presence of chloride. The anion is isolated as its 2,4,6-triphenylpyrylium salt, ( TPPy )[ Ir ( aC )( Cl ) Pc 2−]. Its monohydrate crystallizes in the monoclinic space group P1n1 (#7). The cell parameters are a = 12.452(3) Å, b = 12.339(3) Å, c = 15.352(4) Å, β = 100.75(2) °, Z = 2. Hexa-coordinated Ir is located slightly out of the centre (ct) of the Pc core (d( Ir-ct ) = 0.02 Å) and directed towards the acetonato C atom. It coordinates four isoindole N atoms ( N iso ) together with a Cl atom and a C-bonded acetonate in a mutual trans position. The average Ir – N iso distance is 1.966 Å;, the Ir – Cl distance is 2.501(5) Å; and the Ir –C distance is 2.11(2) Å.
Interaction of Porphyrins with Cetyltrimethylammonium Bromide Micelles in Methylene Chloride
Authors: BAG NILKAMAL , DHATHATHREYAN ARUNA , MANDAL ASIT BARAN , RAMASAMI TIRUMALACHARI
Published: December 2005

The formation of micelles of cetyltrimethylammonium bromide (CTAB) in CH2Cl2solution has been reported for the first time. The critical micelle concentrations (cmc) of CTAB in CH2Cl2solution were determined using conductivity and fluorescence techniques in both the absence and presence of 1,3,5,7-tetramethyl-2,4,6,8-tetra(2,4,6-triisopropylphenyl)porphyrin (TMTIP). The cmc values obtained by conductivity and fluorescence methods were found to be 75 and 78 mM, respectively. The aggregation numbers (N) of CTAB and porphyrin–CTAB in CH2Cl2solution were determined using pyrene and N-cetylpyridinium chloride (CPC) as the fluoroprobe and quencher, respectively. The N of CTAB in CH2Cl2solution was also determined using the porphyrin (in lieu of pyrene) as the fluoroprobe and CPC as the quencher. The N of CTAB obtained by these probes was found to be 134 ± 3 and 140 ± 5, respectively. This suggests that the porphyrin could be used as an excellent fluoroprobe for determination of the aggregation number of CTAB micelles. The results of both cmc and aggregation number suggest that the micelle formation of CTAB in CH2Cl2solution is favored in the presence of the porphyrin. The standard free energy change for micelle formation of CTAB in CH2Cl2solution was calculated using a biphasic model. The standard free energy transfer [Formula: see text] of CTAB micelles from CH2Cl2to porphyrin environment has been found to be −1.0 kJ mol−1at 25 °C, suggesting that the above transfer is difficult. However, the reverse situation, i.e. binding of the porphyrin to CTAB micelles, is more probable. The Langmuir–Blodgett (LB) film formation of the porphyrin and metalloporphyrins ( Fe , Co , Cu , Zn ) has also been studied and the UV-vis spectra of these films have been analyzed.
Synthesis and Crystal Structure of 5,10,15,20-Tetrakis(3,5-dinitrophenyl)porphyrin
Authors: BHYRAPPA P. , SUSLICK K. S.
Published: December 2005

The synthesis, characterization and crystal structure of the octanitro-substituted porphyrin 5,10,15,20-tetrakis(3,5-dinitrophenyl)porphyrin, H 2 T (3,5- DNP ) P , are described. The solid state structure has two porphyrins in the unit cell with eight pyridine solvates and is made up from columnar arrays of the porphyrins. X-ray crystal structure data: monoclinic, space group P1 21/n1, a = 14.9996(9) Å, b = 8.2489(5) Å, c = 24.818(2) Å, α = 90 °, β = 104.172(1) °, γ = 90 °, V = 2977.3(3) Å3, dcalc = 1.440 g m-3, Z = 2.
Magnetic and Spectroscopic Investigations of Tetra(4-t-butyl)phthalocyano Complexes of Cobalt(II) and Copper(II)
Authors: HEUCHER REIMAR , CHANDRAMOULI G. V. R. , MANOHARAN PERIAKARUPPAN T.
Published: December 2005

The tetra(4-t-butyl)phthalocyanine derivatives of Co and Cu have been studied by ESR spectroscopy in solution owing to their solubility in polar and non-polar solvents. The cobalt complex gives a well-resolved EPR spectrum in toluene glass at 77 K with g‖ = 2.018, g⊥ = 2.785, A‖ = 0.0155 cm -1, A⊥ = 0.0208 cm -1, P = 0.0201 cm -1 and K = 0.0079 cm -1. Although the low-field lines due to A⊥ seem a lot more broadened than the high-field ones due to A‖, both sets have been shown to have highly MI-dependent linewidths. The experimental data for g and A available in the literature have been plotted and compared with McGarvey's theoretical equations. The copper complex in toluene glass at 110 K gives a well-resolved EPR spectrum at Q-band frequency with g‖ = 2.163, g⊥ = 2.048, A‖ = 0.0212 cm -1 and A⊥ = 0.0032 cm -1.
Synthesis and Biological Evaluation of Thioglycosylated meso-Arylporphyrins
Authors: SYLVAIN ISABELLE , BENHADDOU RACHIDA , CARRE VINCENT , COTTAZ SYLVAIN , DRIGUEZ HUGUES , GRANET ROBERT , GUILLOTON MICHEL , KRAUSZ PIERRE
Published: December 2005

A new class of porphyrins bearing thioglycosyl groups is presented in order to improve targeting of malignant cells and resistance to glycosidases. These compounds were synthesized in four steps. They produced 1 O 2 and their photocytotoxicity against the yeast Saccharomyces cerevisiae was compared with the effect of haematoporphyrin.
Characterization and Electrical Conductivity of Dithallium Phthalocyanine (Tl2Pc)
Authors: SUGA TAKEO , ISODA SEIJI , KOBAYASHI TAKASHI
Published: December 2005

Dithallium phthalocyanine ( Tl 2 Pc ) has been synthesized from pure Tl metal and o-phthalodinitrile. The isolated compound was characterized by elemental analysis, X-ray powder diffraction, electron diffraction and EDX spectroscopy. Based on these results, the compound synthesized by the present method was concluded to be Tl 2 Pc . The electrical conductivity of this powdery Tl 2 Pc was measured and it exhibited the semiconductive property, in contrast with a previous report.
Syntheses of Octaalkynylphthalocyanines from Halophthalonitriles
Authors: LEZNOFF CLIFFORD C. , LI ZHAOPENG , ISAGO HIROAKI , D'ASCANIO ANNA M. , TEREKHOV DMITRI S.
Published: December 2005

Coupling of 4,5-diiodophthalonitrile with tert-butyldimethylsilylacetylene and a palladium catalyst gave 4,5-bis(tert-butyldimethylsilylethynyl)phthalonitrile. Cleavage of the silyl moiety with tetrabutylammonium fluoride gave 4,5-diethynylphthalonitrile, while condensation in 2-N,N-dimethylaminoethanol without or with Zn ( OAc )2 gave metal-free 2,3,8,9,16,17,23,24-octakis(tert-butyldimethylsilylethynyl)phthalocyanine or its zinc derivative. Cleavage of the silyl groups of the zinc derivative gave an insoluble product whose 1 H NMR spectrum was indicative of 2,3,9,10,16,17,23,24-octaethynylphthalocyaninato zinc(II). Bromination of phthalonitrile with N,N-dibromoisocyanuric acid gave a separable mixture of 3,6-, 3,4- and 4,5-dibromophthalonitrile along with the monobromophthalonitriles. Coupling of 3,4-dibromophalonitrile with tert-butylacetylene gave 3,4-bis(tert-butylethynyl)phthalonitrile, which on condensation with lithium 1-pentanolate gave 1,2,8,9,15,16,22,23-octakis(3,3-dimethyl-1-butynyl)phthalocyanine as a single isomer, the first known 1,2,8,9,15,16,22,23-octasubstituted phthalocyanine.
Phthalocyanines as Photosensitizers in the Photodynamic Therapy of Cancer
Authors: LUKYANETS EUGENY A.
Published: December 2005

The application of phthalocyanine derivatives in medicine as photosensitizers for photodynamic therapy of cancer diseases is reviewed. The emphasis is on the work of Russian authors, which is less covered in the scientific literature.
The Phthalocyanines — Molecules of Enduring Value; a Two-dimensional Analysis of Redox Potentials
Authors: LEVER A. B. P.
Published: December 2005

The sensor applications of MPc derivatives on carbon-type electrodes are briefly reviewed. The electrochemical properties of metallophthalocyanines in solution and on a surface are reviewed with emphasis on predicting redox potentials using Hammett substituent constants and using ligand electrochemical parameters. Design requirements for a two-electron redox process at a metallophthalocyanine center are discussed. A two-dimensional approach using both Hammett parameters and ligand electrochemical parameters is introduced. Some preliminary test examples are presented.
The Involvement of Phycocyanin Pigment in the Photodecomposition of the Cyanobacterial Toxin, Microcystin-LR
Authors: ROBERTSON PETER K. J. , LAWTON LINDA A. , CORNISH BENJAMIN J. P. A.
Published: December 2005

While investigating the destruction of the cyanobacterial hepatotoxin microcystin-LR in the presence of phycocyanin pigment via semiconductor photocatalysis, it became apparent that the pigment was catalysing the toxin decomposition. The mechanism of this process in terms of phycocyanin acting as a photo-oxygenation sensitizer via singlet oxygen and superoxide attack is explored. The absorption and fluorescence spectra of phycocyanin have been obtained and data on the properties of the excited state calculated. The established photo-oxygenation sensitizer rose bengal was also used as a catalyst for the photolytic decomposition of microcystin-LR to help elucidate the decomposition mechanism.
Electron Crystallography of Phthalocyanines
Authors: FRYER J. R.
Published: December 2005

It is shown that it is possible to obtain structural information from small (<100 nm) phthalocyanine crystals by using crystallographic direct phasing methods applied to electron diffraction data. This technique is both quantitative and does not suffer from the difficulties associated with high-resolution electron microscopy. Structural information has been obtained from both tetra- and octa chloro-copper phthalocyanines, and the results compared with the hydrogenated and perchloro members of the series.
Role of Metal Phthalocyanine in Redox Complex Conductivity of Polyaniline and Aniline Black
Authors: XAVIER FRANCIS P. , INIGO ANTO REGIS , GOLDSMITH GEORGE J.
Published: December 2005

Polyaniline (PA) and aniline black (AB) were prepared in powder form by the chemical method of oxidative polymerization, from which free-standing thin films were obtained by solvent evaporation using N-methyl pyrrolidinone ( NMP ). The thin films contained 2, 4, 6 or 8 wt% AB. Electrical measurements showed that the samples containing 4% AB exhibited the highest photoconductivity of the four concentrations. Thus there appears to be a critical ratio of PA to AB for maximum photoconductivity. Annealing up to 570 K has little effect on the conductivity. Upon adding a small quantity of copper phthalocyanine ( CuPc ) to the PA + AB, the electrical conductivity increased considerably and the optical absorption was extended from the UV to the near IR. The electrical conductivity mechanism is a consequence of a redox process, since AB is the oxidized state of PA and, upon illumination, there is an exchange of charge carriers. The extension of the range of optical absorption upon addition of CuPc is interpreted to suggest that CuPc photosensitizes the material and enhances the carrier transport process in the redox couple. The activation energy from the temperature-dependent conductivity and the band gap from the electrolyte electroreflectance method were determined. The activation energy for 0.4% CuPc is lowest (0.52 eV) and the corresponding band gap is determined to be 3.0 eV. This organic compound could be a good candidate for inexpensive, reliable and efficient solar energy-converting devices.
Plant Layout
Authors: Meissner Roland E.
Published: December 2005

This article discusses the process by which a plant plot plan is developed and the spacing and orientation between equipment. It describes the step‐by‐step procedures that a designer goes through in selecting the arrangement of equipment and providing the necessary space between the equipment items. Examples are included that illustrate the concepts presented. This article also presents an evaluation and discussion of the three principle types of layout presentations: orthographic drawings, plastic models, and computer‐aided design models. Practical uses and limitations of each of these presentation mediums are covered. Many practical design tips are included. Sufficient background information is provided for the reader to appreciate the subtleties of plant layout. The piperack design and its use as the arterial system for the plant are also covered.
Potassium Compounds
Authors: Freilich Mark B. , Petersen Richard L. ,   Updated by Staff
Published: December 2005

Water‐soluble salts of potassium, collectively called potash, are important for the manufacture of numerous articles of commerce and for direct application as fertilizers. Other uses of potassium compounds range from use in specialty glass to that of food additives. Potassium chloride, the most commonly used potash and the raw material for the manufacture of most of the other potassium compounds, is principally obtained from the mining of sylvinite. The ore refinement process, which includes crushing, scrubbing, hydraulic desliming, froth flotation, centrifugation, and drying is described. Potassium hydroxide is produced industrially by electrolysis of the chloride. The hydroxide is used for the production of the commercially important potassium carbonate and potassium phosphates. Several processes are used to convert potassium chloride to other potassium compounds such as the sulfate. Potassium magnesium sulfate is also an important fertilizer. Other compounds of commercial importance include the potassium salts of acetate, bromide, bicarbonate, formate, iodide, permanganate, and acid tartrate. Potassium has an essential role for the biochemistry of both plants and animals. Potassium compounds commonly used in fertilizers are not considered to be hazardous; however, potassium may be paired with a poisonous, corrosive, or oxidizing anion and requires special handling.
Polysaccharides
Authors: Rinaudo Marguerite
Published: December 2005

This article is a short review on polysaccharides based on their recognized applications. The main techniques for polysaccharides characterization are discussed. Cellulose and starch are examined as well as their main derivatives. It is shown how the three‐dimensional (3D) structure influences the distribution of the substituents and the physical properties. Hemicelluloses, pectins, galactomannans, and glucomannans are briefly described. The main source of each of these polymers is presented.

Chitin and chitosan are described before introducing the microbial polysaccharides. Bacterial polysaccharides are now developed widely due to the great number of new structures available. The main characteristics of these stereoregular polysaccharides are given.
Mass Synthesis of Large, Single‐Crystal Au Nanosheets Based on a Polyol Process
Authors: Li C. C. , Cai W. P. , Cao B. Q. , Sun F. Q. , Li Y. , Kan C. X. , Zhang L. D.
Published: November 2005

Single‐crystal gold nanosheets, with triangular, hexagonal, or truncated triangular shapes, from several to tens of micrometers across and tens of nanometers thick, have been successfully synthesized in high yield via a simple and low‐cost chemical route in an ethylene glycol solution, on the basis of a polyol process. The planar surfaces of the Au nanosheets are atomically flat and correspond to {111} planes; the lateral surfaces are {110} planes. The nanosheets show strong optical absorption in the near infrared region of the electromagnetic spectrum. Both the ethylene glycol and the surfactant polyvinylpyrrolidone (PVP), in the solution play important roles in the formation of the Au nanosheets. The concentrations of the precursors (PVP, HAuCl4) and the reaction temperature are also crucial to the morphology and size of the final product. The formation of such large, single‐crystal nanosheets is explained by the preferential adsorption of some species of molecules from the solution onto the {111} planes of Au nuclei, and the connection of small, triangular nanosheets. These nanosheets could be used easily, for example, in gas sensors, in the fabrication of nanodevices and substrate materials, in property studies, and also for inducing hypothermia in tumors.
Spectroscopic and Photophysical Properties of a Highly Derivatized C60 Fullerol
Authors: Vileno B. , Marcoux P. R. , Lekka M. , Sienkiewicz A. , Fehér T. , Forró L.
Published: November 2005

Hydroxylated C60 molecules, also called fullerols, are a class of water‐soluble fullerenes. Here we report the synthesis in acidic conditions of a highly derivatized fullerol (up to 36 carbons per C60 are oxidized). Spectroscopic investigations (X‐ray photoelectron spectroscopy and infrared absorption) highlight the coexistence of both acidic and basic forms for the hydroxyl addends of derivatized C60. pH titrimetry reveals that, at millimolar concentrations, only ten protons per fullerol molecule are labile. Such a low value, as compared to 36 hydroxyl groups, is explained by the formation of clusters. A UV‐vis absorption study performed over a large range of concentrations also points to the aggregation phenomenon. Moreover, this study shows that the clusters of fullerols appear at relatively low (micromolar) concentrations. An electron spin resonance (ESR) study, based on the attack of singlet oxygen (1Δg) on 2,2,6,6‐tetramethyl‐4‐piperidinol (TMP‐OH), has proved the potential of hydroxylated C60 for performing efficient generation of singlet oxygen in aqueous solution. ESR measurements, which allow detection and quantification of 1Δg, have also revealed the generation of reactive oxygen species (ROS). The yield of generation of 1Δg and ROS is strongly correlated to the concentration of fullerol, thus also pointing to the aggregation of fullerol molecules. Exposing glioblastoma cells to oxidative stress in the presence of hydroxylated C60 and visible light has also been performed. Atomic force microscopy is used to monitor the relevant diminishment of the Young's modulus values for cells exposed to the oxidative stress. These results point to a possible application field of fullerols for performing bio‐oxidations.
Force Spectroscopic Investigations During the Local Oxidation of n‐Octadecyltrichlorosilane Monolayers
Authors: Hoeppener S. , van Schaik J. H. K. , Schubert U. S.
Published: November 2005

Scanning force spectroscopy (SFS) is a powerful tool for investigating surface properties with high precision. Unlike most common spectroscopic techniques, information about local properties can also be obtained from surface areas with nanometer dimensions. This makes SFS a useful investigative tool for small lithographic structures. We apply the continuous recording of force curves to extract valuable information about the local oxidation of a monolayer of n‐octadecyltrichlorosilane molecules self‐assembled on silicon. The oxidation is carried out while simultaneously recording the force curves during the application of a bias voltage to the tip. The dynamics of the induced surface modifications and changes in the surface properties are followed by analyzing specific spots in the force curves.
Fluorescence‐Amplifying Detection of Hydrogen Peroxide with Cationic Conjugated Polymers, and Its Application to Glucose Sensing
Authors: He F. , Tang Y. , Yu M. , Wang S. , Li Y. , Zhu D.
Published: November 2005

A highly sensitive hydrogen peroxide probe that takes advantage of the amplified fluorescence quenching of conjugated polymers has been developed. The cationic conjugated polymer, poly(9,9‐bis(6′‐N,N,N‐trimethylammonium‐hexyl) fluorene phenylene) (PFP‐NMe3+) and peroxyfluor‐1 with boronate protecting groups (Fl‐BB) are used to detect H2O2 optically. Without the addition of H2O2, the absence of electrostatic interactions between the cationic PFP‐NMe3+ and the neutral Fl‐BB keeps the Fl‐BB well separated from the PFP‐NMe3+, and no fluorescence quenching of the PFP‐NMe3+ occurs. In the presence of H2O2, the formation of the anionic quencher, fluorescein, by specific reaction of the Fl‐BB with H2O2 results in strong electrostatic interactions between the PFP‐NMe3+ and the fluorescein, and therefore efficient fluorescence quenching of the PFP‐NMe3+ occurs. The absorption of fluorescein overlaps the emission of PFP‐NMe3+, which encourages fluorescence resonance energy transfer (FRET) from the PFP‐NMe3+ to the fluorescein. The H2O2 probe has very good sensitivity, with a detection range of 15 to 600 nM. Since glucose oxidase (GOx) can specifically catalyze the oxidation of β‐D‐(+)‐glucose to generate H2O2, glucose detection is also realized with the H2O2 probe as the signal transducer.
Liquid Phase Oxidation of Toluene to Benzaldehyde with Molecular Oxygen over Copper‐Based Heterogeneous Catalysts
Authors: Wang Feng , Xu Jie , Li Xiaoqiang , Gao Jin , Zhou Lipeng , Ohnishi Ryuichiro
Published: December 2005

We conducted the liquid phase oxidation of toluene with molecular oxygen over heterogeneous catalysts of copper‐based binary metal oxides. Among the copper‐based binary metal oxides, iron‐copper binary oxide (Fe/Cu=0.3 atomic ratio) was found to be the best catalyst. In the presence of pyridine, overoxidation of benzaldehyde to benzoic acid was partially prevented. As a result, highly selective formation of benzaldehyde (86% selectivity) was observed after 2 h of reaction (7% conversion of toluene) at 463 K and 1.0 MPa of oxygen atmosphere in the presence of pyridine. These catalytic performances were similar or better than those in the gas phase oxidation of toluene at reaction temperatures higher than 473 K and under 0.5–2.5 MPa. It was suggested from competitive adsorption measurements that pyridine could reduce the adsorption of benzaldehyde. At a long reaction time of 4 h, the conversion increased to 25% and benzoic acid became the predominant reaction product (72% selectivity) in the absence of pyridine. The yield of benzoic acid was higher than that in the Snia‐Viscosa process, which requires corrosive halogen ions and acidic solvents in the homogeneous reaction media. The catalyst was easily recycled by simple filtration and reusable after washing and drying.
New Carbohydrate‐Based Phosphite‐Oxazoline Ligands as Highly Versatile Ligands for Palladium‐Catalyzed Allylic Substitution Reactions
Authors: Mata Yvette , Diéguez Montserrat , Pàmies Oscar , Claver Carmen
Published: December 2005

We have designed and synthesized a new family of readily available phosphite‐oxazoline ligands for Pd‐catalyzed asymmetric allylic substitution reactions. These ligands can be tuned in two regions to explore their effect on catalytic performance. By carefully selecting the ligand components, we obtained high enantioselectivities in the Pd‐catalyzed allylic substitution in substrates with different steric properties
Topological Mapping of Bidentate Ligands: A Fast Approach for Screening Homogeneous Catalysts
Authors: Burello Enrico , Rothenberg Gadi
Published: December 2005

The challenge of predicting the catalytic properties of large libraries of homogeneous catalysts is introduced. A new concept is presented that combines fundamental chemical topology principles with linear and non‐linear statistical analysis. These models can predict key properties of bidentate ligand‐metal complexes, namely the ligand bite angle and the backbone flexibility, without computing any 3D structural parameters and without using any force fields or any quantum mechanics. The model's performance is demonstrated on a set of 80 biphosphine and biphosphite complex crystal structures. With non‐linear methods, the prediction accuracy is 93% for bite angles and 90% for flexibilities. The link between the descriptors and the ligand structures, and the possibilities that this approach opens in the search for new homogeneous catalysts are discussed.
Palladium Nanoclusters in Sonogashira Cross‐Coupling: A True Catalytic Species?
Authors: Thathagar Mehul B. , Kooyman Patricia J. , Boerleider Romilda , Jansen Eveline , Elsevier Cornelis J. , Rothenberg Gadi
Published: December 2005

The question of whether palladium nanoclusters are the actual catalysts in the so‐called ‘cluster–catalyzed Sonogashira cross‐coupling’ is investigated, using the coupling of phenylacetylene with 4‐bromobenzonitrile as a model reaction. By combining a detailed kinetic analysis with transmission electron microscopy (TEM), we show that a soluble species must be present in the system when Pd nanoclusters are used as catalysts. Various Pd clusters show similar kinetic profiles to that of a homogeneous Pd(dba)2 complex. Most importantly, TEM analysis of samples taken before, during, and after the reaction shows that the cluster size decreases during the reaction. Based on these findings, we present a possible two‐path mechanism for Sonogashira cross‐coupling reactions in the presence of Pd nanoclusters.
A New Chiral P,N‐Ligand Derived from 1‐Phenylphospholane‐2‐carboxylic Acid (Phenyl‐P‐proline) for Palladium‐Catalyzed Asymmetric Allylic Substitution Reactions
Authors: Sun Xiang‐Min , Koizumi Masatoshi , Manabe Kei , Kobayashi Shū
Published: December 2005

New types of P,N‐ligands, cis‐ and trans‐3, containing a tetrahydroisoquinoline skeleton as an N‐donor were synthesized from (1R,2S)‐1‐phenylphospholane‐2‐carboxylic acid (phenyl‐P‐proline, 1). The cis isomer, cis‐3, was found to act as an excellent ligand in palladium‐catalyzed asymmetric allylic substitution reactions. The reactions of 1,3‐diphenyl‐2‐propenyl acetate (5) with several nucleophiles in the presence of [Pd(π‐allyl)Cl]2, cis‐3 (Pd : ligand=1 : 2), and a base afforded the desired products in high yields with high enantioselectivity. It was suggested that these ligands did not serve as P,N‐bidentate ligands but as P‐monodentate ligands in these reactions.
L‐Prolinethioamides – Efficient Organocatalysts for the Direct Asymmetric Aldol Reaction
Authors: Gryko Dorota , Lipiński Radosław
Published: December 2005

A series of novel L‐proline derived thioamides has been synthesised. They have been evaluated as organocatalysts in the direct asymmetric aldol reaction for the first time. Thioamides exhibit catalytic ability higher than proline itself and the model aldol reaction of 4‐cyanobenzaldehyde with acetone proceeds well in the presence of 5 mol % of catalyst (ee up to 100%). Other aromatic aldehydes gave aldol products with high ees and moderate yields. Small changes in the catalyst's structure [e.g., N‐Bn versus N‐CH(CH3)Ph] as well as the addition of an acid have a profound effect on their activity. The unexpected formation of the catalyst‐derived cyclic adducts was observed and their reactivity was established giving valuable insight into the course of the reaction.
Vanadium‐Catalyzed Enantioselective Sulfoxidation and Concomitant, Highly Efficient Kinetic Resolution Provide High Enantioselectivity and Acceptable Yields of Sulfoxides
Authors: Zeng Qingle , Wang Heqing , Wang Tongjian , Cai Yimin , Weng Wen , Zhao Yufen
Published: December 2005

Simple, inexpensive, preformed vanadium‐Schiff base complexes were facilely prepared and used in enantioselective sulfoxidation. Both the amount of aqueous H2O2 and reaction time greatly influenced the ee values and yields of chiral sulfoxides. High enantioselectivities (up to 99% ee) and reasonable yields (>40%) for various chiral sulfoxides were achieved by combining enantioselective sulfoxidation and appropriate concomitant kinetic resolution.
Isolated 6q terminal deletions: An emerging new syndrome
Authors: Bertini Veronica , De Vito Giuseppe , Costa Rosa , Simi Paolo , Valetto Angelo
Published: December 2005

Deletions of the distal part of the 6q chromosome have not been associated with a clearly distinctive and recognizable phenotype. In order to determine if a “6q terminal deletion syndrome” could be delineated, we compared the phenotype of two new cases with those patients reported in literature presenting with a similar deletion. Cases with more complex karyotypes were excluded. The deletion in our patients was accurately analyzed by loss of heterozygosity (LOH) and fluorescence in situ hybridization (FISH) with a panel of probes located around the putative breakpoint. Interestingly, the breakpoints were located in 6q26 in both our patients, distally to clone RP11‐150P20 and proximally to clone RP11‐152P19, with a deletion size of approximately 8 Mb. The breakpoints fall within the fragile site FRA6E. From a careful evaluation of the selected patients, a common phenotype emerged, including psychomotor retardation, hypotonia, seizures, short neck, and typical facial anomalies, along with nonspecific anomalies. While these features are shared by other chromosome syndromes and are not sufficient on their own for a clinical diagnosis, when considered together, the pattern can allow the identification of the “6q terminal deletion syndrome.” Moreover, the potential role of FRA6E in generating these deletions is suggested. © 2005 Wiley‐Liss, Inc.
HRAS mutation analysis in Costello syndrome: Genotype and phenotype correlation
Authors: Gripp Karen W. , Lin Angela E. , Stabley Deborah L. , Nicholson Linda , Scott Charles I. , Doyle Daniel , Aoki Yoko , Matsubara Yoichi , Zackai Elaine H. , Lapunzina Pablo , Gonzalez‐Meneses Antonio , Holbrook Jennifer , Agresta Cynthia A. , Gonzalez Iris L. , Sol‐Church Katia
Published: December 2005

Costello syndrome is a rare condition comprising mental retardation, distinctive facial appearance, cardiovascular abnormalities (typically pulmonic stenosis, hypertrophic cardiomyopathy, and/or atrial tachycardia), tumor predisposition, and skin and musculoskeletal abnormalities. Recently mutations in HRAS were identified in 12 Japanese and Italian patients with clinical information available on 7 of the Japanese patients. To expand the molecular delineation of Costello syndrome, we performed mutation analysis in 34 North American and 6 European (total 40) patients with Costello syndrome, and detected missense mutations in HRAS in 33 (82.5%) patients. All mutations affected either codon 12 or 13 of the protein product, with G12S occurring in 30 (90.9%) patients of the mutation‐positive cases. In two patients, we found a mutation resulting in an alanine substitution in position 12 (G12A), and in one patient, we detected a novel mutation (G13C). Five different HRAS mutations have now been reported in Costello syndrome, however genotype–phenotype correlation remains incomplete. © 2005 Wiley‐Liss, Inc.
Inbreeding and surnames: A projection into Easter Island's past
Authors: González‐Martín Antonio , García‐Moro Clara , Hernández Miguel , Moral Pedro
Published: December 2005

The population of Easter Island is one of the most interesting extant human communities due to its unique demographic history, its geographic isolation, and the development of an incomparable culture characterized by the towering “Moais” and its enigmatic writing. Following the colonization of its population by Polynesians from the Mangarevan Islands in the 5th century AD, the island remained isolated up until the middle of the 20th century. Under these conditions, with endogamy levels fluctuating between 61.04–96.54% and given such a small population, a high rate of inbreeding, and consequently, an elevated level of genetic relationships would be expected. Using data from church and civil records, we calculated the consanguinity of the population of Rapa Nui. The results of this analysis do not support the hypothesis of a high level of consanguinity (α = 0.00028 and Ft = 0.0007, with Fr = 0.00586 and Fn = −0.00519), suggesting instead the existence of a strategy used to avoid marriage between close relatives. To explain these observations, the structure and exchange dynamics of the population were studied in the tribes, known locally as “Mata.” The results of this analysis suggest a tendency toward the avoidance of inbreeding within tribes, in order to decrease the rate of endogamy in each group. This is consistent with ethnographic observations from the beginning of the 20th century that support the existence of strict regulations to prevent inbreeding between closely related individuals. Furthermore, we confirm that this situation dates back to a period before the “refounding” of Easter Island. Our results demonstrate that conditions of geographical isolation are not in themselves sufficient to produce an elevated inbreeding coefficient, revealing Easter Island as an interesting example of how cultural rules can shape the genetic structure of a population. Am J Phys Anthropol, 2006. © 2005 Wiley‐Liss, Inc.
New solid polymer electrolytes based on PEO/PAN hybrids
Authors: Chun‐Guey Wu , Chiung‐Hui Wu , Ming‐I Lu , Huey‐Jan Chuang
Published: November 2005

Hybrid polymer dry electrolytes comprised of poly(ethylene oxide) (PEO), polyacrylonitrile (PAN), and LiClO4 were investigated. The impedance spectroscopy showed that the effect of PAN on the ion conductivity of PEO‐based electrolytes depends on the concentration of lithium salt. When the mole ratio of lithium to oxygen is 0.062 (15%LiClO4‐PEO), adding PAN will increase the ionic conductivity. Differential scanning calorimetry, NMR, and IR data suggested that the enhanced conductivity was due to both the decreasing of the PEO crystallinity and increasing of the degree of ionization of lithium salt. There was obviously no interaction between PAN and lithium ions, and PAN acts as a reinforcing filler, and hence contributes to the mechanical strength besides reducing the crystallinity of the polymer electrolytes. When the LiClO4‐PEO‐PAN hybrid polymer electrolyte was heated at 200°C under N2, PAN crosslinked partially, which further decreased the crystallinity of PEO and increased the ionic conductivity, and at the same time prevented the recrystallization of PEO upon sitting at ambient environment. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 1530–1540, 2006
Generation of neoantigenic epitopes after posttranslational modification of type II collagen by factors present within the inflamed joint
Authors: Nissim Ahuva , Winyard Paul G. , Corrigall Valerie , Fatah Rewas , Perrett David , Panayi Gabriel , Chernajovsky Yuti
Published: December 2005

Objective

Collagen‐induced arthritis is a commonly accepted model of rheumatoid arthritis (RA). However, it has been difficult to substantiate the involvement of autoimmunity to type II collagen (CII) in the pathogenesis of RA. The aim of this investigation was to determine if CII, modified by reactive oxidant species present within the inflamed joint, could generate neoantigenic epitopes.

Methods

Oxidants that play a role in acute and chronic inflammation and are present in the rheumatoid joint (hydroxyl radical, hypochlorous acid, and peroxynitrite) were used for modification of native CII. In addition, CII was glycated with ribose, since nonenzymatic oxidative reactions by glycation are evident in RA. Modifications were analyzed by sodium dodecyl sulfate–polyacrylamide gel electrophoresis and 3‐dimensional fluorescence followed by enzyme‐linked immunosorbent assay (ELISA) and Western blotting, using, as probes, sera from patients with RA and from patients with other inflammatory and noninflammatory joint diseases.

Results

Only 1 RA serum sample showed strong binding to native CII. In contrast, binding to modified CII was increased in 14 of 31 RA sera, of which 7 were strong binders and 7 were moderate binders. Among the non‐RA serum samples, only 1 yielded a strong reaction to modified CII and 5 of 41 were moderate binders. Samples that showed the strongest binding to modified CII in ELISA also showed strong binding to various fragmented or aggregated forms of CII in Western blots, as well as strong binding to fragmented CII present in RA synovial fluid.

Conclusion

When modified by conditions found within the inflamed joint, CII acts as an autoantigen in RA.
Tissue trafficking patterns of effector memory CD4+ T cells in rheumatoid arthritis
Authors: Zhang Xiaoyu , Nakajima Takako , Goronzy Jörg J. , Weyand Cornelia M.
Published: December 2005

Objective

Clonal populations of CD4+,CD28− T cells accumulating in rheumatoid arthritis functionally resemble end‐differentiated, nondividing, short‐lived effector memory cells that reside in peripheral tissues. We undertook this study to examine the tissue niche for CD4+,CD28− T cells and the signals regulating their survival and tissue homing patterns.

Methods

Chemokine receptor expression on CD4+,CD28− T cell clones and peripheral blood lymphocytes was assessed by multicolor cytometry. In vitro chemotaxis and transendothelial migration were examined in a Transwell system. In vivo tissue‐homing patterns were established by adoptively transferring fluorescence‐labeled T cell clones into SCID mice engrafted either with rheumatoid synovium or with human lymph nodes.

Results

CD4+,CD28− T cell clones adoptively transferred into human tissue–SCID mouse chimeras infiltrated rheumatoid synovium but preferentially homed to lymph nodes. Such T cells coexpressed the chemokine receptors CCR7, CCR5, and CXCR4 and migrated in response to both inflammatory chemokines (CCL5) and homing chemokines (CXCL12). T cell receptor crosslinking abrogated chemotactic responsiveness. In contrast, interleukin‐12 stimulation induced the up‐regulation of CCR5 and a shift in the in vivo homing pattern away from the lymph nodes toward the inflamed synovium.

Conclusion

CD4+,CD28− T cells resemble both short‐lived effector memory cells and long‐lived central memory cells, and they find a niche both in inflamed synovium and in lymph nodes. Nonspecific cytokine stimulation, not antigen recognition, triggers the transition from the lymph node to the synovium. By maintaining CCR7 expression, these end‐differentiated T cells can home to lymphoid organs, enhance their survival, support clonal expansion, and perpetuate autoreactivity.