The pyrrolo-1,5-benzoxazepine, PBOX-6, inhibits the growth of breast cancer cells in vitro independent of estrogen receptor status and inhibits breast tumour growth in vivo

Members of a novel series of pyrrolo-1,5-benzoxazepine (PBOX) compounds have been shown to induce apoptosis in a number of human leukemia cell lines of different haematological lineage, suggesting their potential as anti-cancer agents. In this study, we sought to determine if PBOX-6, a well characterised member of the PBOX series of compounds, is also an effective inhibitor of breast cancer growth. Two estrogen receptor (ER)-positive (MCF-7 and T-47-D) and two ER-negative (MDA-MB-231 and SK-BR-3) cell lines were examined. The 3,4,5-dimethylthiazol-2-yl-2,5-diphenyl-tetrazolium bromide (MTT) assay was used to determine reduction in cell viability. PBOX-6 reduced the cell viability of all four cell lines tested, regardless of ER status, with IC(50) values ranging from 1.0 to 2.3 microM. PBOX-6 was most effective in the SK-BR-3 cells, which express high endogenous levels of the HER-2 oncogene. Overexpression of the HER-2 oncogene has been associated with aggressive disease and resistance to chemotherapy. The mechanism of PBOX-6-induced cell death was due to apoptosis, as indicated by the increased proportion of cells in the pre-G1 peak and poly(ADP-ribose) polymerase (PARP) cleavage. Moreover, intratumoural administration of PBOX-6 (7.5 mg/kg) significantly inhibited tumour growth in vivo in a mouse mammary carcinoma model (p=0.04, n=5, Student's t-test). Thus, PBOX-6 could be a promising anti-cancer agent for both hormone-dependent and -independent breast cancers.

Testing two different doses of tiotropium Respimat® in cystic fibrosis: Phase 2 randomized trial results

Background: Tiotropium is a once-daily, long-acting anticholinergic bronchodilator with the potential to alleviate airway obstruction in cystic fibrosis. Our objective was to evaluate the efficacy and safety of 2.5 and 5 μg once-daily tiotropium delivered via the Respimat Soft Mist Inhaler vs. placebo in people with cystic fibrosis. Methods: This phase 2, 12-week, randomized, double-blind, placebo-controlled parallel-group study of tiotropium Respimat as add-on to usual cystic fibrosis maintenance therapy included people with cystic fibrosis with pre-bronchodilator forced expiratory volume in 1 second (FEV₁) ≥25% predicted. Co-primary efficacy end points were change from baseline in percent-predicted FEV₁area under the curve from 0 to 4 hours (FEV₁AUC_0-4h), and trough FEV₁at the end of week 12. Findings: A total of 510 subjects with cystic fibrosis aged 5-69 years were randomized. Both doses of tiotropium resulted in significant improvement compared with placebo in the co-primary efficacy end points at the end of week 12 (change from baseline in percent-predicted FEV₁AUC_0-4h: 2.5 μg: 2.94%, 95% confidence interval 1.19-4.70, p = 0.001; 5 μg: 3.39%, 95% confidence interval 1.67-5.12, p = 0.0001; in percent-predicted trough FEV₁:2.5 μg: 2.24%, p = 0.2; 5 μg: 2.22%, p = 0.02). There was a greater benefit with tiotropium 5 vs. 2.5 μg. No treatment-related adverse events or unexpected safety findings were observed in patients taking tiotropium. Conclusions: Tiotropium significantly improved lung function in people with cystic fibrosis. The improvement was greater with the higher dose than the lower dose, with no difference in adverse events.

Acute Cocoa Supplementation Increases Postprandial HDL Cholesterol and Insulin in Obese Adults with Type 2 Diabetes after Consumption of a High-Fat Breakfast

BACKGROUND: Dietary cocoa is an important source of flavonoids and is associated with favorable cardiovascular disease effects, such as improvements in vascular function and lipid profiles, in nondiabetic adults. Type 2 diabetes (T2D) is associated with adverse effects on postprandial serum glucose, lipids, inflammation, and vascular function.

OBJECTIVE: We examined the hypothesis that cocoa reduces metabolic stress in obese T2D adults after a high-fat fast-food-style meal.

METHODS: Adults with T2D [n = 18; age (means ± SEs): 56 ± 3 y; BMI (in kg/m(2)): 35.3 ± 2.0; 14 women; 4 men) were randomly assigned to receive cocoa beverage (960 mg total polyphenols; 480 mg flavanols) or flavanol-free placebo (110 mg total polyphenols; <0.1 mg flavanols) with a high-fat fast-food-style breakfast [766 kcal, 50 g fat (59% energy)] in a crossover trial. After an overnight fast (10-12 h), participants consumed the breakfast with cocoa or placebo, and blood sample collection [glucose, insulin, lipids, and high-sensitivity C-reactive protein (hsCRP)] and vascular measurements were conducted at 0.5, 1, 2, 4, and 6 h postprandially on each study day. Insulin resistance was evaluated by homeostasis model assessment.

RESULTS: Over the 6-h study, and specifically at 1 and 4 h, cocoa increased HDL cholesterol vs. placebo (overall Δ: 1.5 ± 0.8 mg/dL; P ≤ 0.01) but had no effect on total and LDL cholesterol, triglycerides, glucose, and hsCRP. Cocoa increased serum insulin concentrations overall (Δ: 5.2 ± 3.2 mU/L; P < 0.05) and specifically at 4 h but had no overall effects on insulin resistance (except at 4 h, P < 0.05), systolic or diastolic blood pressure, or small artery elasticity. However, large artery elasticity was overall lower after cocoa vs. placebo (Δ: -1.6 ± 0.7 mL/mm Hg; P < 0.05), with the difference significant only at 2 h.

CONCLUSION: Acute cocoa supplementation showed no clear overall benefit in T2D patients after a high-fat fast-food-style meal challenge. Although HDL cholesterol and insulin remained higher throughout the 6-h postprandial period, an overall decrease in large artery elasticity was found after cocoa consumption. This trial was registered at clinicaltrials.gov as NCT01886989.

Síntese e transformações de compostos do tipo pirazol e 1,2,3-triazol

Compostos do tipo pirazol e 1,2,3-triazol encontram-se presentes em inúmeras moléculas biologicamente ativas. Muitos fármacos atualmente comercializados ou em fase de estudos clínicos contêm na sua estrutura base núcleos de pirazol ou 1,2,3-triazol. Por isso, estes compostos têm sido alvo de intensa pesquisa na procura de novas moléculas com potenciais aplicações medicinais e agroquímicas. Nesta dissertação são descritas novas vias de síntese de novos compostos do tipo pirazol e 1,2,3-triazol. No primeiro capítulo apresenta-se uma breve revisão bibliográfica sobre a atividade biológica, ocorrência natural e métodos de síntese de pirazóis e seus derivados. O segundo capítulo foca-se na síntese de (E)-2-estiril-3-halo-4H-cromen-4-onas e sua transformação em 3(5)-aril-5(3)-[2-(2-hidroxifenil)-2-oxoetil-1H-pirazóis. Em primeiro lugar faz-se uma revisão bibliográfica sobre as (E)-2-estiril-4H-cromen-4-onas e a sua semelhança estrutural com as flavonas, a sua importância e ocorrência natural e métodos de síntese. São ainda abordadas as metodologias mais utilizadas para a síntese de derivados halogenados de (E)-2-estiril-4H-cromen-4-onas. Seguidamente são apresentados e discutidos os resultados da síntese de (E)-3-bromo-2-estiril-4H-cromen-4-onas através da reação de 5-aril-3-hidroxi-1-(2-hidroxifenil)penta-2,4-dien-1-onas com NBS, sob irradiação com micro-ondas, tendo sido estabelecida uma nova metodologia mais eficiente, rápida e regiosseletiva para a síntese de (E)-3-bromo-2-estiril-4H-cromen-4-onas, na ausência de solvente. São igualmente apresentados os resultados da síntese regiosseletiva de (E)-2-estiril-3-iodo-4H-cromen-4-onas através da reação de 5-aril-3-hidroxi-1-(2-hidroxifenil)penta-2,4-dien-1-onas com NIS e TFA/TFAA/NaOAc. Em ambos os métodos de halogenação desenvolvidos, obtiveram-se como produtos secundários as (E)-2-estiril-4H-cromen-4-onas correspondentes. Seguidamente é apresentado o estudo da reação de (E)-2-estiril-3-halo-4H-cromen-4-onas com hidrato de hidrazina. Ao contrário do esperado, obtiveram-se os 3(5)-aril-5(3)-[2-(2-hidroxifenil)-2-oxoetil-1H-pirazóis através de uma reação de adição conjugada 1,6-, de hidrazina à posição C- da cromona com consequente abertura do anel, seguida de uma adição conjugada 1,4- intramolecular. Estes resultados demonstraram que esta reação segue um mecanismo diferente daquele que está reportado na literatura para a reação de (E)-2-estiril-4H-cromen-4-onas não halogenadas em C-3 com hidrato de hidrazina. No terceiro capítulo apresenta-se uma breve revisão bibliográfica sobre as propriedades, aplicações e metodologias de síntese de 1,2,3-triazóis, dando mais relevância às reações de cicloadição 1,3-dipolar e de “click-chemistry”. Seguidamente descrevem-se os resultados obtidos na reação de (E)-5(3)-estiril-3(5)-(2-hidroxifenil)-1H-pirazóis com a azida de sódio para obtenção de díades pirazol-1,2,3-triazol. No entanto esta reação deu origem a novos 5(3)-(2-aril-2-azidoetil)-3(5)-(2-hidroxifenil)-1H-pirazóis e não às díades pirazol-1,2,3-triazol pretendidas. Como o resultado não foi o esperado, desenvolveu-se outra metodologia de síntese, que envolve, num primeiro, a reação de (E)-2-estiril-4H-cromen-4-onas com azida de sódio, dando origem a 5(4)-aril-4(5)-(cromon-2-il)-1H-1,2,3-triazóis. No passo seguinte, efetuou-se a reação destes compostos com hidrato de hidrazina tendo ocorrido a formação das diades 5(4)-aril-4(5)-[3(5)-(2-hidroxifenil)-1H-pirazol-5(3)-il]-1H-1,2,3-triazol pretendidas. No quarto capítulo, estudou-se a reatividade de (E)-5(3)-estiril-3(5)-(2-hidroxifenil)-1H-pirazóis em reações de iodação com vista à obtenção de 4-iodo-1H-pirazóis. Apresenta-se uma breve revisão bibliográfica sobre os diferentes métodos descritos na literatura para a iodação de compostos heterocíclicos aromáticos, nomeadamente para a obtenção de 4-iodo-1H-pirazóis. Dos vários sistemas de iodação testados, o sistema oxidativo I2/CAN foi o que deu melhores resultados na iodação dos (E)-5(3)-estiril-3(5)-(2-hidroxifenil)-1H-pirazóis. Este método permitiu iodar a posição C-4 do núcleo de pirazol apenas para os derivados que possuem o grupo nitro ou o átomo de cloro no anel do grupo estirilo, obtendo-se o 3(5)-(2-hidroxifenil)-4-iodo-5(3)-(4-nitrofenil)vinil-1H-pirazol e o 5(3)-(4-clorofenil)vinil)-3(5)-(2-hidroxi-5-iodofenil)-4-iodo-1H-pirazol; no entanto, para os restantes derivados, verificou-se apenas a iodação nas posições ativadas do anel fenólico. Todos os novos compostos sintetizados foram caraterizados estruturalmente recorrendo a estudos de espetroscopia de ressonância magnética nuclear (RMN) mono e bidimensionais. Sempre que possível, para uma caraterização estrutural mais completa, foram efetuados espetros de massa (EM) e análises elementares ou espetros de massa de alta resolução (EMAR) para todos os novos compostos sintetizados. Finalmente são apresentadas as conclusões gerais deste trabalho e perspetivas futuras.

La Giovinezza del conte di Cavour, saggi storici secondo lettere e documenti inediti.... Partie 2 / Francesco Ruffini,...

Collection : Biblioteca di storia contemporanea ; 5-6

Synthèse et étude de nouvelles molécules potentiellement polymérisables pour la fabrication de matériaux électroluminescents : analogues du 1,3,5 benzènetripyrrole, méthyle 3,5-bipyrrolebenzoate et 6,12-diméthyle-1,5-dipyrrolediazocane

Pyrroles are found in various natural products and in the chemical composition of certain drugs because of their interesting biological properties. Lipitor, Tolmetin and Amtolmetin are examples of drugs with 1,2,5-substituted pyrroles in their composition, in which biological activities have been certified. Moreover, pyrroles are used as precursors of semiconductor polymers, oligomers and dendrimers useful for the synthesis of electroluminescent materials used in devices, such as organic light-emitting diodes, field-effect transistors, solar and organic photovoltaic cells. We are interested in conjugated polymers based on pyrrole due to their optical properties, electrochemical and the conductivity produced by electron delocalization along their carbon chains. The overall objective of the work presented in this thesis is the synthesis of new molecules based on pyrrole for studying their electronic and electrochemical properties as well for the synthesis of conjugated polymers. Initially, we performed the synthesis of 1,3,5-tri-(1-alkyl-5-methylpyrrol-2-yl)benzenes, which may serve as precursors for the synthesis of conjugated dendrimers. Their synthesis was made in three steps starting from trimethyl 1,3,5-benzene-tricarboxylate which was converted to 1,3,5-tri-(pent-4-enoyl)benzene using vinylmagnesium bromide in a Grignard reaction catalyzed by copper cyanide. The olefins of 1,3,5-tri-(pent-4-enoyl)benzene were oxidized to produce 1,3,5-tri-(4-oxopentanoyl)benzene using a modified protocol of the Tsuji-Wacker reaction. Subsequent, Paal-Knorr condensation reactions on 1,3,5-tri-(4-oxopentanoyl)benzene with different amines were used to synthesize 1,3,5-tri-(1-alkyl-5-methylpyrrol-2-yl)benzenes with different N-substituents in yields between 44 and 60%. Incomplete reaction of vinylmagnesium bromide with trimethyl 1,3,5-benzenetricarboxylate gave the methyl-3,5-di(pent-4-enoyl)benzoate, which was converted to methyl-3,5-dipyrrolylbenzoate following the reaction of Tsuji- Wacker and Paal-Knorr with yields between 30 and 60%. The photochemical and electrochemical properties of the 1,3,5-tri-(1-alkyl-5-methylpyrrol-2-yl)benzenes and methyl-3,5-dipyrrolylbenzoates were studied in collaboration with the research group of professor William Skene. The results have shown that both types of pyrrole have potential for the synthesis of conjugated polymers and dendrimers used in the manufacture of electroluminescent materials. Following these encouraging results, we performed the synthesis of 6,12-dimethyl-1,5-dipyrrolediazocane. Methyl N-(Boc)-β-alaninate was converted to its corresponding homoallylic ketone, which was oxidized to N-(Boc)aminoheptan-3,6-dione. The Paal-Knorr condensation between N-(Boc)aminoheptan-3,6-dione and aminoheptan-3,6-dione hydrochloride gave 6,12-dimethyl-1,5-dipyrrolediazocane in 17% yield. In sum, we have synthesized and characterized seven new molecules, six of them having photochemical and electrochemical properties interesting for the synthesis of conjugated polymers and dendrimers. The latter offering potential as precursor for the conception of compounds of therapeutic interest.

COMP3016 Web Technology - Strand 3 "History" Lecture 5

Lecture 5: Web 2.0 and Social Hypertext Contains Powerpoint Lecture slides and Hypertext Research Papers: What Is Web 2.0 Design Patterns and Business Models for the Next Generation of Software . Tim O'Reilly (2005); Web 2.0: Hypertext by Any Other Name? (Millard & Ross, 2006)

Synthesis, Antifungal and Antitumor Activity of Novel (Z)-5-Hetarylmethylidene-1,3-thiazol-4-ones and (Z)-5-Ethylidene-1,3-thiazol-4-ones

New hetaryl- and alkylidenerhodanine derivatives 3a-d, 3e, and 4a-d were prepared from heterocyclic aldehydes 1a-d or acetaldehyde 1e. The treatment of several rhodanine derivatives 3a-d and 3e with piperidine or morpholine in THF under reflux, afforded (Z)-5-(hetarylmethylidene)-2-(piperidin-1-yl) thiazol-4(5H)-ones and 2-morpholinothiazol-4(5H)-ones 5a-d, 6a-d, and (Z)-5-ethylidene-2-morpholinothiazol-4(5H)-one (5e), respectively, in good yields. Structures of all compounds were determined by IR, 1D and 2D NMR and mass spectrometry. Several of these compounds were screened by the U.S. National Cancer Institute (NCI) to assess their antitumor activity against 60 different human tumor cell lines. Compound 3c showed high activity against HOP-92 (Non-Small Cell Lung Cancer), which was the most sensitive cell line, with GI(50) = 0.62 mu M and LC50 > 100 mu M from the in vitro assays. In vitro antifungal activity of these compounds was also determined against 10 fungal strains. Compound 3e showed activity against all fungal strains tested, but showed high activity against Saccharomyces cerevisiae (MIC 3.9 mu g/mL).

Pauta de observación de patrones motores en niños de 4 a 5 años.

Los objetivos de esta investigación son: 1. Diseñar y validar una pauta de observación de las conductas motoras básicas o patrones motores fundamentales en niños y niñas chilenos de 4 y 5 años. 2. Identificar en una muestra representativa de la región de Maule, el grado de adquisición de los patrones motores fundamentales de los niños y niñas chilenos de 4 a 5 años. 3. Detectar y analizar los procedimientos de intervención utilizados en las aulas de párvulos chilenos para ayudar a la adquisición de los patrones motores fundamentales en niños de 4 a 5 años. 4. Elaborar y proponer actividades de estimulación motriz utilizables en las escuelas de párvulos de la región del Maule, para ayudar al desarrollo de los patrones motores fundamentales en niños de 4 a 5 años. 5. Aplicar un programa de estimulación motriz a un grupo experimental, compuesto por niños de 4 a 5 años de ambos sexos para verificar su efectividad y comprobar el periodo requerido para la adquisición de un determinado patrón motor fundamental. La muestra de la investigación está decidida de acuerdo a un estudio descriptivo regional sobre el diagnóstico de la presencia de los patrones motores fundamentales, un estudio de caso y finalmente un estudio pre-experimental. La muestra de aplicación de la pauta de observación de las conductas motoras para párvulos corresponde a 2249 niños y niñas de 4 a 5 años 11 meses de edad correspondientes a los que se encontraban presentes en el momento de evaluación y pertenecientes a jardines infantiles de Junji, Integra y Mineduc de la Región de Maule. El trabajo constituye un diseño descriptivo pre-experimental, considerando procedimientos cualitativos. En la primera fase de la investigación se elaboró una pauta de observación para cotejar la presencia o ausencia de los patrones motores fundamentales de locomoción, manipulación y de estabilidad, una vez estructurada la batera se aplicó en una muestra piloto de 100 párvulos, la mitad de cada sexo y posteriormente se aplicó a la población que constituyó la muestra definitiva. El instrumento utilizado para llevar a cabo esta investigación fue una pauta de observación para verificar el desarrollo de los patrones motores en niños de 4 a 5 años creada por el doctorando y que considera las siguientes variables: equilibro, cuadrupedia, marcha, vertical, salto, lanzamiento, carrera y golpear. Estas variables se definen conforme a la descripción que Mc Clenaghan y Gallahue (1985) realizan sobre los patrones motores fundamentales clasificándolos en tres grupos: locomoción, manipulación y estabilidad. El método utilizado para la recogida de datos fue la observación no participante y el instrumento para la recogida de los datos de una cámara de vídeo. Posteriormente se transcribieron y ordenaron los datos en una hoja de registros para describir la información y el posterior análisis de los mismos. Los resultados indican que en la muestra de la región del Maule, todas las conductas en términos de promedio porcentual presentan una mayor presencia de mayor edad, incluso con un nivel de dispersión menor en la medida en que los niños aumentan en edad. La única variable que no se presenta adquirida a la edad de 4 años, es golpear, ni el indicador botar con una mano 3 veces. El estudio pre-experimental indica que en el sexo femenino se advierten diferencias significativas en las variables equilibrio, marcha, salto, carrera y golpear. Asimismo los varones presentan diferencias significativas en carrera y golpear, e independiente del sexo, existen diferencias significativas en casi todas las variables excepto en cuadrupedia y lanzamiento. Desde el punto de vista teórico-conceptual este estudio aporta las características que deben presentar los patrones motores fundamentales de locomoción, estabilidad y manipulación. Además, presenta un resumen una serie de pautas de evaluación en el ámbito de la psicomotricidad que pueden ayudar a los maestros de educación infantil.

Síntesi de base sòlida de pèptids biarílics contenint 5-arilhistidines

Els aminoàcids biarílics es troben en una àmplia varietat de pèptids naturals amb important activitat biològica. Concretament, les arilhistidines formen part de les aciculitines, pèptids amb activitat citotòxica i antifúngica, La reacció de Suzuki-Miyaura és el mètode més versàtil per obtenir biarils assimètrics, encara que, fins el moment, no s'havia aplicat per a l'arilació de l'imidazole de la histidina. L'objectiu general d'aquesta tesi fou demostrar que es podia arilar l'imidazole de la histidina en fase sòlida mitjançant una reacció de Suzuki-Miyaura. En primer lloc, es sintetitzaren 4(5)-metil-5(4)-fenilimidazole i 4(5)-metil-5(4)-(2-metoxifenil)imidazole a través de l'acoblament creuat entre un N-benzilbromoimidazole i el corresponent àcid arilborònic. Posteriorment, s'arilaren 5-bromohistidines utilitzant diversos àcids arilborònics mitjançant una reacció de Suzuki-Miyaura assistida per irradiació micrones, tant en dissolució com en fase sòlida. I finalment, mitjançant aquesta metodología, es sintetitzaren pèptids antimicrobians contenint 5-arilhistidines actius contra bacteris gram-negatius responsables d'importants malalties en plantes com el foc bacterià.

Synteza analogów nukleozydów i pronukleotydów z zastosowaniem reakcji Huisgena katalizowanej jonami miedzi(I) oraz badania ich aktywności biologicznej

Wydział Chemii: Pracownia Chemii Nukleozydów i Nukleotydów

Birding 2.0: Citizen Science and Effective Monitoring in the Web 2.0 World

The amateur birding community has a long and proud tradition of contributing to bird surveys and bird atlases. Coordinated activities such as Breeding Bird Atlases and the Christmas Bird Count are examples of "citizen science" projects. With the advent of technology, Web 2.0 sites such as eBird have been developed to facilitate online sharing of data and thus increase the potential for real-time monitoring. However, as recently articulated in an editorial in this journal and elsewhere, monitoring is best served when based on a priori hypotheses. Harnessing citizen scientists to collect data following a hypothetico-deductive approach carries challenges. Moreover, the use of citizen science in scientific and monitoring studies has raised issues of data accuracy and quality. These issues are compounded when data collection moves into the Web 2.0 world. An examination of the literature from social geography on the concept of "citizen sensors" and volunteered geographic information (VGI) yields thoughtful reflections on the challenges of data quality/data accuracy when applying information from citizen sensors to research and management questions. VGI has been harnessed in a number of contexts, including for environmental and ecological monitoring activities. Here, I argue that conceptualizing a monitoring project as an experiment following the scientific method can further contribute to the use of VGI. I show how principles of experimental design can be applied to monitoring projects to better control for data quality of VGI. This includes suggestions for how citizen sensors can be harnessed to address issues of experimental controls and how to design monitoring projects to increase randomization and replication of sampled data, hence increasing scientific reliability and statistical power.

Thermal expansion of deuterated hopeite, Zn-3(PO4)(2)center dot 4D(2)O

The lattice parameters extracted from Lebail analysis of neutron powder diffraction data collected between 2 and 300 K have been used to calculate the temperature evolution of the thermal expansion tensor for hopeite, Zn-3(PO4)(2)center dot 2H(2)O, Pnma,Z=4with a= 10.6065(4) angstrom, b = 18.2977(4) angstrom, c= 5.0257(2) A at 275 K. The a lattice parameter shows a negative thermal expansion, the b lattice parameter appears to saturate at 275 K while the c lattice parameter has a more typical positive thermal expansion. At 275 K, the magnitudes of the thermal expansion coefficients are alpha(a) = -1. 1(4) x 10(-5) K-1, alpha(b) = 2.4(9) x 10(-6) K-1 and alpha(c) = 3.6(2) x 10(-1) K-1. Under the conditions of these experiments, hopeite begins to dehydrate to the dihydrate between 300 and 325 K, and between 480 and 500 K the monohydrate is formed. The thermal expansion of the dihydrate has been calculated between 335 and 480 and at 480 K the magnitudes of the thermal expansion coefficients are alpha(a) = 1(2) x 10(-5) K-1, alpha(b) = 4(l) x 10(-6) K-1, alpha(c) = 4(2) x 10(-5) K-1, alpha(beta) = 1 (1) x 10(-1) K-1, and alpha(v) = 2(2) x 10(-1) K-1. The thermal expansion of hopeite is described in terms of its crystal structure and possible dehydration mechanisms for the alpha and beta modifications of hopeite are discussed.

Synthesis, structure and magnetic characterisation of a new layered ammonium manganese(II) diphosphate hydrate, (NH4)(2)[Mn-3(P2O7)(2)(H2O)(2)]

A new layered ammonium manganese(II) diphosphate, (NH4)(2)[Mn-3(P2O7)(2)(H2O)(2)], has been synthesised under solvothermal conditions at 433 K in ethylene glycol and the structure determined at 293 K using single-crystal X-ray diffraction data (M-r = 584.82, monoclinic, space group P2(1)/a, a = 9.4610( 8), b = 8.3565( 7), c = 9.477(1) Angstrom, beta = 99.908(9) degrees, V = 738.07 Angstrom(3), Z = 2, R = 0.0351 and R-w = 0.0411 for 1262 observed data (I > 3(sigma(I))). The structure consists of chains of cis- and trans-edge sharing MnO6 octahedra linked via P2O7 units to form layers of formula [Mn3P4O14(H2O)(2)](2-) in the ab plane. Ammonium ions lie between the manganese-diphosphate layers. A network of interlayer and ammonium-layer based hydrogen bonding holds the structure together. Magnetic measurements indicate Curie - Weiss behaviour above 30 K with mu(eff) = 5.74(1) mu(B) and theta = -23(1) K, consistent with the presence of high-spin Mn2+ ions and antiferromagnetic interactions. However, the magnetic data reveal a spontaneous magnetisation at 5 K, indicating a canting of Mn2+ moments in the antiferromagnetic ground state. On heating (NH4)(2)[Mn-3(P2O7)(2)(H2O)(2)] in water at 433 K under hydrothermal conditions, Mn-5(HPO4)(2)(PO4)(2).4H(2)O, synthetic hureaulite, is formed.

Solvent extraction and lanthanide complexation studies with new terdentate ligands containing two 1,3,5-triazine moieties

The extracting agent 2,6-bis(4,6-di-pivaloylamino-1,3,5-triazin-2-yl)-pyridine (L-5) in n-octanol was found, in synergy with 2-bromodecanoic acid, to give D-Am/D-Eu separation factors (SFs) between 2.4 and 3.7 when used to extract the metal ions from 0.02-0.12 M HNO3. Slightly higher SFs (4-6) were obtained in the absence of the synergist when the ligand was used to extract Am(III) and Eu(III) from 0.98 M HNO3. In order to investigate the possible nature of the extracted species crystal structures of L-5 and the complex formed between Yb(III) with 2,6-bis(4,6-di-amino-1,3,5-triazin-2-yl)-pyridine (L-4) were also determined. The structure of L-5 shows 3 methanol solvent molecules all of which form 2 or 3 hydrogen bonds with triazine nitrogen atoms, amide nitrogen or oxygen atoms, or pyridine nitrogen atoms. However, L-5 is relatively unstable in metal complexation reactions and loses amide groups to form the parent tetramine L-4. The crystal structure of Yb(L-4)(NO3)(3) shows ytterbium in a 9-coordinate environment being bonded to three donor atoms of the ligand and three bidentate nitrate ions. The solvent extraction properties of L-4 and L-5 are far inferior to those found for the 2,6-bis-(1,2,4-triazin-3-yl)-pyridines (L-1) which have SF values of ca. 140 and theoretical calculations have been made to compare the electronic properties of the ligands. The electronic charge distribution in L-4 and L-5 is similar to that found in other terdentate ligands such as terpyridine which have equally poor extraction properties and suggests that the unique properties of L-1 evolve from the presence of two adjacent nitrogen atoms in the triazine rings.