bluuebunny/crossref_metadata_2025 huggingface dataset:
Genetic and Molecular Characterization of the I Locus of Phaseolus vulgaris
Authors: Vallejos C Eduardo , Astua-Monge Gustavo , Jones Valerie , Plyler Tammy R , Sakiyama Ney S , Mackenzie Sally A
Published: December 2005

The I locus of the common bean, Phaseolus vulgaris, controls the development of four different phenotypes in response to inoculation with Bean common mosaic  virus, Bean common mosaic necrosis virus, several other related potyviruses, and one comovirus. We have generated a high-resolution linkage map around this locus and have aligned it with a physical map constructed with BAC clones. These clones were obtained from a library of the cultivar “Sprite,” which carries the dominant allele at the I locus. We have identified a large cluster of TIR–NBS–LRR sequences associated within this locus, which extends over a distance >425 kb. Bean cultivars from the Andean or Mesoamerican gene pool that contain the dominant allele share the same haplotypes as revealed by gel blot hybridizations with a TIR probe. In contrast, beans with a recessive allele display simpler and variable haplotypes. A survey of wild accessions from Argentina to Mexico showed that this multigene family has expanded significantly during evolution and domestication. RNA gel blot analysis indicated that the TIR family of genes plays a role in the response to inoculations with BCMV or BCMNV.
zds1, a Novel Gene Encoding an Ortholog of Zds1 and Zds2, Controls Sexual Differentiation, Cell Wall Integrity and Cell Morphology in Fission Yeast
Authors: Yakura Miyo , Ozoe Fumiyo , Ishida Hideki , Nakagawa Tsuyoshi , Tanaka Katsunori , Matsuda Hideyuki , Kawamukai Makoto
Published: December 2005

While screening for genes that reverse the sporulation-deficient phenotype of the ras1Δ diploid Schizosaccharomyces pombe strain, we identified zds1. This gene shares sequence homology with the ZDS1 and ZDS2 genes from Saccharomyces cerevisiae, which appear to be involved in multiple cellular events. Expression of Zds1 in ras1Δ diploid cells elevated their sporulation rate from 0.3 to 11.2%. Expression of the Zds1 C-terminal region increased the sporulation rate further (to 21.9%) while introduction of the Zds1 N-terminal region had no effect. zds1 expression did not induce sporulation in strains with mutations in genes participating in the downstream MAP kinase cascade. The zds1-disrupted strain is sensitive to CaCl2, and this effect is suppressed by the C-terminal region of Zds1. The growth of the zds1Δ strain is markedly inhibited by cold temperatures, while its viability decreased in the stationary phase. Moreover, the zds1Δ strain is round in shape and very sensitive to zymolyase, and its cell wall becomes thicker than that of wild type. Thus, zds1 must be required to maintain cell wall integrity. The Zds1–GFP fusion protein localized to the cytosol, the septum, and the cell cortex. Its localization in the septum was dependent on its C-terminal region. Overexpression of the C-terminal region of Zds1 induced multi-septa and abnormal zygotes. We propose that the C-terminal region is the functional domain of Zds1 while the N-terminal region is a negative regulatory region. Thus, Zds1 is involved in multiple cellular events in fission yeast, including sexual differentiation, Ca2+ tolerance, cell wall integrity, viability in the stationary phase, and cell morphology.
Patterns of Nucleotide Diversity in Wild and Cultivated Sunflower
Authors: Liu Aizhong , Burke John M
Published: December 2005

Interest in the level and organization of nucleotide diversity in domesticated plant lineages has recently been motivated by the potential for using association-based mapping techniques as a means for identifying the genes underlying complex traits. To date, however, such data have been available only for a relatively small number of well-characterized plant taxa. Here we provide the first detailed description of patterns of nucleotide polymorphism in wild and cultivated sunflower (Helianthus annuus), using sequence data from nine nuclear genes. The resuflts of this study indicate that wild sunflower harbors at least as much nucleotide diversity as has been reported in other wild plant taxa, with randomly selected sequence pairs being expected to differ at 1 of every 70 bp. In contrast, cultivated sunflower has retained only 40–50% of the diversity present in the wild. Consistent with this dramatic reduction in polymorphism, a phylogenetic analysis of our data revealed that the cultivars form a monophyletic clade, adding to the growing body of evidence that sunflower is the product of a single domestication. Eight of the nine loci surveyed appeared to be evolving primarily under purifying selection, while the remaining locus may have been the subject of positive selection. Linkage disequilibrium (LD) decayed very rapidly in the self-incompatible wild sunflower, with the expected LD falling to negligible levels within 200 bp. The cultivars, on the other hand, exhibited somewhat higher levels of LD, with nonrandom associations persisting up to ∼1100 bp. Taken together, these results suggest that association-based approaches will provide a high degree of resolution for the mapping of functional variation in sunflower.
Patterns of Diversity and Linkage Disequilibrium Within the Cosmopolitan Inversion In(3R)Payne in Drosophila melanogaster Are Indicative of Coadaptation
Authors: Kennington W Jason , Partridge Linda , Hoffmann Ary A
Published: December 2005

The cosmopolitan inversion In(3R)Payne in Drosophila melanogaster decreases in frequency with increasing distance from the equator on three continents, indicating it is subject to strong natural selection. We investigated patterns of genetic variation and linkage disequilibrium (LD) in 24 molecular markers located within and near In(3R)Payne to determine if different parts of the inversion responded to selection the same way. We found reduced variation in the markers we used compared to others distributed throughout the genome, consistent with the inversion having a relatively recent origin (<Ne generations). LD between markers and In(3R)Payne varied significantly among markers within the inversion, with regions of high association interspersed by regions of low association. Several factors indicate that these patterns were not due to demographic factors such as admixture and bottlenecks associated with colonization, but instead reflected strong epistatic selection. Furthermore, we found that nonadjacent regions with high association to the inversion contained markers with the strongest clinal patterns in allele frequency; in most cases, the level of clinal variation was beyond what could be explained by hitchhiking with In(3R)Payne, indicating that genes within these regions are targets of selection. Our results provide some support for the hypothesis that inversions persist in natural populations because they hold together favorable combinations of alleles that act together to facilitate adaptive shifts.
Mothers’ Reflections on Raising a Child with a Craniofacial Anomaly
Authors: Klein Tovah , Pope Alice W. , Getahun Eskedar , Thompson Jill
Published: December 2005

Objective:

To conduct a qualitative evaluation of parenting among families with school-aged and young adolescent children with craniofacial anomalies (CFAs).

Methods:

Interview responses were obtained from nine mothers of children ages 9 to 14 years old with CFAs. Mothers were asked to describe their perceptions of their children, their children's special needs because of CFAs, and their parenting strategies. Narratives were coded into categories, including maternal concerns and worries, children's strengths, proactive maternal behaviors, and role of CFAs in the families’ lives.

Results and Conclusions:

Mothers’ responses indicated concern and protectiveness because of the challenges of having a CFA, as well as parenting strategies intended to promote autonomy and positive social and emotional adjustment.
Immunophenotype of Human Adipose-Derived Cells: Temporal Changes in Stromal-Associated and Stem Cell–Associated Markers
Authors: Mitchell James B. , McIntosh Kevin , Zvonic Sanjin , Garrett Sara , Floyd Z. Elizabeth , Kloster Amy , Di Halvorsen Yuan , Storms Robert W. , Goh Brian , Kilroy Gail , Wu Xiying , Gimble Jeffrey M.
Published: December 2005

Adipose tissue represents an abundant and accessible source of multipotent adult stem cells and is used by many investigators for tissue engineering applications; however, not all laboratories use cells at equivalent stages of isolation and passage. We have compared the immunophenotype of freshly isolated human adipose tissue-derived stromal vascular fraction (SVF) cells relative to serial-passaged adipose-derived stem cells (ASCs). The initial SVF cells contained colony-forming unit fibroblasts at a frequency of 1:32. Colony-forming unit adipocytes and osteoblasts were present in the SVF cells at comparable frequencies (1:28 and 1:16, respectively). The immunophenotype of the adipose-derived cells based on flow cytometry changed progressively with adherence and passage. Stromal cell–associated markers (CD13, CD29, CD44, CD63, CD73, CD90, CD166) were initially low on SVF cells and increased significantly with successive passages. The stem cell–associated marker CD34 was at peak levels in the SVF cells and/or early-passage ASCs and remained present, although at reduced levels, throughout the culture period. Aldehyde dehydrogenase and the multidrug-resistance transport protein (ABCG2), both of which have been used to identify and characterize hematopoietic stem cells, are expressed by SVF cells and ASCs at detectable levels. Endothelial cell–associated markers (CD31, CD144 or VE-cadherin, vascular endothelial growth factor receptor 2, von Willebrand factor) were expressed on SVF cells and did not change significantly with serial passage. Thus, the adherence to plastic and subsequent expansion of human adipose-derived cells in fetal bovine serum-supplemented medium selects for a relatively homogeneous cell population, enriching for cells expressing a stromal immunophenotype, compared with the heterogeneity of the crude SVF.
Influence of oestradiol and tamoxifen on oestrogen receptors-α and -β protein degradation and non-genomic signalling pathways in uterine and breast carcinoma cells
Authors: Horner-Glister E , Maleki-Dizaji M , Guerin C J , Johnson S M , Styles J , White I N H
Published: December 2005

Tamoxifen acts as an oestrogen antagonist in the breast reducing cell proliferation, but in the uterus as an oestrogen agonist resulting in increased cell proliferation. Tamoxifen exerts its tissue-specific effects through the oestrogen receptors (ERα or ERβ). The levels and functions of the two ERs affect the response of the target tissue to oestrogen and tamoxifen. We examined the control of ER stability in breast and uterine cell lines using western blotting and RT-PCR. In MCF-7 breast-derived cells, ERα and ERβ proteins were rapidly degraded via the proteasome pathway in response to oestradiol; conversely tamoxifen stabilised both receptors. In Ishikawa uterine-derived cells, oestradiol and tamoxifen stabilised ERα but led to degradation of ERβ by the proteasome pathway. Further investigations showed that oestradiol induced activation of the non-genomic ERα/Akt signalling pathway in MCF-7 cells. We have demonstrated that the alternative Erk signalling pathway is activated in Ishikawa cells following oestradiol treatment in the absence of an active proteasome pathway and therefore increased levels of ERβ. In conclusion, our data have demonstrated tamoxifen or oestradiol control of ER subtype stability and that non-genomic activation of transcription pathways is cell specific.
Episodic evolution of prolactin receptor gene in mammals: coevolution with its ligand
Authors: Li Ying , Wallis Michael , Zhang Ya-ping
Published: December 2005

Divergence of proteins in signaling pathways requires ligand and receptor coevolution to maintain or improve binding affinity and/or specificity. In this paper we show a clear case of coevolution between the prolactin (PRL) gene and its receptor (prolactin receptor, PRLR) in mammals. First we observed episodic evolution of the extracellular and intracellular domains of the PRLR, which is closely consistent with that seen in PRL. Correlated evolution was demonstrated both between PRL and its receptor and between the two domains of the PRLR using Pearson’s correlation coefficient. On comparing the ratio of the nonsynonymous substitution rate to synonymous substitution rate (ω =dN/dS) for each branch of the star phylogeny of mammalian PRLRs, separately for the extracellular domain (ECD) and the transmembrane domain/intracellular domain (TMD/ICD), we observed a lower ω ratio for ECD than TMD/ICD along those branches leading to pig, dog and rabbit but a higher ratio for ECD than TMD/ICD on the branches leading to primates, rodents and ruminants, on which bursts of rapid evolution were observed. These observations can be best explained by coevolution between PRL and its receptor and between the two domains of the PRLR.
Regulation of corticotropin-releasing hormone receptor-2 expression in human cord blood-derived cultured mast cells
Authors: Papadopoulou Nikoletta G , Oleson Lauren , Kempuraj Duraisamy , Donelan Jill , Cetrulo Curtis L , Theoharides Theoharis C
Published: December 2005

Corticotropin-releasing hormone (CRH) is secreted under stress and regulates the hypothalamic-pituitary-adrenal (HPA) axis; it is also secreted outside the brain where it exerts proinflammatory effects, possibly through mast cell activation. Mast cells are necessary for allergic reactions, but are increasingly implicated in acquired immunity and inflammatory diseases worsened by stress. Acute stress and intradermal CRH induced murine skin mast cell activation and increased vascular permeability that was absent in W/Wv mast cell deficient mice. The presence of functional CRH receptors (CRH-R) was recently reported on human mast cells. Here, we studied the expression of CRH-R1 and CRH-R2 by semiquantitative reverse transcriptase-polymerase chain reaction (RT-PCR) and fluorescent immunocytochemistry in human umbilical cord blood-derived cultured mast cells (hCBMCs) treated with Interleukin (IL)-1, IL-4 or lipopolysaccharide (LPS). Ten week-old hCBMCs cultured in the presence of Stem cell factor (SCF) and IL-6 were positive for both CRH-R1 and CRH-R2. However, the expression of only CRH-R2 mRNA and protein was induced by priming hCBMCs with IL-4 for the last three weeks of culture. Further analysis of the CR-H R2 mRNA expression showed that addition of IL-1 or LPS for 6 h increased only CRH-R2 gene expression. CRH had negligible effect on IL-6 secretion from non-primed hCBMCs, but induced release from IL-4 primed cells. Interestingly, LPS alone increased IL-6 release in non-primed cells, but lost this effect in primed cells. These results further implicate mast cells and CRH in either initiating or potentiating inflammatory diseases, especially those affected by stress.
Role of aspartate 351 in transactivation and active conformation of estrogen receptor α
Authors: Kim Jeong Hoon , Lee Mee Hyun , Kim Byoung Jin , Kim Jun Hyun , Han Seong Jun , Kim Hak Yeop , Stallcup Michael R
Published: December 2005

Estrogen-dependent transcriptional activation by estrogen receptor α (ERα) depends on the conformation of helices 3 and 12 in the ligand-binding domain. To better understand the function of helix 3 in ERα, we examined the role of charged residues, which are conserved in most steroid receptors in helix 3, in estrogen-dependent transactivation. The replacement of Asp-351 with lysine (D351K) or leucine (D351 L) completely abolished estrogen-dependent transactivation without affecting estrogen-binding, DNA-binding and homodimerization activities in ERα. The mutations dramatically reduced the ligand-dependent activation function 2 activity and impaired the ability of ERα to bind p160 coactivators. In addition, the D351K mutant effectively inhibited the transcriptional activation activity of wild-type ERα. Furthermore Asp-351 was required not only for the estrogen-dependent conformational change of wild-type ERα but also for the constitutive transcriptional activity and ligand-independent active conformation of ERα mutant Y537N. Similarly, in the orphan nuclear receptor called estrogen-related receptor 3 (ERR3), the replacement of Asp-273 (the corresponding amino acid to Asp-351 in ERα) with lysine abolished constitutive transcriptional activity of ERR3 without affecting DNA-binding activity and impaired the ability of the receptor to interact with p160 coactivators. These data suggest a role of Asp-351 in inducing and stabilizing the active conformation of ERα, and our results experimentally confirm the concept that Asp-351 in helix 3 interacts with the amide hydrogen of L540 in helix 12 to form a transcriptionally competent surface for binding p160 coactivators.
Role of estrogen receptor (ER) α in insulin-like growth factor (IGF)-I-induced responses in MCF-7 breast cancer cells
Authors: Zhang S , Li X , Burghardt R , Smith R , Safe S H
Published: December 2005

Insulin-like growth factor-I (IGF-I) is a mitogenic polypeptide that induces proliferation of MCF-7 breast cancer cells, and cotreatment with the phosphoinositide 3-kinase (PI3-K) inhibitor LY294002 and the antiestrogen ICI 182780 inhibits IGF-I-induced growth. The role of estrogen receptor α (ERα) in mediating responses induced by IGF-I was investigated in cells transfected with small inhibitory RNA for ERα (iERα). The results showed that IGF-I-dependent phosphorylation of Akt and mitogen-activated protein kinase, induction of G1–S-phase progression and enhanced expression of cyclin D1 and cyclin E were dependent on ERα. Moreover, these same IGF-I-induced responses were also inhibited by the antiestrogen ICI 182780 and this was in contrast to a previous report suggesting that ICI 182780 did not affect IGF-I-dependent activation of PI3-K or induction of cyclin D1 expression. ICI 182780 exhibits antimitogenic activity and iERα inhibits G1–S-phase progression and proliferation of MCF-7 cells treated with IGF-I, suggesting that the effects of the antiestrogen are primarily related to downregulation of ERα.
Hyperglycemia- and hyperinsulinemia-induced alteration of adiponectin receptor expression and adiponectin effects in L6 myoblasts
Authors: Fang X , Palanivel R , Zhou X , Liu Y , Xu A , Wang Y , Sweeney G
Published: December 2005

Adiponectin has been shown to regulate glucose and fatty acid uptake and metabolism in skeletal muscle. Here we investigated the role of the recently cloned adiponectin receptor (AdipoR) isoforms in mediating effects of both globular (gAd) and full-length (fAd) adiponectin, and their regulation by hyperglycemia (25 mM, 20 h) and hyperinsulinemia (100 nM, 20 h). We used L6 rat skeletal muscle cells, which were found to express both AdipoR1 and AdipoR2 mRNA in a ratio of over 6:1 respectively. Hyperglycemia and hyperinsulinemia both decreased AdipoR1 receptor expression by approximately 50%, while the latter induced an increase of approximately threefold in AdipoR2 expression. The ability of gAd to increase GLUT4 myc translocation, glucose uptake, fatty acid uptake and oxidation, as well as AMP-activated protein kinase (AMPK) and acetyl-CoA carboxylase (ACC) phosphorylation, was decreased by both hyperglycemia and hyperinsulinemia. Interestingly, hyperinsulinemia induced the ability of fAd to elicit fatty acid uptake and enhanced fatty acid oxidation in response to fAd. In summary, our results suggest that both hyperglycemia and hyperinsulinemia cause gAd resistance in rat skeletal muscle cells. However, hyperinsulinemia induces a switch toward increased fAd sensitivity in these cells.
Popular Health Education and Propaganda in Times of Peace and War in Mexico City, 1890s–1920s
Authors: Agostoni Claudia
Published: December 2005

Health education and propaganda acquired importance during the late 19th and early 20th centuries in Mexico City, as physicians, hygienists, and schoolteachers attempted to teach the principles of public health to a culturally and socially heterogeneous urban population.

I explore the organization of the Popular Hygiene Exhibition of 1910 and the importance of health education before and after the armed phase of the Mexican Revolution, and why children and the indigenous populations became the main recipients of health education programs.
Outcomes of Recognizing Depressed Chinese American Patients in Primary Care
Authors: Yeung Albert , Kung Winnie W. , Murakami Jessica L. , Mischoulon David , Alpert Jonathan E. , Nierenberg Andrew A. , Fava Maurizio
Published: December 2005

Purpose:

This study aims to examine the effect of identifying Chinese American patients as having major depressive disorder (MDD) to their primary care physicians (PCPs) on the latter's attention given to the treatment of depression.

Methodology:

Forty Chinese American patients from a primary care clinic were identified as having major depressive disorder (MDD), and their primary care physicians (PCPs) were notified of the diagnosis by letter. Three months later, medical records of subjects in the study were reviewed to see if their PCPs had intervened through referral and/or initiated treatment of depression.

Results:

PCPs documented intervention in 19 patients (47%) regarding their depression. Two of these patients (11%) were started on an antidepressant. Four (21%) accepted and 13 (68%) declined referral to mental health services. No intervention was recorded for 21 (53%) patients.

Conclusion:

We conclude that recognition alone of MDD among Chinese Americans in the community primary care setting does not lead to adequate initiation of treatment for depression by PCPs.
Written Emotional Expression and Religion: Effects on PTSD Symptoms
Authors: Chen Yung Y.
Published: December 2005

Objective:

Previous research has found an association between writing about traumatic events and well-being. This study examined the effects of taking a religious perspective during a trauma-writing exercise.

Method:

Participants included 177 college students who were assigned randomly to either a conventional trauma writing or a religious trauma writing condition. Participants in the conventional writing condition were instructed to write about a traumatic experience, while participants in the religious writing condition were instructed to write about the trauma from a religious/spiritual perspective. Well-being was assessed by symptoms of PTSD at one-month follow-up.

Results:

Writing condition was found to interact with trauma severity and gender to affect PTSD symptoms at follow-up. Conventional writing was more effective (in reducing PTSD symptoms) for participants reporting lower trauma severity than for those who reported higher trauma severity. Effects of religious writing on PTSD symptoms were not influenced by trauma severity. Also, women benefited more from religious writing than men did with regard to reductions in PTSD symptoms.

Conclusion:

It appears possible to adapt the conventional written emotional expression procedure in a way that encourages individuals to take a religious perspective, thereby augmenting effects on distress. These findings support further investigation of integrating religion into trauma interventions, particularly for individuals exposed to highly traumatic events.
To What Extent are the Spiritual Needs of Hospital Patients Being Met?
Authors: Flannelly Kevin J. , Galek Kathleen , Handzo George F.
Published: December 2005

Although a substantial number of studies have documented the spiritual needs of hospitalized patients, few have examined the prevalence of these needs and even fewer have attempted to measure the extent to which they are being met. Since chaplains are the primary providers of spiritual care, chaplains' visits to patients would appear to provide a reasonable proxy for the latter. Based on the limited data available, we estimated the proportion of hospitalized patients who are visited by chaplains. Our analyses yielded a point estimate of 20% (+ 10%), depending on a number of factors.
Working at the Check-in: Consequences for Health
Authors: Rosskam Ellen
Published: December 2005

No body of literature exists related specifically to the occupational health of airport check-in workers. The problems encountered by airport check-in workers are typical of other service-sector occupations with similar work-related health hazards, particularly those characterized by a high level of demand with low worker control, performed predominantly by women. The knowledge gap could be narrowed by broadening the scope in both traditional occupational health and ergonomics studies to take into equal consideration jobs performed by women. In an attempt to reduce the knowledge gap specific to airport check-in workers, literature was reviewed on several other worker populations whose job characteristics include elements similar to airport check-in work: computer clerical workers, supermarket check-in workers, and airport baggage handlers. This cross-population review identified the major elements that have been studied in the comparison groups, compared with the factors examined in a study of check-in workers. The review demonstrates that jobs that may appear completely different from the outside, might, upon closer examination, have numerous common exposures from a variety of sources. Thus, knowledge about one job may be useful for another that has not been investigated. The literature review reveals that it would be useful to extend to airport check-in workers recommendations from studies of the three comparison populations.
Porphyrins with Exocyclic Rings: Part 9 [1] Synthesis of Porphyrins by
the ‘3 + 1’ approach
Authors: LASH TIMOTHY D.
Published: December 2005

Tripyrrane dibenzyl esters are readily available from the reaction of
two equivalents of 5-acetoxymethylpyrrole-2-carboxylates with
2,5-diunsubstituted pyrroles in refluxing acetic acid-ethanol.
Hydrogenolysis of the benzyl ester moieties affords the corresponding
dicarboxylic acids, and subsequent condensation with 2,5-diformylpyrroles in
5% trifluoroacetic acid-dichloromethane, followed by neutralization with
triethylamine and oxidation with DDQ, gives porphyrin products in good to
excellent yields. The isomeric purity of these products has been rigorously
demonstrated by proton and carbon-13 NMR spectroscopy. This chemistry allows
the direct synthesis of porphyrin structures that would otherwise only be
accessible via multistep procedures. In addition, this approach provides a
convenient synthetic entry to the geochemically important
tetrahydrobenzoporphyrins and cycloalkanoporphyrins. The first examples of
tripyrranes with tetrahydroindole subunits are reported and their utility in
the synthesis of novel cycloalkanoporphyrins is disclosed.
Synthesis and Characterization of Highly Conjugated Unsymmetrically Substituted Phthalocyanines
Authors: DE LA TORRE GEMA , TORRES TOMÁS
Published: December 2005

Unsymmetric push-pull phthalocyanines with a high degree of conjugation achieved by introducing π-delocalized electron substituents were synthesized by statistical condensation of two different diiminoisoindolines. The characterization and spectroscopic properties of these push-pull phthalocyanines are described. These compounds are targeted for the study of their second-order non-linear optical responses.
Synthesis of a Monofunctional Phthalocyanine on Silica
Authors: HIRTH ANDREAS , SOBBI ABDOL KHEZER , WÖHRLE DIETER
Published: December 2005

Silica of different surface area and grain size modified by aminopropyl groups reacted with 4-(3,4-dicyanophenoxy)benzoic acid chloride. The reaction of these benzamidophenoxydicarbonitrile modified silica gels with 4-(4-tert-butyl-phenoxy)-1,2-benzenedicarbonitrile in the presence of a zinc(II) salt results in covalently bonded phthalocyanine zinc(II) complexes with a loading between 1.8 × 10−5 and 1.7 × 10−6 mol g −1 silica. UV/vis reflectance spectra show that the phthalocyanines on the surface exist in a monomeric state. Cleavage at the amide bond between the silica and the phthalocyanine led to the corresponding monocarboxylic acid phthalocyanine derivative.
Structures of Germanium and Silicon Phthalocyanine Thin Films: Polymorphism and Isomorphism
Authors: KOBAYASHI TAKASHI , FURUKAWA CHIEKO , OGAWA TETSUYA , ISODA SEIJI
Published: December 2005

The polymorphism and isomorphism of Ge ( OH )2 Pc and Si ( OH )2 Pc ( Pc : phthalocyanine ligand) are reported as well as those of the polymeric molecules of ( GeOPc )n and ( SiOPc )n. The polymeric Pcs were produced through dehydration polymerization by heating the respective monomer of Ge ( OH )2 Pc or Si ( OH )2 Pc . We also report the thin film structures of these phthalocyanine derivatives and discuss the similarities and differences in the structures formed by vacuum deposition, in relation to the coordinating metal species.
Manganese Phthalocyanine Coordination Chemistry: Recent Results and Present Status
Authors: DOLOTOVA O. V. , BUNDINA N. I. , KALIYA O. L. , LUKYANETS E. A.
Published: December 2005

A number of substituted manganese phthalocyanines ( PcMn ), which are easily soluble in organic solvents, have been synthesized with good yields (up to 76%) and high purity. PcMn with manganese +2 oxidation state without axial ligands was obtained for the first time and thoroughly characterized. It was shown that PcMn forms, PcMn III X , PcMn II or [ LPcMn III]2 O , depending on substituents nature, can be stable in usual conditions. It was found that some PcMn II derivatives can be oxidized by water to PcMn III OH . The stages of substituted PcMn electrochemical reduction and oxidation have been studied and the correlation of redox potentials with electronic properties of substituents has been established. For the first time, the idea has been proposed and confirmed that PcMn II, when treated by organic bases in solution forms an equilibrium mixture of three electronic isomers — Pc +· Mn I, PcMn II and Pc −· Mn III. A new scheme of PcMn photoreactions has been proposed and the possibility of using PcMn as a model of a photosystem component has been discussed. All the data are summarized in the complete scheme of photo and dark transformations between valence and coordination PcMn derivatives in solution.
Fabrication of p-n Junction Diodes from Phthalocyanine and Electropolymerized Perylene Derivatives
Authors: KUDO TERUHISA , KIMURA MUTSUMI , HANABUSA KENJI , SHIRAI HIROFUSA
Published: December 2005

Perylene derivative films doped with metal ion were deposited on indium tin oxide ( ITO )-coated glass electrodes by electrodeposition from solutions of N, N″-4-hydroxyphenyl-3,4,9,10-perylenetetracarboxylic-diimide (hph-PTC) and CaCl 2, PbCl 2, ZnCl 2 or CoBr 2 as a supporting electrolyte in N, N-dimethylformamide ( DMF ). The p-n junction diodes consisting of a p-type phthalocyanine (Pc) sublimed film and an n-type hph-PTC electrodeposited film doped with metal ion exhibited Zener-type breakdown and photocurrent enhancement. The device with a p-n junction consisting of a Pc sublimed film and an hph-PTC electrodeposited film doped with Ca 2+ showed the largest amplification of photocurrent. This result suggests that the dopant ion in hph-PTC is an important factor in the preparation of p-n junction diodes.
Coordinated Acylimido Complexes Formed by Reaction of Nitridorhenium and Nitridomolybdenum Porphyrins with Substituted Acetic Anhydrides
Authors: TONG CHENG , BOTTOMLEY LAWRENCE A.
Published: December 2005

Acylimidorhenium and molybdenum porphyrin complexes were prepared by reaction of the corresponding nitridometalloporphyrins with substituted acetic anhydrides and their spectral and electrochemical properties were determined. Analysis of the electronic spectral changes with time and initial reactant concentration confirmed that the acylimido formation reaction was first-order in each reactant and second-order overall. Second-order rate constants for formation of the chloroacetic anhydride complex increased in the order Mn < Cr < Re < Mo . In contrast with the previously reported reactivity of acylimidomanganese and chromium porphyrin complexes, the rhenium and molybdenum derivatives were unreactive towards triphenylphosphine, strained olefins and silyl ethylene ethers.
Lateral, Chiral Tin(IV) Porphyrin Assemblies
Authors: ROSENGARTEN BIANCA , BÖTTCHER CHRISTOPH , SCHULZ ANDREA , FUHRHOP J.-H. , SIGGEL ULRICH
Published: December 2005

The μ-Oxo stacks of tin(IV) porphyrins rearrange to staircase-type and lateral aggregates upon replacement of the oxygen ligands by chloride ions. The lateral aggregation of tin(IV) 2,18-dipropionate porphyrins in hydrochloric acid at pH 0–0.5 is favoured by 8,13-ethyl groups instead of the natural 8,13-vinyl groups of protoporphyrin IX and is impeded by hydrogen atoms at these positions. Replacement of axial chloride counterions to the tin(IV) central ions by cyanate counterions at pH 4.5 leads to similar aggregates if the cyanate ions are connected by hydrogen bonding to acetic or lactic acid. In this case, aggregation is not necessarily impeded by hydrogen atoms at positions 8 and 13. D- and L-lactic acid enforce chiral assemblies of the tin(IV) deuteroporphyrin 1a with mirror image CD (circular dichroism) spectra (θ ≈ 8 × 105deg cm2dmol−1), whereas the gluconoyl hydrazide-substituted tin(IV) deuteroporphyrin 1d does not form aggregates at all.
Magnetic and Spectroscopic Investigations of Tetra-(4-t-butyl)phthalocyano Complexes of μ-Oxo-bridged Iron(II) Dimer
Authors: Heucher Reimar , Chandramouli G. V. R. , Manoharan Periakaruppan T.
Published: December 2005

The tetra(4-t-butyl)phthalocyanine derivative of the μ-oxo dimer of Fe was studied by ESR and Mössbauer spectroscopic and magnetic susceptibility methods. The Mössbauer spectrum of the iron complex shows ΔEQ= 1.34 mm s-1and δ = 0.14 mm s-1. The susceptibility data measured as a function of temperature fit the S1= S2= 1 dimer with J = -5.2 cm-1and thus the oxidation state of iron is suggested as +2. The weak exchange coupling is attributed to the presence of the bulky t-butyl groups on phthalocyanine. It is proposed that the two phthalocyanine moieties are not superimposable on one another owing to the steric hindrance posed by the t-butyl groups of Pct. This is likely to lead to a rotation of one of the FePctmoieties about the Fe - O - Fe axis as well as an increase in Fe - O distance.
Excited State Dynamics of Novel Diporphyrins with Dissimilar Cores
Authors: RAVIKUMAR M. , PANDIAN R. P. , CHANDRASHEKAR T. K.
Published: December 2005

The singlet and triplet excited state properties of two diporphyrins, H 2- H and Zn - H , are described. Steady state fluorescence studies indicate that the emission of the H 2- H diporphyrin is dependent on the excitation wavelength and is dominated by the emission of the individual constituent monomers at their respective excitation. Time-resolved studies show two lifetimes ascribable to the normal and thiaporphyrin subunits. However, the emission of the Zn - H diporphyrin is dominated by the thiaporphyrin subunit irrespective of the wavelength of excitation, suggesting an energy transfer from the Zn porphyrin subunit to the thiaporphyrin subunit. Lifetime measurements in toluene show two lifetimes due to open and folded conformations, while in DMF an additional component due to axial ligation is observed. The efficiency of energy transfer is moderately higher in DMF (72%) than in toluene (68%). Triplet ESR studies on the H 2- H dimer reveal a localized triplet with ZFS parameters and ESP pattern the same as for the individual monomers. On the other hand, triplet ESR of the Zn - H diporphyrin reveals triplet characteristics of the thiaporphyrin subunit, indicating an energy transfer in the triplet state.
Preparation, Isolation and Electrochemical Characterization of Cobalt Porphyrins with Ru(NH3)52+ Complexes Coordinated to 4-Cyanophenyl Substituents in the 5, 10, 15 and 20 Positions on the Porphyrin Ring
Authors: STEIGER BEAT , ANSON FRED C.
Published: December 2005

A procedure has been devised by which quantitative coordination of Ru ( NH 3)52+ groups to the nitrile sites in [5,10,15,20-tetrakis(4-cyanophenyl)porphyrinato]cobalt(II) and [5,10,15,20-tetrakis(4-cyano-2,6-dimethylphenyl)porphyrinato]cobalt(II) can be achieved. The procedure takes advantage of the solubility of both [ Ru ( NH 3)5( OSO 2 CF 3)]( CF 3 SO 3)2 and either porphyrin in a mixed solvent consisting of 1,2-dimethoxyethane/N,N-dimethylacetamide (27:1 v/v). This new synthetic procedure allowed the fully ruthenated porphyrins to be isolated as solids in milligram quantities. The products were characterized using cyclic and rotating disk voltammetry and infrared and NMR spectroscopy.
Electronic Absorption, MCD and Fluorescence Studies on Phthalocyaninatosilicon Covalently Linked to One or Two TEMPO Radicals
Authors: ISHII KAZUYUKI , HIROSE YOSHIHARU , KOBAYASHI NAGAO
Published: December 2005

The UV-vis absorption, MCD and fluorescence spectra of phthalocyaninatosilicon ( SiPc ) covalently linked to one or two TEMPO radicals have been studied in comparison with those of (dihydroxy) SiPc . The electronic absorption and MCD spectra show little change on substitution of TEMPO radicals, indicating that the electronic interaction between excited singlet SiPc (1 SiPc *) and doublet TEMPO (2 TEMPO ) is very weak or non-existent. In contrast, fluorescence quantum yields decrease markedly with increasing number of TEMPO radicals. This result is interpreted reasonably by assuming that the decay from 1 SiPc * to excited triplet SiPc (3 SiPc *) partially becomes a spin-allowed transition owing to the interaction between 3 SiPc * and 2 TEMPO .
Synthesis, Optical Properties, Structures and Molecular Orbital Calculations of Subazaporphyrins, Subphthalocyanines, Subnaphthalocyanines and Related Compounds
Authors: KOBAYASHI NAGAO
Published: December 2005

The synthesis of and spectroscopic data on subazaporphyrins, subphthalocyanines, subnaphthalocyanines and their related compounds reported to date are summarized, together with the results of molecular orbital (MO) calculations from our laboratory. Thus the problems and key points in the synthesis of these subazamacrocycles and their electronic absorption and magnetic circular dichroism (MCD) spectra are discussed, together with those of the monosubstituted-type low-symmetrical phthalocyanines obtained by their ring expansion reaction. The Q bands of these subazamacrocycles are orbitally doubly degenerate, and in the Soret band region, three transitions to the orbitally degenerate state are found. The MO calculations suggest that the HOMO levels destabilize considerably while the LUMO levels change slightly with increasing size of the π system. In addition, the electronic adsorption data are reproduced by the calculation only when the two pyrrole hydrogens in the monosubstituted-type phthalocyanines are assumed to be linked to the two pyrrole nitrogens along the short axis.
Azaporphyrins and Phthalocyanines as Multicentre Conjugated Ampholites
Authors: STUZHIN PAVEL A.
Published: December 2005

Molecules of azaporphyrins combine two acidic pyrrole-type NH groups and several basic centres—two internal pyrrolenine nitrogen atoms and from one to four meso-nitrogen atoms—in one highly conjugated aromatic system. The acid–base properties of such unique multicentre ampholites have been the subject of numerous studies and discussions. Along with a short critical historical review the paper presents the latest results of a systematic investigation of the influence of successive aza substitution on the spectral properties and thermodynamic stability of the acid–base forms of azaporphyrins.
Approaches to the Stepwise Synthesis of Benzoporphyrins and Phthalocyanines Part 2: Synthesis of a 5-Azadibenzo[b,g]porphyrin from Benzopyrromethene Intermediates
Authors: BONNETT RAYMOND , OKOLO KAWULIA
Published: December 2005

An azadibenzoporphyrin (13,17-diethyl-12,18-dimethyl-5-azadibenzo[b,g]porphyrin, 6) is prepared by a 2 × 2 synthesis from a 1-bromobenzopyrromethene precursor by treatment with sodium azide at 140 °C in solvent. Yields depend on solvent, 35% being obtained in quinoline and 84% in DMF. Treatment of 1-bromo-8-ethyl-7,9-dimethylbenzopyrromethene hydrobromide with sodium azide at 60 °C in DMF gives the fused tetrazolo system 8 (8-ethyl-7,9-dimethyltetrazolo[1,5-i]benzopyrromethene) (X-ray structure), which appears to be, or to lead to, an intermediate in the macrocyclization at the higher temperature.
The Effect of Crystal Properties on the Manufacture and Application Performance of Copper Phthalocyanine Pigments
Authors: MATHER ROBERT R.
Published: December 2005

Copper phthalocyanines are commercially important organic pigments for blue shades of colour. They are dispersed by mechanical means as tiny molecular crystals (of dimensions 0.02—0.5 μm) into a wide range of commercial media to form products such as printing inks, paints and coloured plastics. Many important technological properties of copper phthalocyanine pigments, including colour strength and dispersion performance, depend on the physical properties of their crystals, notably crystal lattice type, crystal size and crystal shape. The roles which these crystal properties play in determining a copper phthalocyanine pigment's technological performance are briefly reviewed. The reduction of crystal aggregation during the manufacture of a copper phthalocyanine pigment and the control of flocculation in an application medium are also highlighted.
Ozone
Authors: Wojtowicz John A.
Published: December 2005

This article discusses solubility, absorptivity, explosivity, as well as thermodynamic, spectral, structural, and other physical properties of ozone in the gaseous, liquid, and solid states; it reviews both organic and inorganic chemistry and offers various analytical methods for determining ozone in the solution and the gas phase. It examines, from a mechanistic viewpoint, not only the thermal and photochemical decomposition of gaseous and aqueous ozone, but also its generation, including gas preparation, electrical requirements and characteristics, efficiency, costs, and design. In addition, the article investigates atmospheric ozone formation in the troposphere and the stratosphere from the standpoint of photochemical smog, surveying the effect of natural and anthropogenic contaminants on ozone decomposition. Finally, the article considers numerous health and safety issues, including such topics as the depletion of ozone layer, environmental and human exposure, and ozone disinfection by‐products. Ozone can be used in drinking water, high purity water for bottling and canning plants, as well as the pharmaceutical and electronics industry; it can be used to bleach textiles and natural products, to control industrial wastewater pollution and sewage, to disinfect wastewater as well as water for large aquariums and shrimp hatcheries, to treat process water, swimming pools, and spas; it can also be used for pulp bleaching, organic synthesis, medical applications, and food preservation.
Plant Location
Authors: Meissner Roland E.
Published: December 2005

The primary siting factors that influence the selection of a plant location are as follows: environmental and safety considerations, labor availability and productivity, raw material availability, accessibility to transportation, proximity to market, property cost, tax incentives, electric power availability and cost, and living conditions. In the selection of a plant site, it is a good idea to get broad‐based input, including information from sales, production, plant engineering, and from the general manager. The first objective is to narrow the range of possible choices. This involves focusing on the most important criteria, which differ widely for each type of facility. Table 3 presents some of the factors to consider for plant siting. An objective rating system needs to be used; a listing of the important criteria and a point system which affords the evaluation committee a means of scoring the pluses and the minuses has been found to be useful. The scoring may need to be weighted so that the factors which most heavily affect the bottom‐line profit are more heavily counted. At the end of this phase, the less desirable sites should be discarded so that a more in‐depth evaluation of the final candidates can be made.
Vanadium Compounds
Authors: Woolery Mike
Published: December 2005

Vanadium is widely dispersed in the earth crust. Primary industrial compounds produced directly from vanadium raw materials are principally fused pentoxide, air‐dried pentoxide, the sesquioxide and technical‐grade ammonium metavanadate. Recovery of vanadium from titaniferous magnetites by salt roasting, acid leaching, and amine solvent extraction is common. Conversion of fused pentoxide to alloy additives is by far the largest use of vanadium compounds. Air‐dried pentoxide, ammonium vanadate, and some fused pentoxide are used as such, purified, or converted to other forms for catalytic, chemical, ceramic, or specialty applications. Physical and chemical properties, manufacturing, health and safety factors, and economic aspects are discussed.
Metathesis
Authors: Delaude Lionel , Noels Alfred F.
Published: December 2005

In organic synthesis and polymer science, the metathesis reaction consists of a unique metal‐catalyzed carbon skeleton redistribution in which a mutual exchange of unsaturated carbon–carbon bonds takes place. The reaction is generally reversible and limited to an equilibrium. In its most common embodiment, alkenes serve as reagents. Hence, olefin metathesis constitutes a powerful catalytic method for both cleaving and forming CC double bonds. Alkyne metathesis and ene–yne metathesis are also important synthetic pathways. All three types of metathesis occur intra‐ or intermolecularly and numerous combinations thereof are possible (ring‐closing metathesis, ring‐opening metathesis polymerization, cross‐metathesis, etc).

Metathesis has opened up new routes to important petrochemicals, oleochemicals, polymers, and specialty chemicals. The transformation often gives access with remarkable atom economy to structures that are not available by any other means, or only via multistep painstaking procedures. Major industrial processes rely on metathesis for the production of olefins. They are usually based on inexpensive, ill‐defined, multicomponent catalytic systems derived from tungsten, molybdenum, rhenium, or ruthenium salts. Research laboratory applications take advantage of well‐defined metal‐alkylidene complexes of molybdenum and ruthenium that combine high activities and ease of set‐up under reproducible conditions, albeit at the price of a higher cost.
A General Method for the Enantioselective Hydrogenation of β‐Keto Esters using Monodentate Binaphthophosphepine Ligands
Authors: Hagemann Bernhard , Junge Kathrin , Enthaler Stephan , Michalik Manfred , Riermeier Thomas , Monsees Axel , Beller Matthias
Published: December 2005

17 monodentate phosphepine ligands with a 4,5‐dihydro‐3H‐dinaphtho[2,1‐c;1′,2′‐e]phosphepine structural motif have been synthesized and tested in the asymmetric hydrogenation of various β‐keto esters. By variation of the substituents of the aryl group on the phosphorus atom a fine tuning of the selectivity of the catalytic system is possible. Quantitative yield and enantioselectivities up to 95% ee have been achieved for the hydrogenation of methyl acetoacetate (7a), methyl 3‐oxovalerate (7b) and ethyl 4‐phenyl‐3‐oxo‐propionate (7d) using 4‐(4‐methoxyphenyl)‐4,5‐dihydro‐3H‐dinaphtho‐[2,1‐c;1′,2′‐e]phosphepine (4g) as ligand. Best enantioselectivities were obtained at comparably high temperatures (100–120 °C), which had the advantage of increased reaction rates.
Silica‐Supported Vanadium‐Catalyzed N‐Oxidation of Tertiary Amines with Aqueous Hydrogen Peroxide
Authors: Rout Laxmidhar , Punniyamurthy Tharmalingam
Published: December 2005

A recyclable silica supported vanadium 1 catalyzes the oxidation of tertiray amines to the corresponding N‐oxides with 30% H2O2 in high yield.