bluuebunny/crossref_metadata_2025 huggingface dataset:
Extragalactic Globular Clusters and Galaxy Formation
Authors: Brodie Jean P. , Strader Jay
Published: June 2006

Globular cluster (GC) systems have now been studied in galaxies ranging from dwarfs to giants and spanning the full Hubble sequence of morphological types. Imaging and spectroscopy with the Hubble Space Telescope and large ground-based telescopes have together established that most galaxies have bimodal color distributions that reflect two subpopulations of old GCs: metal-poor and metal-rich. The characteristics of both subpopulations are correlated with those of their parent galaxies. We argue that metal-poor GCs formed in low-mass dark matter halos in the early universe and that their properties reflect biased galaxy assembly. The metal-rich GCs were born in the subsequent dissipational buildup of their parent galaxies and their ages and abundances indicate that most massive early-type galaxies formed the bulk of their stars at early times. Detailed studies of both subpopulations offer some of the strongest constraints on hierarchical galaxy formation that can be obtained in the near-field.
X-Ray Emission from Extragalactic Jets
Authors: Harris D.E. , Krawczynski Henric
Published: June 2006

This review focuses on the X-ray emission processes of extragalactic jets on scales resolvable by the subarcsec resolution of the Chandra X-ray Observatory. It is divided into four parts. The introductory section reviews the classical problems for jets, as well as those associated directly with the X-ray emission. Throughout this section, we deal with the dualisms of low-powered radio sources versus high-powered radio galaxies and quasars and of synchrotron models versus inverse Compton models; and the distinction between the relativistic plasma responsible for the received radiation and the medium responsible for the transport of energy down the jet. The second section collects the observational and inferred parameters for the currently detected X-ray jets and attempts to put their relative sizes and luminosities in perspective. In the third section we first give the relevant radio and optical jet characteristics, and then examine the details of the X-ray data and how they can be related to various jet attributes. The last section is devoted to a critique of the two nonthermal emission processes and to prospects for progress in our understanding of jets.
First Fruits of the Spitzer Space Telescope: Galactic and Solar System Studies
Authors: Werner Michael , Fazio Giovanni , Rieke George , Roellig Thomas L. , Watson Dan M.
Published: June 2006

The Spitzer Space Telescope, launched in August 2003, is the infrared member of NASA's Great Observatory family. Spitzer combines the intrinsic sensitivity of a cryogenic telescope in space with the imaging and spectroscopic power of modern infrared detector arrays. This review covers early results from Spitzer that have produced major advances in our understanding of our own solar system and phenomena within the Galaxy. Spitzer has made the first detection of light from extrasolar planets, characterized planet-forming and planetary debris disks around solar-type stars, showed that substellar objects with masses smaller than 10 MJup form through the same processes as do solar-mass stars, and studied in detail the composition of cometary ejecta in our Solar System. Spitzer's major technical advances will pave the way for yet more powerful future instruments. Spitzer should operate with full capabilities well into 2009, enabling several additional cycles of discovery and follow-up.
Cholesterol Sensing, Trafficking, and Esterification
Authors: Chang Ta-Yuan , Chang Catherine C.Y. , Ohgami Nobutaka , Yamauchi Yoshio
Published: June 2006

Mammalian cells acquire cholesterol from low-density lipoprotein (LDL) and from endogenous biosynthesis. The roles of the Niemann-Pick type C1 protein in mediating the endosomal transport of LDL-derived cholesterol and endogenously synthesized cholesterol are discussed. Excess cellular cholesterol is converted to cholesteryl esters by the enzyme acyl-coenzyme A:cholesterol acyltransferase (ACAT) 1 or is removed from a cell by cellular cholesterol efflux at the plasma membrane. A close relationship between the ACAT substrate pool and the cholesterol efflux pool is proposed. Sterol-sensing domains (SSDs) are present in several membrane proteins, including NPC1, HMG-CoA reductase, and the SREBP cleavage–activating protein. The functions of SSDs are described. ACAT1 is an endoplasmic reticulum cholesterol sensor and contains a signature motif characteristic of the membrane-bound acyltransferase family. The nonvesicular cholesterol translocation processes involve the START domain proteins and the oxysterol binding protein–related proteins (ORPs). The properties of these proteins are summarized.
Modification of Proteins by Ubiquitin and Ubiquitin-Like Proteins
Authors: Kerscher Oliver , Felberbaum Rachael , Hochstrasser Mark
Published: June 2006

Following the discovery of protein modification by the small, highly conserved ubiquitin polypeptide, a number of distinct ubiquitin-like proteins (Ubls) have been found to function as protein modifiers as well. These Ubls, which include SUMO, ISG15, Nedd8, and Atg8, function as critical regulators of many cellular processes, including transcription, DNA repair, signal transduction, autophagy, and cell-cycle control. A growing body of data also implicates the dysregulation of Ubl-substrate modification and mutations in the Ubl-conjugation machinery in the etiology and progression of a number of human diseases. The primary aim of this review is to summarize the latest developments in our understanding of the different Ubl-protein modification systems, including the shared and unique features of these related pathways.
Governmentality
Authors: Rose Nikolas , O'Malley Pat , Valverde Mariana
Published: June 2006

▪ Abstract  This review surveys the development of Michel Foucault's analysis of political power in terms of governmentality and outlines its key characteristics. It examines the spread of this perspective, focusing in particular on how this genealogical approach to the analysis of the conduct of each and of all has been taken up and developed in the English-speaking world. It evaluates some of the key criticisms that have been made of the analytics of governmentality and argues for the continuing productivity and creativity of these ways of analyzing the emergence, nature, and consequences of the arts of government.
Defining Virulence Genes in the Dimorphic Fungi
Authors: Rappleye Chad A. , Goldman William E.
Published: June 2006

Most dimorphic fungal pathogens cause respiratory disease in mammals and must therefore possess virulence mechanisms to combat and overcome host pulmonary defenses. Over the past decade, advances in genetic tools have made it possible to investigate the basis of dimorphic fungal pathogenesis at the molecular level. Gene disruptions and RNA interference have now formally demonstrated the involvement of six virulence factors: CBP, α-(1,3)-glucan, BAD1, SOWgp, Mep1, and urease. Additional candidate virulence-associated genes have been identified on the premise that factors necessary for pathogenicity are associated specifically with the parasitic form. This principle continues to form the foundation for genomics-based analyses to further augment the list. Thus, the stage is set and the tools are in place for the next phase of medical mycology research: defining the virulence-associated factors underlying the success of dimorphic fungal pathogens.
Subterfuge and Manipulation: Type III Effector Proteins of Phytopathogenic Bacteria
Authors: Grant Sarah R. , Fisher Emily J. , Chang Jeff H. , Mole Beth M. , Dangl Jeffery L.
Published: June 2006

Diverse gram-negative bacteria deliver effector proteins into the cells of their eukaryotic hosts using the type III secretion system. Collectively, these type III effector proteins function to optimize the host cell environment for bacterial growth. Type III effector proteins are essential for the virulence of Pseudomonas syringae, Xanthomonas spp., Ralstonia solanacearum and Erwinia species. Type III secretion systems are also found in nonpathogenic pseudomonads and in species of symbiotic nitrogen-fixing Rhizobium. We discuss the functions of type III effector proteins of plant-associated bacteria, with an emphasis on pathogens. Plant pathogens tend to carry diverse collections of type III effectors that likely share overlapping functions. Several effectors inhibit host defense responses. The eukaryotic host targets of only a few type III effector proteins are currently known. We also discuss possible mechanisms for diversification of the suite of type III effector proteins carried by a given bacterial strain.
Hydrodynamic Models for Heavy Ion Collisions
Authors: Huovinen P. , Ruuskanen P.V.
Published: June 2006

▪ Abstract  Application of hydrodynamics for modeling of heavy ion collisions is reviewed. We consider several physical observables that can be calculated in this approach and compare them to the experimental measurements.
Primordial Neutrinos
Authors: Hannestad Steen
Published: June 2006

▪ Abstract  This review discusses in detail the connection between cosmological observations and neutrino physics. Neutrinos decouple from thermal contact in the early universe at a temperature of order 1 MeV, which coincides with the temperature at which light-element synthesis occurs. Observations of light-element abundances therefore provide important information about properties such as neutrino energy density and chemical potential. Precision observations of the cosmic microwave background and large-scale structure of galaxies can be used to probe neutrino masses with greater precision than current laboratory experiments. This review discusses current cosmological bounds on neutrino properties, as well as possible bounds from upcoming measurements.
Protecting Freedom of and from Religion: Questioning the Law's Ability to Protect Against Unethical Conversions in Sri Lanka
Authors: Owens Alexandra
Published: June 2006

In recent years, the issue of improper and unethical conversions has attracted much attention in Sri Lanka. The issue is a highly emotive one, with members of the majority Buddhist population calling for measures to protect their religion from 'threats' from other minority religions, and members of these other religious groups expressing growing feelings of discrimination and unequal treatment. This article examines recent case law in the field of unethical conversions in Sri Lanka. An analysis of the decisions of Sri Lanka's Supreme Court relating to the incorporation of Christian organizations suggests that the legal system in Sri Lanka has struggled in its attempt to secure the right to freedom of religion and the right to manifest a religion for all people. Moreover, it is argued that the law has ultimately fuelled the growing religious tensions across the island. This article questions the law's ability to protect against unethical conversions in Sri Lanka, and therefore seeks to add weight to the calls for a non-legislative approach to the issue in order to allow for respect for the human rights of all concerned.
“The Streets”
Authors: Oliver William
Published: June 2006

The primary purpose of this article is to describe the social significance of “the streets” as an alternative to the family, church, and other communitybased institutions that facilitate Black male socialization. A major assumption of this discussion is that for many marginal Black males, “the streets” is a socialization institution that has a major influence on their psychosocial development and life-course trajectories and transitions. In addition, the article addresses some of the problematic consequences associated with the pursuit of manhood and social recognition in “the streets.”
“The Great Negro State of the Country?”
Authors: Parry Janine A. , Miller William H.
Published: June 2006

Scholarship on African American political participation—like research on political participation generally—has focused largely on the national-level preferences of citizens and policy makers. Considerably less attention has been paid to such dynamics in the American states. This article provides an introduction to Black legislative activity in the State of Arkansas with an eye on descriptive and substantive representation issues. Specifically, the article investigates the presence and role of Black Arkansans in the state's General Assembly in the post-1960s era of civil rights reforms, assessing their acquisition of legislative seats, their ascendancy to committee and chamber leadership positions, and—especially—their attempt to present an influential voting bloc. The article concludes that though African American legislators in Arkansas are disadvantaged by their small numbers, they have found other ways to exercise power in the state legislature.
Differences and Similarities Between the Rastafari Movement and the Nation of Islam
Authors: Barnett Michael
Published: June 2006

The two Black social movements under consideration in this article are now well established among Black communities in America and, although widely thought to be distinct from each other, have much in common. As such, this article seeks to explore the similarities and differences between the movements. One overarching similarity is that both movements empower their largely Black adherents by providing them with a positive Black identity. This may be viewed as an outcome of both movements being inspired by Marcus Garvey. In addition, because these movements emphasize change within the individual rather than change in the surrounding social structure, they are considered to be expressive social movements. A key difference between the movements is the specific type of positive Black identity that is inculcated. For the Rastafari movement, it is an African-centered, Afrocentric identity, whereas for the Nation of Islam it is a Blackcentric identity (that is not geographically anchored).
Gebrehiwot Baykedagn, Eurocentrism, and the Decentering of Ethiopia
Authors: Kebede Messay
Published: June 2006

The article critically evaluates the analysis that Gebrehiwot Baykedagn, a prominent intellectual among the early Ethiopians who were exposed to Western education, gives of Ethiopia's social and technological lag behind European countries. It shows how the Eurocentric conception of history prevented Baykedagn from developing any positive view about Ethiopian history and culture and how this failure led him to prescribe wrong remedies despite his remarkable insights into the dangers of economic dependency. The need to get out of Eurocentrism is strengthened by an attempt to approach Ethiopian history from the viewpoint of Ethiopians themselves rather than from European norms.
Philosophy Against Empire
Authors: Verharen Charles C.
Published: June 2006

What should be the politics of Afrocentricity? How should Afrocentrists fight globalization's empire, the continuation of slavery by other means? This article grounds political resistance to empire in an ancient Egyptian philosophy of holism. The article's theme is that four powerful movements are converging on a new philosophy. Paradoxically, this “new” philosophy is prefigured in the oldest recorded philosophy, that of ancient Egypt. The four converging philosophies are Afrocentricity, ecofeminism, deep ecology or radical environmentalism, and Marxism. These movements are contemporary expressions of resistance to centuries if not millennia of violent oppression. The article's aim is to create a synergy among these movements to build a coalition that can challenge empire. The article briefly examines the historical career of holism in the area of ontology before considering expressions of holism in the areas of ethics and politics.
“Wicked Problems,” Public Policy, and Administrative Theory
Authors: Durant Robert F. , Legge Jerome S.
Published: June 2006

As societies worldwide struggle to address what policy analysts call “wicked problems” such as world hunger, malnutrition, and ecological sustainability, analysts from a variety of perspectives have questioned the administrative state’s abilities to deal with them. Ascendant since the early 1990s as a prescription for remedying these shortcomings is a market, technocratic, and non-deliberative theory of administration that some have called “neo-managerialism” and others the “managerialist ideology.” This study uses European attitudes toward promoting the use of genetically modified (GM) foods as a “policy window” for exploring how well or ill-suited the neo-managerialist philosophy informing the U.S. government’s promotional campaign was with the factors driving European opposition to GM foods. Causal modeling of the “calculus of dissent” that led to a the European Union (EU) moratorium on GM foods suggests that deliberative (rather than neo-managerialist) theories of administration are better suited for the “collective puzzlement of society” that wicked problems require.
The Evolving Role of the Public Sector in Managing Catastrophic Disasters
Authors: Kapucu Naim , Van Wart Montgomery
Published: June 2006

This article focuses on the emerging role of the public sector in dealing with catastrophic disasters. An empirical analysis of the 9/11 response operations provides a detailed case study with an eye to its implications for not only emergency management practice but public policy as well. The “horde of hurricanes” inundating Florida in 2004 provides a brief example of a “routine” disaster for comparative purposes. The argument is made that the response to the extreme event of 9/11 provides clear evidence of (a) the different standards expected of the public sector in the 21st century and (b) the fundamental difference in kind between routine disasters and catastrophic disasters. The article states that the public increasingly expects better public sector leadership before, during, and after catastrophic disasters than has been seen in the past. High standards of responsiveness and the ubiquitous media compel public leaders to coordinate resources effectively.
Home-Based Service Delivery: Introducing Family Counselors in Training to the Home as a Therapeutic Milieu
Authors: Woodford Mark S. , Bordeau Wendy Charkow , Alderfer Charleen
Published: June 2006

The provision of family counseling services in home- and communitybased settings is becoming an increasingly common and viable option for many human service organizations, either as the primary mode of service delivery or as part of a continuum of services. This article discusses the importance of providing family counselors in training with an introduction to home-based service delivery and provides methods for helping students to explore the home as a therapeutic milieu.
Controversy, Constraints, and Context: Understanding Family Violence Through Family Systems Theory
Authors: Murray Christine E.
Published: June 2006

This article discusses the controversies surrounding the use of family systems theory as a framework for understanding family violence. The author examines potential implications for the exclusion of family systems approaches in the research and treatment of family violence. In addition, the author describes several opportunities that may arise through the application of family systems theory to family violence for theory, practice, and research.
Parental Influences on Adolescent Adjustment: Parenting Styles Versus Parenting Practices
Authors: Lee Sang Min , Daniels M. Harry , Kissinger Daniel B.
Published: June 2006

The study identified distinct patterns of parental practices that differentially influence adolescent behavior using the National Educational Longitudinal Survey (NELS:88) database. Following Brenner and Fox's research model (1999), the cluster analysis was used to classify the four types of parental practices. The clusters of parenting practices in the current study showed convergence with Baumrind's parenting style. The results indicated that these four clusters differentially affected students' self-concept, locus of control, and academic achievement. The authors discuss how these identified parenting behavior patterns are linked with children's adjustment, development, and achievement.
Serial-Episodic Brief Treatment for Borderline Spectrum Families: Employing the Matrix of Projections in a Child Abuse Case
Authors: Clark Steven
Published: June 2006

The author addresses the fact that many families with a borderline structure receive treatment throughout the life cycle. Serial episodic brief treatment is recommended, utilizing projective identification as an organizing principle to promote incremental change during each treatment episode. The author selects a child abuse case to review, that reflects the tendency of these families to have broad involvement in the social service network. Of interest is the influence of social control systems on the treatment process and the treatment relation-ship. These contextual variables are explored, utilizing the concept of a projective matrix that promotes treatment options.
Robert Kegan, PhD: Subject-Object Theory and Family Therapy
Authors: Eriksen Karen
Published: June 2006

This article explores the constructive developmental theory of Robert Kegan and his work regarding ongoing psychological transformation in adulthood. The interview offers some interesting insights and examples of individuals constructing or self-authoring their own experiences. Kegan relates his theory and recent professional work to family counseling.
The Constructive Developmental Theory of Robert Kegan
Authors: Eriksen Karen
Published: June 2006

Counselors pride themselves in their developmental focus; however, they have predominantly limited themselves to applications of phasic, or life span development. Stage developmental theories have much to offer to understandings of individuals and families, and yet such theories are largely absent from the counseling literature. This article begins to remedy that absence by introducing one stage theory: Robert Kegan's subject-object theory. The article is followed in this journal by an interview with Kegan on applications of his theory to family work.
Feeling the Tug: Creative Use of Ropes and Felt Board to Promote Family Change
Authors: Bruhn Rick A. , Lykke Debra B. , Duhl Bunny S.
Published: June 2006

Experiential metaphor has been used in marriage and family therapy for many years. One example of metaphor application involves the use of ropes and felt board to identify and explore relationships in families. In this case, the mother of a son who was socially isolated is treated by a marriage and family therapy intern, using ropes and felt board as media to exemplify the tugs of relationships, demands, and expectations. Responding to the metaphors, the mother changed relationships with her son, other children, and her former and current husbands. Literature supporting the use of metaphors in therapeutic contexts sets the stage for the description of the efficacy of ropes as metaphor in therapy. The case study offers a detailed account of techniques used.
Male and Female Circumcision Today
Authors: Renshaw Domeena C.
Published: June 2006

The article explores historical and contemporary practices in male and female circumcision. Genital mutilation is reviewed in its cultural contexts.
The Family Journal Reader Interests: An Internet Survey
Authors: Nelson Kaye W. , Southern Stephen , Cade Rochelle , Livingston Patrisha K.
Published: June 2006

An Internet-based survey was completed with members of the International Association of Marriage and Family Counselors (IAMFC) regarding their interests in topics and sections published in The Family Journal. In addition, the survey addressed future reading preferences of respondents. The results confirmed the stated mission of the journal, including the practice-orientation of IAMFC readers, past editorial directions, and conclusions from a recent content analysis. Based on the findings, the editorial team hopes to solicit additional manuscripts concerned with adolescents, addiction, sexual issues, healthy marriage, grief, and supervision.
Nascent Internal-State Distribution of Product OH(A2Σ) Observed in a Crossed Beam Reaction of Hot H Atom with N2O
Authors: Tsuboi Shinji , Sawai Toshihiro , Ohoyama Hiroshi , Kasai Toshio
Published: June 2006

The chemiluminescence spectrum of product OH(A2Σ) in a crossed beam reaction of the hot H atom with N2O was observed for the first time. The nascent internal-state distribution of OH(A2Σ) was identified by spectral simulation. The rotational distribution was found to be characterized by a Boltzmann temperature of 750 ± 100 K, and the vibrational distribution is non-Boltzmann with the populations of v = 0, 1, and 2 being 1 : 0.75 : 0.15, respectively. These results indicate that the product rotation is poorly excited while vibration is highly excited to the contrary.
Markaracter Tables and Q-Conjugacy Character Tables for Cyclic Groups. An Application to Combinatorial Enumeration
Authors: Fujita Shinsaku
Published: June 2006

Q-Conjugacy character tables for cyclic groups are obtained by starting from character tables. Thus, irreducible representations for a cyclic group are classified into primitive and non-primitive ones. They are collected to form a matrix corresponding to each subgroup. Such a matrix is shown to be a representation (called Q-conjugacy representation) for characterizing Q-conjugacy and dominant classes. The traces of the Q-conjugacy representation are collected to form a Q-conjugacy character table, which is shown to be a square matrix. The elements of such a Q-conjugacy character table for a cyclic group are shown to be integers, which are related to the values of the corresponding character tables. They are also correlated to the markaracter tables for the cyclic group. Characteristic monomial tables for cyclic groups are obtained by starting from the Q-conjugacy character tables and dominant unit-subduced-cycle-index tables. They are applied to combinatorial enumeration of isomers derived from a skeleton belonging to a cyclic group.
High Complexation Ability of Thiacalixarene with Transition Metal Ions. The Effects of Replacing Methylene Bridges of Tetra(p-t-butyl)calix[4]arenetetrol by Epithio Groups
Authors: Iki Nobuhiko , Morohashi Naoya , Narumi Fumitaka , Miyano Sotaro
Published: June 2006

The ability of tetra(p-t-butyl)tetrathiacalix[4]arenetetrol (TCA, H4L), a cyclic tetramer of p-(t-butyl)phenol bridged with four epithio groups, to bind metal ions was investigated via a solvent extraction study. Although tetra(p-t-butyl)calix[4]arenetetrol (CA) has very poor affinity for transition metal ions (M2+), TCA is an excellent extractant of these metal ions. The chemical formulae of the extracted TCA metal complexes were found by slope analysis to be neutral 1 : 1 complexes [MH2L]. The origin of the high affinity of TCA for transition metal ions is discussed, in which it is suggested that ligation of the epithio group is important as evidenced by an NMR study of the [ZnH2L] complex.
Formation of Stable Carbocations or Zwitterions by a Specific Interaction with Alkali Metal or Alkaline-Earth Metal Ions in Acetonitrile
Authors: Hojo Masashi , Hasegawa Hiroshi , Tsurui Hitoshi , Kawamura Kazushi , Minami Sei-ichiro , Mizobe Atsuko
Published: June 2006

In an acetonitrile solution, the extents of ionization of trityl halides (Ph3CX: X = Cl, Br) in the presence of various concentrations of alkali metal (M+ = Li+, Na+) and alkaline-earth metal (M2+ = Mg2+, Ca2+, Sr2+, Ba2+) perchlorates were examined by spectrophotometry. The promoted formation of the trityl ion (Ph3C+) in the presence of metal ions was attributed to “chemical” interactions, such as coordination or covalent bonding between the halide ions and M+ or M2+ ions, and not merely the electrostatic interaction. The salt effects increased with methoxy-substituents on trityl chloride as non-substituted < 4-methoxy < 4,4′-dimethoxy < 4,4′,4″-trimethoxytrityl. At higher RX (or X−) concentrations, not only “coordination”, but also precipitation reactions between X− and M+ or M2+ (except for Li+ and Mg2+) seemed to promote the ionization of RX. In the co-presence of a small amount of CH3SO3H, trityl benzoate gave the Ph3C+ ion upon the addition of LiClO4 or Mg(ClO4)2. A red color with strong fluorescence due to the zwitterion (R+–COO−) of Rhodamine (Rhodamine B base) was observed upon the addition of M+ and M2+, which should have been caused by an interaction between the metal ions and the intramolecule carboxylate (from the γ-lactone) of Rhodamine in the solution. The γ-lactone ring of Crystal Violet lactone in acetonitrile was cleaved by the addition of Mg(ClO4)2 to give a strong violet color, whereas, LiClO4, NaClO4, or Ba(ClO4)2 had no (or very small) effects in the solution. It was found that the interactions between X− or RCOO− and M+ or M2+ in acetonitrile were strong enough to promote the ionization of partly ionized covalent bonds.
Reactions of Bis(2,6-dimethoxyphenyl)methanol in Common Organic Solvents in the Presence of an Acid
Authors: Wada Masanori , Konishi Hideki , Kai Takanori , Takeuchi Hiroshi , Natsume Satoko , Erabi Tatsuo
Published: June 2006

The title compound, Φ2CHOH [Φ = 2,6-(MeO)2C6H3] (1), reacted in acetone under mild conditions in the presence of acid to give a new ketone, Φ2CHCH2COMe. Analogous reactions were observed in some other alkyl ketones and aldehydes, such as diethyl ketone, methyl phenyl ketone, 2,4-pentanedione, propanal, and butanal. In ethyl methyl ketone, an 80 : 20 mixture of Φ2CHCHMeCOMe and Φ2CHCH2COEt was obtained in agreement with the pKE values of two enols derived from ethyl methyl ketone. Compound 1 reacted in primary and secondary alcohols to give the reduced compound, Φ2CH2 (6), and the corresponding aldehyde and ketone derived from the alcohols, respectively. The reactivity of the alcohols was in the order, 1-propanol ≈ 1-butanol < ethanol < 2-butanol < 2-propanol. Compound 1 also reacted in ethers, such as tetrahydrofuran and diethyl ether, to give 6. It was either recovered unreacted from 2-methyl-2-propanol and from dimethyl sulfoxide, or it reacted under more forcing conditions to give products derived by Φ–C bond cleavage, followed by reactions of 1 with ΦH.
Novel [1, N]-Carbon to Carbon Rearrangement of an Ester Group via Organotitanium Intermediates Wherein the N Varies from 2 to 5. Full Scope and Limitation Leading Predominantly to the Rearrangement
Authors: Yamazaki Takanori , Urabe Hirokazu , Sato Fumie
Published: June 2006

Malonates and methanetricarboxylates having an unsaturated side chain such as 2, 12, 20, 22, 24, 31, or 37 underwent a new ester rearrangement reaction promoted by (η2-propene)Ti(O-i-Pr)2 to afford the succinate derivative 4 or α,β-unsaturated ester 17, 21, 23, 25, 34, or 38 via the migration of the ester group from its original bis- or tris-ester position to the acetylene- or olefin-titanium complex. It has been found that the side reactions competing with the desired migration are dealkylation of the side chain of the ester and a simple cyclization. The substrates and conditions which allow the ester migration a preferential path were determined as well as the scope and limitation of this reaction.
One-Step Synthesis of Naphthofurandione, Benzofurandione, and Phenalenofuranone Derivatives by the CAN-Mediated Cycloaddition
Authors: Kobayashi Kazuhiro , Uneda Tomokazu , Tanaka Koujirou , Mori Masako , Tanaka Hideo , Morikawa Osamu , Konishi Hisatoshi
Published: June 2006

The 3+2-type cycloaddition reaction of 2-hydroxy-1,4-naphthoquinones with various alkenes or phenylacetylene was mediated by ammonium cerium(IV) nitrate (CAN) to give the corresponding naphtho[2,3-b]furan-4,9-dione and naphtho[1,2-b]furan-4,5-dione derivatives. The reaction of 2-hydroxy-1,4-benzoquinones with alkenes in the presence of CAN similarly proceeded to give benzofuran-4,7-dione and benzofuran-4,5-dione derivatives. 3-Hydroxy-1H-phenalen-1-one also underwent the CAN-mediated cycloaddition with alkenes or phenylacetylene to give the corresponding 7H-phenaleno[1,2-b]furan-7-one derivatives.
In Vitro Selection of a DNA Aptamer Binding to Thyroxine
Authors: Kawazoe Naoki , Ito Yoshihiro , Shirakawa Masahiro , Imanishi Yukio
Published: June 2006

A DNA aptamer that selectively binds to a hormone, thyroxine, was isolated using the in vitro selection method. A pool of single-stranded DNAs consisting of random sequences was incubated with the thyroxine-immobilized agarose gel; bound DNAs were then collected and amplified by the polymerase chain reaction. This selection process was repeated nine times. The selected DNAs were cloned and sequenced. Some of the cloned DNA contained a consensus sequence. Several DNAs containing the sequence were chemically synthesized and the binding ratios to the thyroxine-immobilized gel were determined. Among them a DNA containing 14 nucleotides was found to bind selectively to thyroxine.
Intermolecular Hydrogen Bonds of 5-Benzylidene-2,4-thiazolidinedione Derivatives and Related Compounds in Crystalline State
Authors: Okazaki Masaki , Uchino Nobuhiko , Ishihara Makoto , Fukunaga Hiroo
Published: June 2006

From the viewpoint of noncentrosymmetric molecular arrangement design in crystalline state, which is indispensable to second order nonlinear optical materials, intermolecular hydrogen bond formation of eight 5-benzylidene-2,4-thiazolidinedione derivatives and related compounds were investigated by X-ray crystallography. 5-Benzylidene-2,4-thiazolidinedione (1) itself forms centrosymmetric head-to-head (or tail-to-tail) intermolecular hydrogen bonds and takes a centrosymmetric molecular arrangement in crystalline state. Introduction of 4-methoxy group into the phenyl moiety of 1 was the only useful means for head-to-tail type intermolecular hydrogen bond formation. 5-(4-Methoxybenzylidene)-2,4-thiazolidinedione shows head-to-tail type intermolecular hydrogen bonds and noncentrosymmetric molecular arrangement in crystalline state. Similarities in both hydrogen bond formation and molecular arrangement in crystalline state are obtained by conversion of 2,4-thiazolidinedione to 2-thioxo-4-oxazolidinone, but in the case of conversion to 2,4-oxazolidinedione only hydrogen bond formation is shown in a similar manner. In the case of conversion to rhodanine, no similarity in either hydrogen bond formation or molecular arrangement in crystalline state was shown. Such behaviors were considered from viewpoints of pKa and hydrogen bond energy.
Persistent Spectral Hole Burning of Phenoxazine and Phenothiazine Derivatives in Poly(vinyl alcohol) and the Effect of the Addition of N,N,N′,N′-Tetramethyl-p-phenylenediamine
Authors: Nishiyama Satoko , Machida Shinjiro , Yamashita Takashi , Horie Kazuyuki
Published: June 2006

The photochemical behavior at cryogenic temperatures of phenoxazine and phenothiazine dyes in poly(vinyl alcohol) was investigated by using persistent spectral hole burning. The importance of hydrogen-bondings has been confirmed by measuring the effects of the addition of N,N,N′,N′-tetramethyl-p-phenylenediamine on the holewidth and the hole area of various cationic dyes at 20 K. The hydrogen bonds around the ring-N atom affect the total dephasing time, while the hydrogen bonds around the amino groups as the substituents and around the ring-N atom control the efficiency of hole formation.
Functional Micropore Chemistry of Crystalline Metal Complex-Assembled Compounds
Authors: Kitagawa Susumu , Kondo Mitsuru
Published: June 2006

Syntheses of new porous frameworks with specific pore size and type are of considerable interest for the appearance of zeolite-like functionalities. It is useful to take advantage of metal complex-assembled compounds because of designable frameworks, high microporosity, and flexible frameworks based on a variety of coordination geometries of metal centers and multifunctionality of bridging organic parts. Many recent reports show that the synthesis procedures are developing from serendipitious to rational level. Therefore, the micropore chemistry of metal complex-based assemblages is directed toward not only new frameworks but also functionalities such as gas and small molecule adsorption, ion exchange, heterogeneous catalysis, photo-chemical and -physical properties. For chemical and physical functionalities robustness of a framework is required even in the absence of guest molecules in the cavity. The stability is largely dependent on the structural dimensionality of the assemblages. A wide variety of structures of metal complex-based assemblages are listed and recent findings in this functional chemistry are described.
Hydrogen Bonds of Poly[(n-alkyl methacrylate)-co-(methacrylic acid)]’s in Dilute Solutions
Authors: Noguchi Akihiro , Masui Yasusi , Oda Hirohisa , Kuzuya Masayuki
Published: June 2006

The nature of the association of poly[(n-alkyl methacrylate)-co-(methacrylic acid)]’s (poly(RMA-co-MAA)’s) in dilute chloroform solutions was investigated by Fourier transform infrared (FT-IR) spectroscopy and the solution viscosity. The proportions (Pfree) of free carboxyls increased with the length of the alkyl groups in RMA’s and with the decreasing MAA composition. From the relationships between Pfree and the effective concentration (Ceff) of carboxyls attached to the polymer chain, it was shown that the major substituent effects of the alkyl groups on the hydrogen bonds in the copolymers are the extension of the polymer chain and the steric effect on the association between carboxyls and ester groups. Also, from the features of the shrinkage of the polymer chains accompanied with the intrachain association of carboxyls it was suggested that the hydrogen bonds in the copolymers are formed chiefly between neighboring sites along the chain.
Spectral Characteristics of the Aggregation of α,β,γ,δ-Tetrakis(p-sulfophenyl)porphyrin in the Presence of Proteins
Authors: Huang Cheng Zhi , Li Yuan Fang , Li Na , Li Ke An , Tong Shen Yang
Published: June 2006

With the aid of absorption, fluorescence, and resonance light-scattering measurements, the aggregation of protonated water-soluble porphyrin, α,β,γ,δ-tetrakis(p-sulfophenyl)porphyrin, [H4tpps4]2−, in the presence of proteins has been characterized. At pH 1.86, proteins dissolved in water can form a positively charged microphase, which can neutralize the negative charges of [H4tpps4]2− distributed in it, leading to the J- and H-aggregation of [H4tpps4]2−. Exciton splitting signals, which are generally associated with the aggregation of porphyrins, as described by molecular-exciton theory, are observed at 436.1 nm on the resonance light-scattering spectra, supporting the porphyrin–porphyrin interactions in the positively charged microphase of proteins. It has been proved that positively charged microphase can protect aggregates of [H4tpps4]2− from water dilution and high temperature.
Coordination Polymers Self-Assembling from Cadmium(II) Ions and Flexible Pyridine-Based Bridging Ligands
Authors: Fujita Makoto , Aoyagi Masaru , Ogura Katsuyuki
Published: June 2006

This paper describes coordination polymers assembled from cadmium nitrate and flexible bridging ligands, py–X–py (py = 4-pyridyl, 1a: X = CH2, 1b: X = C(=CH2), 1c: X = CH2CH2). The X-ray structure analysis of these complexes showed that their infinite topologies are quite different from each other, despite the structural similarity of ligands 1a—1c. Upon treatment with Cd(NO3)2, 1a gave an infinite two-dimensional sheet structure with a stoichiometry of ML2 (M and L denote metal and ligand, respectively). Ligand 1b also afforded an infinite polymer possessing the same ML2 composition. However, the polymer structure is characterized by one-dimensionally bounded macrocyclic frameworks where adjacent Cd ions are linked by two ligand molecules. Interestingly, ligand 1c gave an infinite polymer of M2L3 composition whose structure was shown to be a unique one-dimensional framework having macrocyclic frameworks (M2L2) linked together by the third L molecules.
A Sulfur-Capped Triangular Cobalt–Tributylphosphine–Aminobenzenethiolato Complex: Synthesis, Structure and Properties of Co3(μ3-S)(abt)3(PBun3)3
Authors: Chen Zhong-Ning , Kang Bei-Sheng , Zhou Zhong-Yuan , Li Wen-Jie , Tong Ye-Xiang , Lu Zhong-Lin , Su Cheng-Yong
Published: June 2006

The reaction of CoCl2, Habt (2-aminobenzenethiol), NaOMe and PBun3 (tributylphosphine) in an equimolar ratio under anaerobic conditions, followed by the addition of an excess of Li2S led to the triangular cluster complex Co3(μ3-S)(abt)3(PBun3)3. It crystallizes in the triclinic space group , with a = 13.231(2), b = 14.201(2), c = 18.890(2) Å, α = 79.970(10)°, β = 87.560(10)°, γ = 67.040(1)°, V = 3216.6(12) Å3 and Z = 2. The molecule consists of three “Co(abt)(PBun3)” units with the Co3 plane capped by the bridging μ3-S atom to form an approximately equilateral triangle with an average Co–Co distance of 2.709 Å. The cobalt atoms located in distorted trigonal-bipyramidal environments are further bridged by μ2-S atoms from the three abt ligands and terminally coordinated by N and P donors. The cyclic voltammogram showed three quasi-reversible redox processes with E1/2 = 0.79, −0.07, and −0.81 V, vs. SCE. The variable-temperature magnetic susceptibility measurements showed an antiferromagnetic exchange interaction within the triangular spin cluster.
Chain Compounds of Molybdenum(II) Trifluoroacetate Linked by p-Quinones [Mo2(O2CCF3)4(p-quin)]n, p-quin = 9,10-anthraquinone, 2,6-dimethyl-1,4-benzoquinone, and 1,4-naphthoquinone
Authors: Handa Makoto , Matsumoto Hiroki , Yoshioka Daisuke , Nukada Ryoji , Mikuriya Masahiro , Hiromitsu Ichiro , Kasuga Kuninobu
Published: June 2006

A series of chain complexes of molybdenum(II) trifluoroacetate linked by p-quinones, [Mo2(O2CCF3)4(p-quin)]n, p-quin = 9,10-anthraquinone (9,10-aq), 2,6-dimethyl-1,4-benzoquinone (2,6-dmbq), and 1,4-naphthoquinone (1,4-nq) have been prepared. The X-ray structure analyses showed that the carbonyl oxygens of the p-quinones are coordinated to the Mo2 dimers with distances of 2.478(6) and 2.532(5) Å (for 9,10-aq), 2.619(9) and 2.596(10) Å (for 2,6-dmbq), and 2.522(8) Å (for 1,4-nq), respectively. The Mo–Mo bond distances are 2.107(1)—2.117(1) Å, which are slightly longer than that of Mo2(O2CCF3)4 (2.090(4) Å). Elongation of the C=O and C=C bonds of the 9,10-aq and 2,6-dmbq molecules on the coordination has been observed, but the bond distances of the coordinated and uncoordinated 1,4-nq molecules are similar to each other. The difference is discussed in terms of the oxidizing abilities and the symmetries of the p-quinones.
Kinetics and Mechanisms of the Reaction of PH2O2− with O2, Photocatalyzed by [Ru(bpy)3]2+* (bpy = 2,2′-bipyridine), Forming Peroxodiphosphate Ions in an Aqueous Solution
Authors: Kimura Masaru , Takahashi Aki , Sakata Tomomi , Tsukahara Keiichi
Published: June 2006

The formation reaction of peroxodiphosphate (denoted by PDP and meaning P2O84−, HP2O83− etc.) by the reaction of molecular oxygen (O2) with the phosphinate ion (PH2O2−) was extremely accelerated by irradiation with visible light of aqueous solutions containing the tris(2,2′-bipyridine)ruthenium(II) ion ([Ru(bpy)3]2+). The [Ru(bpy)3]2+ acted as a photocatalyst during the reaction. The reaction mechanism consists of a chain reaction being accompanied by the O2-quenching of a photoexcited ruthenium(II) complex ([Ru(bpy)3]2+*) to make the superoxide (O2−•) and [Ru(bpy)3]3+, followed by the reduction of [Ru(bpy)3]3+ by PH2O2− to make [Ru(bpy)3]2+ and PH2O2•. However, such PDP once formed in the presence of O2 began to decrease with a rate law of -d[PDP]/dt = kobsd[PDP] after the solution was saturated with N2 gas, and when the solution was again saturated with air, the PDP began to increase again with light irradiation and remained constant in the dark. Such behaviors are discussed while presenting the reaction mechanisms.
Study of Adsorption of Water-Soluble Porphyrin at Glass–Solution Interface in the Presence of Cationic Surfactant Admicelles by Means of Total Internal Reflection Spectroscopy
Authors: Kobayashi Junji , Hinoue Teruo , Watarai Hitoshi
Published: June 2006

Total internal reflection (TIR) spectra were measured in the visible region at an interface between glass and an aqueous solution of 1.00 × 10−6 mol dm−3 5,10,15,20-tetraphenylporphyrintetrasulfonic acid (TPPS) in the presence of admicelles of cetyltrimethylammonium bromide (CTAB). Comparison of the TIR spectra with transmission spectra of TPPS solutions with different CTAB concentrations revealed that the deprotonated ions, TPPS4−, are simultaneously adsorbed at the interface as two complexes with TPPS4-/CTA+ ratios of 1 : 4 and 1 : 7. Interfacial concentrations of the 1 : 7 complex were estimated by using a linear relation between the absorbance and the interfacial concentration derived from a theory of TIR spectroscopy. The concentration data indicated that the adsorption of TPPS hardly occurs below pH 3, is saturated at pHs between 4 and 6, and continuously decreases above pH 6. Assuming an aggregative structure of the admicelle, the pH dependence of the adsorption was mathematically treated with a model including the dissociation, complex formation, and adsorption equilibria.
Convenient Synthesis of the Central 3,6-Di(2-thiazolyl)-2-(4-thiazolyl)pyridine Skeleton of a Macrocyclic Antibiotic, GE 2270 A
Authors: Okumura Kazuo , Saito Hiroyuki , Shin Chung-gi , Umemura Kazuyuki , Yoshimura Juji
Published: June 2006

It was shown that 6-dimethoxymethyl-1,2-dihydro-2-oxo-3-pyridinecarbonitrile (5) is easily convertible into the titled ring system by a stepwise method. Both the 3-cyano and 6-dimethoxymethyl groups of 5 were converted into 2-thiazolyl groups via the thioamide and carbaldehyde groups by Hantzsch and Shioiri methods, respectively. The 2-pyridone function was changed to a bromoacetyl group via the coupling reaction between the corresponding triflate and ethyl vinyl ether, and then converted into the 4-thiazolyl group. Thus, the useful 3,6-di(2-thiazolyl)-2-(4-thiazolyl)pyridine derivative for the total synthesis of GE 2270 A was obtained. In fact, the method was recently applied to the total synthesis of an antibiotic, micrococcin P, which has a similar central skeleton.
Reactions in Solid and Constrained State. IV. Preparation and Solid-State Photoracemization of Optically Active Alkyl Cobaloxime Complexes
Authors: Arai Yoshifusa , Ohgo Yoshiaki
Published: June 2006

Various optically active 1-substituted and 1,2-disubstituted ethyl cobaloxime [bis(dimethylglyoximato)cobalt(III)] complexes including deuterium-labeled complexes were prepared. Their photoracemization was found to occur upon irradiation of visible light in the solid-state. The reaction rate was much greater than that of solid-state racemization by irradiation of X-rays. The rates were not controlled by the electronic character of axial base and alkyl group but by the crystal lattice: the volume and shape of the reaction cavity, flexibility of the cavity, and intermolecular interaction such as hydrogen bonding. The experiments using deuterium-labeled complexes revealed the main reaction path in which the racemization proceeds mainly through out-of-plane rotation of the alkyl radical.
Facile Preparation of Four Stereoisomers of 2,4-Thiazolidinedicarboxylic Acid
Authors: Shiraiwa Tadashi , Katayama Takashi , Kaito Takehiro , Tanigawa Hisashi , Kurokawa Hidemoto
Published: June 2006

(2R,4R)-2,4-Thiazolidinedicarboxylic acid [(2R,4R)-TDA] was diastereoselectively synthesized in 100% de by condensation of l-cysteine (l-Cys) with an equimolar amount of glyoxylic acid monohydrate (GLA·H2O) in acetic acid under reflux. The reaction employing a slight excess of GLA·H2O afforded (2S,4R)-TDA, as a single diastereomer, at 80 °C. (2S,4R)-TDA was also synthesized by reaction of l-Cys with dichloroacetic acid under alkaline conditions. These reactions starting with d-Cys yielded (2S,4S)- and (2R,4S)-TDA.