Synthesis and luminescence properties of a blue-emitting Sr(3.5) Y(6.5) O(2) (PO(4) )(1.5) (SiO(4) )(4.5) :Eu(2+) phosphor

A novel blue‐emitting Sr_3.5Y_6.5O₂(PO₄)_1.5(SiO₄)_4.5:Eu²⁺ phosphor was synthesized via a solid‐state reaction. Powder X‐ray diffraction (XRD) analysis demonstrated that the Sr_3.5Y_6.5O₂(PO₄)_1.5(SiO₄)_4.5 host had a hexagonal crystal structure in the space group P6₃/m and unit cell parameters a = 9.418 Å, c = 6.900 Å. The as‐prepared phosphor showed a blue emission and all the main emission peaks were located at around 466 nm for different excitation wavelengths of 297, 333 and 391 nm. The temperature dependence of the photoluminescence property was investigated in the range 20–250 °C, and the emission intensity decreased to 71% of the initial value at room temperature on increasing the temperature to 150 °C. According to the classical theory of fluorescent thermal quenching, the activation energy (ΔE) for the thermal quenching luminescence of the as‐prepared Sr_3.45Y_6.5O₂(PO₄)_1.5(SiO₄)_4.5:0.05Eu²⁺ phosphor was determined to be 0.20 eV. Copyright © 2011 John Wiley & Sons, Ltd.     

Cationic (tripyrrinato)palladium(II) complexes

The formation of cationic palladium(II)complexes [TrpyPd^II]⁺X⁻ by salt metathesis of the respective trifluoroacetates with different salts of weakly coordinating anions X⁻ was investigated. With non-hydrolizable counterions, cationic mono- and dinuclear complexes are observed depending on the nature of the anion X⁻ and the solvent. The mononuclear cations, which are only formed with X = BAr^F, most probably carry a weakly bound molecule of dichloromethane at the fourth coordination site of Pd^II. When treated with diazoalkanes, only these are sufficiently reactive to form carbene complexes. Four- and five coordinate Lewis base adducts [TrpyPd^IIL]⁺ with L = CH₃NC, tBuNH₂, PMe₃, PEt₃ and PiPr₃ and [TrpyPd^IIL₂]⁺ with L = PMe₃ were prepared from the mononuclear cations [TrpyPd^II]⁺BAr^F−. From structural studies it becomes apparent, that the formation of stable five coordinate Pd^II species is restricted to medium size ligands and depends on the delicate balance between the steric influence of L and the strain, which is induced on the TrpyPd^II unit.     

Spectroscopic investigations of Er(3+) :CdO-Bi(2) O(3) -B(2) O(3) glasses

This article reports on the optical properties of Er³⁺ ions doped CdO–Bi₂O₃–B₂O₃ (CdBiB) glasses. The materials were characterized by optical absorption and emission spectra. By using Judd–Ofelt theory, the intensity parameters Ω_λ (λ = 2, 4, 6) and also oscillatory strengths were calculated from the absorption spectra. The results were used to compute the radiative properties of Er³⁺:CdBiB glasses. The concentration quenching and energy transfer from Yb³⁺–Er³⁺ were explained. The stimulated emission cross‐section, full width at half maximum (FWHM) and FWHM × values are also calculated for all the Er³⁺:CdBiB glasses. Copyright © 2011 John Wiley & Sons, Ltd.     

Tris(pentachlorophenyl) gold(III) complexes

By reaction of Tl(C₆Cl₅)₂Cl with Au(C₆Cl₅)(tht) (tht = tetrahydrothiophen) or [N(PPh₃)₂] [Au(C₆- Cl₅)Cl] the gold(III) complexes [Au(C₆Cl₅)₃(tht)] or [N(PPh₃)₂][Au(C₆Cl₅)₃Cl] respectively, can be prepared. They are the first tris(pentachlorophenyl)- gold(III) complexes to be reported. The ready displacement of tht by other neutral or anionic ligands leads to the synthesis of Au(C₆Cl₅)₃(Ph₂PCH₂PPh₂) or Q[Au(C₆Cl₅)₃X] (Q=N(PPh₃)₂, PPh₃Me or PPh₂Me₂; X=C₆F₅, SCN, Br or I).     

Biology of Bactrocera (Zeugodacus) tau (Walker) (Diptera: Tephritidae)

The biology of the fruit fly Bactrocera tau, an important horticultural pest, was studied under laboratory conditions at 25°C and 60–70% relative humidity on Cucurbita maxima. The duration of mating averaged 408.03 ± 235.93 min. After mating, the female fly had a preoviposition period of 11.7 ± 4.49 days. The oviposition rate was 9.9 ± 8.50 eggs and fecundity was 464.6 ± 67.98 eggs/female. Eggs were elliptical, smooth and shiny white, turning darker as hatching approached, and measured 1.30 ± 0.07 mm × 0.24 ± 0.04 mm. The chorion has polygonal microsculpturing and is species-specific with polygonal walls. The egg period lasts for 1.3 ± 0.41 days. The duration of the larval period is 1.2 ± 0.42, 1.7 ± 0.48 and 4.0 ± 0.94 days for first, second and third instars, respectively. Pupation occurs in the sand or soil and pupal periods are 7.0 ± 0.47 days. The life cycle from egg to adult was completed in 14.2 ± 1.69 days; the longevity of mated females and males was 130.33 ± 14.18 and 104.66 ± 31.21 days, respectively. At least two to three generations were observed from June 2008 to June 2009.     

The helix-coil transitions of poly (dA)-poly (dT) and poly (dA-dT)-poly (dA-dT)

Helix–coil transition curves are calculated for poly (dA) poly(dT) and poly (dA-dT) poly (dA-dT) using the integral equation approach of Goel and Montroll.⁵ The transitions are described by the loop entropy model with the exponent of the loop entropy factor, k, remaining an arbitrary constant. The theoretical calculations are compared with experimental transition curves of the two polymers. Results indicate that the stacking energies for these two polymers differ by about 1 kcal/mole of base pairs. Also, a fit between theory and experiment was not possible for k > 1.70.     

Synthesis and properties of trinuclear polypyridyl complexes Ru(II)-Co(II)-Ru(II) and Ru(II)-Co(III)-Ru(II): Their photoinduced interconversion

The trinuclear [{Ru^II(bpy)₂(bpy-terpy)}₂Co^II]⁶⁺ complex (1⁶⁺) in which a Co(II)-bis-terpyridine-like centre is covalently linked to two Ru(II)-tris-bipyridine-like moieties by a bridging bipyridine-terpyridine ligand has been synthesised and characterised. Its electrochemical, photophysical and photochemical properties have been investigated in CH₃CN. The cyclic voltammetry exhibits two successive reversible oxidation processes, corresponding to the Co^III/Co^II and Ru^III/Ru^II redox couples at E_1/2 = −0.06 and 0.91 V vs Ag/Ag⁺ 10 mM, respectively. The one-electron oxidized form of the complex, [{Ru^II(bpy)₂(bpy-terpy)}₂Co^III]⁷⁺ (1⁷⁺) obtained after exhaustive electrolysis carried out at 0.2 V is fully stable. 1⁶⁺ and 1⁷⁺ are only poorly luminescent, indicating that the covalent linkage of the Ru(II)-tris-bipyridine centre to the cobalt subunit leads to a strong quenching of the Ru^II excited state by an intramolecular process. Luminescence lifetime experiments carried out at different temperatures indicate that the transfer is more efficient for 1⁷⁺ compare to 1⁶⁺ due to lower activation energy. Continuous irradiation of 1⁷⁺ performed at 405 nm in the presence of P(Ph)₃ acting as sacrificial electron donor leads to its quantitative reduction into 1⁶⁺, whereas similar experiment starting from 1⁶⁺ with a sulfonium salt as sacrificial electron acceptor converts 1⁶⁺ into 1⁷⁺ with a slower rate and a maximum yield of 80%. These photoinduced electron transfers were followed by UV-Visible spectroscopy and compared with those obtained with a simple mixture of both mononuclear parent complexes i.e. [Ru^II(bpy)₃]²⁺ and [Co^II(tolyl-terpy)₂]²⁺ or [Co^III(tolyl-terpy)₂]³⁺ (tolyl-terpy = 4′-(4-methylphenyl)-2,2′:6′,2′′-terpyridine).     

Copper (II) and cobalt (II) complexes of chiral tetrathiafulvalene-oxazoline (TTF-OX) and tetrathiafulvalene-thiomethyl-oxazoline (TTF-SMe-OX) derivatives

Synthesis and single crystal X-ray structures of the first paramagnetic transition metal complexes containing chiral ethylenedithio-tetrathiafulvalene-oxazoline (EDT-TTF-OX) 1a-c and ethylenedithio-tetrathiafulvalene-thiomethyloxazoline 2 (EDT-TTF-(SMe)OX) ligands based on copper (II) and cobalt (II) are described. The racemic [EDT-TTF-OX][Cu(hfac)₂] complex 3a crystallizes in the triclinic centrosymmetric space group , whereas the enantiopure counterparts 3b-c crystallize in the triclinic non-centrosymmetric space group P1. Cu(II) adopts a distorted square pyramidal coordination geometry, a much weaker Cu?S_TTF interaction also being identified. The same coordination pattern around Cu(II) is observed in the complex [(rac)-EDT-TTF-(SMe)OX][Cu(hfac)₂] (4) in spite of the bidentate nature of the redox active ligand. DFT theoretical calculations afforded two equilibrium configurations for a corresponding model complex, in which the metal centre establishes secondary coordination either with one S_TTF or with the SMe group. The same ligand coordinates the cobalt (II) to afford the octahedral complex [(rac)-EDT-TTF-(SMe)OX][Co(hfac)₂] (5). In all these novel complexes, the paramagnetic centres are structurally and magnetically isolated. Cyclic voltammetry measurements show the stability of the radical cation species.     

Archaeobotany of capers (Capparis) (Capparaceae)

The origins of capers, their use and cultivation are discussed. Capers seeds and charcoal are often recovered from archaeological sites of the Mediterranean and West Asia. These are referred to as C. Spinosa L. This is mostly a group of cultivars restricted to localities surrounding the Western Mediterranean and some places in the Eastern Mediterranean. Identification of the findings is discussed in terms of seed morphology, present distribution and ancient uses of C. aegyptia Lam., C. sicula Veill., C. cartilaginea Decne, C. orientalis Veill., C. decidua (Forssk.) Edgew. and other species. Citations of Capparis in early Rabbinic, Mesopotamian and Greco-Roman texts are presented. Received June 3, 2002 / Accepted October 8, 2002 Correspondence to: D. Rivera     

Mitochondria-rich cells in the astigmatic mites,Diplaegidia columbae (Buchholz) (Analgidae) and Falculifer rostratus (Buchholz) (Falculiferidae) (Acari: Astigmata)

Mitochondria are well-characterized intracellular organelles usually concentrated in locations of high energy consumption. Light microscopic and transmission electron microscopic observations of the internal anatomy of the feather mites Diplaegidia columbae and Falculifer rostratus were conducted. In the anterior half of the bodies of the mites, we found several dozen of distinctive mitochondria-rich (MR) cells filled with abundant, large mitochondria. Mitochondria are placed individually or enclosed in small groups within an elaborated lamellar system forming a mitochondria–lamellae complex (MLC). The role of the MLC as well as the MR cells is not clear at present, but their involvement in heat generation is hypothesized and briefly discussed.     

Synthesis and structure of chloro(ligand)bis(diphenylglyoximato)cobalt(III) complexes

The synthesis and characterization of trans-chloro- (ligand)bis(diphenylglyoximato)cobalt(III) complexes [ligand = pyridine (py), α-, β-, or γ-picoline (α-pic, β-pic, γ-pic), 3,5-lutidine (lut), p-toluidine (p-tol) and PPh₃] is presented. X-ray crystal structure determination of the pyridine (1) and p-toluidine (6) derivatives has been carried out. Compound 1 crystallizes in the monoclinic system, space group P2₁/n, with Z = 4 and unit cell parameters a = 23.124(4), b = 13.009(3) and c = 11.204(3) Å, and β= 93.14(2)°. Compound 6 crystallizes in the monoclinic system, space group P2₁/n, with Z = 4 and unit cell parameters a = 18.792(3), b = 12.540(2) and c = 15.346(3) Å, and β = 97.54(2)°.     

Die reusenzelle (cyrtocyte) des Dinophilus (archiannelida)

Dinophilus has a protonephridial system with end-cells. These end-cells are cyrtocytes with an inner canal, a tuft of flagella and a cell wall consisting of rods joined by membranes.

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Abkürzungen BS Blutsinus - CC Cytoplasma der Cyrtocyte - CG Zellgrenze - CK Cytoplasma der Kanalzelle - CV Vertiefung der inneren Zelloberfläche an der Geißelbasis - G Geißel - Coe Coelom - MB Membran des Blutsinus - MC Membran um die Cyrtocyte-Basalmembran - MS Membran zwischen den Reusenstäben - NC Kern der Cyrtocyte - NK Kern der Kanalzelle - Pf Cytoplasmapfeiler der Cyrtocyte - Rs Reusenstab - Spd Speicheldrüse Senkrechte Linie in jeder Abbildung = 1      

Mixed copper(II)-palladium(II) acetates

The reaction of [Cu₂(H₂O)₂(MeCO₂)₄] with [Pd₃(MeCO₂)₆] gives the new polynuclear mixed metal acetates [Cu₂Pd(MeCO₂)₆] and [Cu₂Pd_4⁻ (MeCO₂)₁₂]. Electronic, ESR and IR spectra and antiferromagnetism suggest the former has a triangular and the latter an octahedral arrangement of metal atoms. The relative magnitudes of the antiferromagnetic interactions are discussed.     

Conformational preferences of modified nucleoside N(2)-methylguanosine (m(2)G) and its derivative N(2), N(2)-dimethylguanosine (m(2)(2)G) occur at 26th position (hinge region) in tRNA

Conformational preferences of the modified nucleosides N²-methylguanosine (m²G) and N², N²-dimethylguanosine (m₂²G) have been studied theoretically by using quantum chemical perturbative configuration interaction with localized orbitals (PCILO) method. Automated complete geometry optimization using semiempirical quantum chemical RM1, along with ab initio molecular orbital Hartree–Fock (HF-SCF), and density functional theory (DFT) calculations has also been made to compare the salient features. Single-point energy calculation studies have been made on various models of m²G26:C/A/U44 and m₂²G26:C/A/U44. The glycosyl torsion angle prefers “syn” (χ = 286°) conformation for m²G and m₂²G molecules. These conformations are stabilized by N(3)–HC2′ and N(3)–HC3′ by replacing weak interaction between O5′–HC(8). The N²-methyl substituent of (m²G26) prefers “proximal” or s-trans conformation. It may also prefer “distal” or s-cis conformation that allows base pairing with A/U44 instead of C at the hinge region. Thus, N²-methyl group of m²G may have energetically two stable s-trans m²G:C/A/U or s-cis m²G:A/U rotamers. This could be because of free rotations around C–N bond. Similarly, N², N²-dimethyl substituent of (m₂²G) prefers “distal” conformation that may allow base pairing with A/U instead of C at 44th position. Such orientations of m²G and m₂²G could play an important role in base-stacking interactions at the hinge region of tRNA during protein biosynthesis process.     

Preparation and structure of bis(trifluoroacetato)dicarbonyl bis(triethylphosphine)molybdenum(lI)

The Mo(CO)₂(PEt₃)₂(CF₃COO)₂ complex, obtained by prolonged reaction of trifluoroacetic acid with Mo(CO)₃(PEt₃₎₃ in dichloromethane, was characterized by spectroscopic methods and by X-ray crystal structure determination. The crystals belong to the monoclinic space group Cc, with a = 20.037, b = 10.879, _c = 15.176 Å,β/3 = 129.28° and _Z = 4. The structure was refined on 2135 observed reflections to R = 0.047. The Mo(II) atom is 7-coordinated and has a capped trigonal prism geometry, the capping position being occupied by a monodentate CF₃CO₂ ligand. The quadrangular plane contains one CO, one PEt₃ and one bidentate CF₃CO₂ ligand. The remaining CO and PEt₃ molecules are found on the opposite edge.     

Amidino-complexes of iron(II) and (III)

Lithioamidines {R′N(Li)C(R)NR′, I; R = CH₃, R′ = C₆H₅, p-CH₃,C₆H₄} react with iron(III) chloride

in monoglyme to produce navy-blue, high spin Fe{R′NC(R)NR′}₃ complexes which are extremely air and moisture sensitive. The corresponding reaction when R = R′ = C₆H₅ produces a soluble red complex and an air-stable green complex, whereas when R = H, R′ = C₆H₅ and R = R′ = C₆H₅ and the reaction is started at ca. ?20°, red and green complexes respectively are formed. Though all the complexes are formulated Fe{R′NC(R)NR′}₃, their properties reflect association through bridging amidino-groups. Iron(II) chloride reacts with I(R = CH₃, R′ = p-CH₃C₆H₄) to form two complexes, one crimson and soluble in organic solvents, and one brown and insoluble, which are fomulated [Fe{R′NC(R)NR′}₂]_n. The iron(III) complexes failed to react with, or were decomposed by, a variety of reducing, electrophilic and nucleophilic reagents, though blue Fe{p-CH₃C₆H₄NC(CH₃)N-p-CH₃C₆H₄}₃ reacts readily with nitric oxide to form a purple addition complex from which the N-nitroso-compound p-CH₃C₆H₄NC(CH₃)N(NO)-p-CH₃C₆H₄ was obtained in high yield. Treatment of the corresponding brown iron(II) complex with nitric oxide gave no reaction.     

Photosynthesis of F(1) Hybrids between C(4) and C(3)-C(4) Species of Flaveria

Photosynthetic characteristics were studied in several F₁ hybrids between C₄ and C₃-C₄ species of Flaveria. Stable carbon isotope ratios, O₂ inhibition of apparent photosynthesis, and phosphoenolpyruvate carboxylase activities in the hybrids were similar to the means for the parents. Values of CO₂ compensation concentrations were nearer to those of the C₄ parent and apparent photosynthesis was below that of both parents, being only 60 and 74% of that of the lowest (C₃-C₄) parent in two experiments. Reductions of CO₂ compensation concentration and O₂ inhibition of apparent photosynthesis as well as increases in carbon isotope ratios and phosphoenolpyruvate carboxylase activities compared to values in C₃-C₄ species suggest transfer of a limited degree of C₄ photosynthesis to the F₁ hybrids. However, the lower apparent photosynthesis of the hybrids suggests that transfer of C₄ characteristics to non-C₄ species is detrimental unless characteristics associated with C₄ photosynthesis are fully developed. There was a highly significant negative correlation (r = −0.90) between CO₂ compensation concentration and the logarithm of phosphoenolpyruvate carboxylase activity in the parents and hybrids, suggesting involvement of this enzyme in controlling the CO₂ compensation concentration. Although bundle-sheath cells were more developed in leaves of hybrids than in C₃-C₄ parents, they appeared to contain lower quantities of organelles than those of the C₄ parent. Reduced quantities of organelles in bundle-sheath cells could indicate incomplete compartmentation of partial pathways of the C₄ cycle in the hybrids. This may mean that the reduction of CO₂ compensation and O₂ inhibition of apparent photosynthesis relative to the C₃-C₄ parents is less dependent on fully developed Kranz anatomy than is increased apparent photosynthesis.     

Organotin(IV) derivatives containing bis(diphenylphosphine)- and bis(diphenylphosphineoxo)alkanes

Di-organotin(IV)halides R₂SnCl₂ (R=Me or Ph) react with bis(diphenylphosphine)methane (DPPM) and bis(diphenylphosphine)ethane (DPPE) in ethanol in aerobic conditions yielding 1:1 adducts [R₂SnCl₂(DPPM–O₂)] and [R₂SnCl₂(DPPE–O₂)], respectively, containing the bis(diphenylphosphine) in oxidized form. The 1:1 adduct [SnMe₂Cl₂(DPPM–O₂)] is composed of separate molecules containing six-coordinate tin, with the ligands coordinated in the bidentate O₂-fashion, whereas [SnMe₂Cl₂(DPPE–O₂)] is polymeric, with octahedral and centrosymmetric (all trans) tin atoms. In inert atmosphere, the interaction between R₂SnCl₂ and DPPM or DPPE does not take place. Mono-organotin halides RSnCl₃ (R=Me, Buⁿ or Ph) react with DPPM and DPPE yielding 1:1 adducts [RSnCl₃(DPPM)] (R=Me, Buⁿ or Ph) and [RSnCl₃(DPPE)] (R=Buⁿ or Ph).     

NUTRITION OF TRIDACHIA CRISPATA (MORCH) (SACOGLOSSA)

Autotrophic nutrition plays an important role in adult Tridachiacrispata in the western Atlantic Ocean and results from an endosymbioticassociation between the sacoglossan and the kleptoplastids ofChlorophyta. A series of living specimens 7-80 mm in length was studied inthe laboratory. After a body length of 10 mm has been attained,the parapodial lobes of the two sides meet and fuse. Microscopicexamination of faecal strings of specimens undergoing this transitionrevealed that algal remains were produced only by juvenilesless than 13 mm long. Larger specimens defaecated only rarelyand the diminutive faecal strings contained no recognizablealgal debris. This transition probably parallels the physiologicaltransition between juvenile heterotrophic nutrition and adultautotrophic nutrition. Microscopic examination of the radulae of transitional specimensshowed no diminution of the size, number or morphology of theteeth. This indicates that in an emergency heterotrophic nutritionmay be resumed. Growth rates of Tridachia were measured in the laboratory, withand without light and the provision of algal foods. Unfed animalslost weight rather rapidly in captivity, whereas those fed uponsuitable algae (Halimeda discoidea, Caulerpa verticillata, C.racemosa and Chaetomorpha sp) did not.Caulerpa sertularioideswas suitable for food for a limited time, but proved toxic afterabout a week. Of the other species tested, Caulerpa verticillatawas the least suitable, while Halimeda, Chaetomorpha and Caulerparacemosa were the best. Ironically, C. verticillata was theonly one of the algal species tested which is known to be takenin the natural diet in Floridean waters. These experiments confirmedthat heterotrophic feeding will be resumed in Tridachia if theculture-conditions do not favour autotrophic nutrition.     

Bis(oxalato)dioxovanadate(V) and Bis(oxalato)oxoperoxo-vanadate(V) Complexes: Spectroscopic Characterization and Biological Activity

Two structurally related vanadium(V) complexes, K₃[VO₂(C₂O₄)₂]·3H₂O and K₃[VO(O₂)(C₂O₄)₂]·1/2H₂O, were thoroughly characterized by infrared, Raman, and electronic spectroscopies. The effect of both complexes on the viability of the human MG-63 osteosarcoma cells was tested using the MTT assay. The monoperoxo complex shows a very strong antiproliferative activity (at 100-μM concentration, this complex diminished the cell viability ca. 80 %), whereas the dioxo complex was inactive.