Physicochemical and biological properties of 6(1),6(3),6(5)-tri-O-alpha-maltosyl-cyclomaltoheptaose (6(1),6(3),6(5)-tri-O-alpha-maltosyl-beta-cyclodextrin)

A unique multibranched cyclomaltooligosaccharide (cyclodextrin, CD) of 6(1),6(3),6(5)-tri-O-alpha-maltosyl-cyclomaltoheptaose [6(1),6(3),6(5)-tri-O-alpha-maltosyl-beta-cyclodextrin, (G(2))(3)-betaCD] was prepared. The physicochemical and biological properties of (G(2))(3)-betaCD were determined together with those of monobranched CDs (6-O-alpha-D-glucopyranosyl-alpha-cyclodextrin (G(1)-alphaCD), 6-O-alpha-D-glucopyranosyl-beta-cyclodextrin (G(1)-betaCD), and 6-O-alpha-maltosyl-beta-cyclodextrin (G(2)-betaCD)). NMR spectra of (G(2))(3)-betaCD were measured using various 2D NMR techniques. The solubility of (G(2))(3)-betaCD in water and MeOH-water solutions was extremely high in comparison with nonbranched betaCD and was about the same as that of the other monobranched betaCDs. The formation of an inclusion complex of (G(2))(3)-betaCD with stereoisomers (estradiol, retinoic acid, quinine, citral, and glycyrrhetinic acid) depends on the cis-trans isomers of guest compounds. The cis isomers of estradiol, retinoic acid, and glycyrrhetinic acid were included more than their trans isomers, while the trans isomers of citral and quinine fit more tightly than their cis isomers. (G(2))(3)-betaCD was the most effective host compound in the cis-trans resolution of glycyrrhetinic acid. Among the branched betaCDs, (G(2))(3)-betaCD exhibited the weakest hemolytic activity in human erythrocytes and showed negligible cytotoxicity in Caco-2 cells up to 200 microM. These results indicate unique characteristics of (G(2))(3)-betaCD in some biological responses of cultured cells.     

Structure of Poly (U).poly (A).poly (U)

The molecular structure of poly (U).poly (A).poly (U) has been determined and refined using the continuous x-ray intensity data on layer lines in the diffraction pattern obtained from an oriented fiber of the RNA. The final R-value for the preferred structure is 0.24, far lower than that for the plausible alternatives. The polymer forms an 11-fold right-handed triple-helix of pitch 33.5A and each base triplet is stabilized by Crick-Watson-Hoogsteen hydrogen bonds. The ribose rings in the three strands have C3'-endo, C2'-endo and C2'-endo conformations, respectively. The helix derives additional stability through systematic interchain hydrogen bonds involving ribose hydroxyls and uracil bases. The relatively grooveless cylindrical shape of the triple-helix is consistent with the lack of lateral organization.     

Structure of poly (I).poly (A).poly (I)

The molecular structure of poly (I).poly (A).poly (I) has been determined and refined using the continuous intensity data on layer lines in the x-ray diffraction pattern obtained from an oriented fiber of this polymorphic RNA complex. The polymer forms a 12-fold right-handed triple-helix of pitch 39.7A and each base-triplet is stabilized by quasi Crick-Watson-Hoogsteen hydrogen bonds. The ribose rings in all the three strands have C3'-endo conformations. The final R-value for this best structure is 0.24 and the x-ray fit is significantly superior to all the alternative structures where the different chains might have different furanose conformations. This all-purine triple-helix, counter-intuitively, has a diameter roughly 3A shorter than that of DNA and RNA triple-helices containing a homopurine and two complementary homopyrimidine strands. Its compact, grooveless cylindrical shape is consistent with the lack of lateral organization.     

Structure of poly (dT).poly (dA).poly (dT)

The molecular structure of poly (dT).poly (dA).poly (dT) has been determined and refined using the continuous x-ray intensity data on layer lines in the diffraction pattern obtained from an oriented fiber of the DNA. The final R-value for the preferred structure is 0.29 significantly lower than that for plausible alternatives. The molecule forms a 12-fold right-handed triple-helix of pitch 38.4 A and each base triplet is stabilized by a set of four Crick-Watson-Hoogsteen hydrogen bonds. The deoxyribose rings in all the three strands have C2'-endo conformations. The grooveless cylindrical shape of the triple-helix is consistent with the lack of lateral organization in the fiber.     

The frequencies of Gm(1), Gm(2), Gm(4), Gm(12), and Inv(1) in Hessen (Germany)

Summary The serum groups Gm(1) [Gm(a)], Gm(2) [Gm(x)], Gm(4) [Gm(f)]. Gm(12) [Gm(b)] and Inv(1) [Inv(1)] of 2000 sera of healthy blood donors from the land Hesse were examined. The results obtained were compared with those known until now. Three persons, not related to each other, possessed the extremely rare phenotype Gm(-1, 2, 4, 12) [Gm (a-x+b+f+)]. In 0.75% of the cases we found a discordant behaviour of the factors Gm(4) and Gm(12) [Gm(f) and Gm(b)].

---

Zusammenfassung 2000 Seren von gesunden Blutspendern aus Hessen wurden bezüglich der Gamma-Globulin-Serumgruppen Gm(1) [Gm(a)], Gm(2) [Gm(x)], Gm(4) [Gm(f)]. Gm(12) [Gm(b)] und Inv(1) [Inv(1)] untersucht. Die gefundenen Resultate wurden mit den bisher bekannten verglichen. Drei miteinander nicht verwandte Personen wiesen den äußerst seltenen Phänotyp Gm(-1, 2, 4, 12) [Gm(a-x+b+f+)] auf. In 0.75% der Fälle fanden wir ein diskordantes Verhalten der Faktoren Gm(4) und Gm(12) [Gm(f) und Gm(b)].

---

---

Director: Prof. Dr. W. Wachsmuth

---

Director: Prof. Dr. W. Spielmann

---

The nomenclature suggested by WHO at a round-table conference over genes, genotypes and allotypes of immunglobulins is used. The conference took place in Geneva on the 1965 31. 5. to the 5. 6. [5].

---

With technical assistance of S. Mohs.     

Biosynthesis of cobalamin (vitamin B(12))

The biosynthesis of vitamin B(12) is summarized, emphasizing the differences observed between the aerobic and anaerobic pathways. The biosynthetic route to adenosylcobalamin from its five-carbon precursor, 5-aminolaevulinic acid, can be divided into three sections: (1) the biosynthesis of uroporphyrinogen III from 5-aminolaevulinic acid, which is common to both pathways; (2) the conversion of uroporphyrinogen III into the ring-contracted, deacylated intermediate precorrin 6 or cobalt-precorrin 6, which includes the primary differences between the two pathways; and (3) the transformation of this intermediate to form adenosylcobalamin.     

Preparation, characterization and pH-metric measurements of 4-hydroxysalicylidenechitosan Schiff-base complexes of Fe(III), Co(II), Ni(II), Cu(II), Zn(II), Ru(III), Rh(III), Pd(II) and Au(III)

The 4-hydroxysalicylidenechitosan Schiff-base (2CS-Hdhba) was prepared by the condensation of 2,4-dihydroxybenzaldehyde with chitosan, and its metal complexes, [M(2CS-dhba)Cl₂(H₂O)₂] (M(III) = Fe, Ru, Rh), [M′(2CS-dhba)(AcO)(H₂O)₂] (M′(II) = Co, Ni, Cu, Zn), [Pd(2CS-dhba)Cl(H₂O)] and [Au(2CS-dhba)Cl₂], are reported. These complexes were characterized by elemental analysis, by spectral data (FTIR, solid-phase ¹³C NMR, UV–vis and ESR spectroscopy), by morphological observations (SEM and XRD), and by magnetic and thermal measurements. The Schiff base (2CS-Hdhba) behaves as a bidentate chelate with a single negative charge. The azomethine nitrogen and the deprotonated 2-hydroxy centres with the pendant glucosamine hydroxy functionality play no role in coordination. The dissociation constants of 2CS-Hdhba and the stability constants of some of its metal complexes have been determined pH-metrically.     

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     

N-(2-Pyridyl)acetamide complexes of palladium(II), cobalt(II), nickel(II), and copper(II)

N-(2-Pyridyl)acetamide (aapH) complexes of palladium(II), cobalt(II), nickel(II), and copper(II) have been studied by means of magnetic susceptibilities, and infrared, electronic, and PMR spectra. In the octahedral complexes M(aapH)₂X₂(M = Co, Ni, Cu; X = Cl, Br, NCS, NO₃), bidentate aapH is chelated through the pyridine-N and amid-O atomes, whereas in the square-planar Pd(aapH)₂X₂ (X = Cl, Br) unidentate aapH is coordinated through the pyridine-N atom alone. Under alkaline conditions aapH is deprotonated in the presence of palladium(II) to form Pd(aap)₂·4H₂O, aap being an anionic bidentate ligand and chelating through the pyridine-N and amide-O atoms.     

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.     

New complexes of La(III), Ce(III), Pr(III), Nd(III), Sm(III), Eu(III) and Gd(III) ions with morin

New solid complex compounds of La(III), Ce(III), Pr(III), Nd(III), Sm(III), Eu(III) and Gd(III) ions with morin were synthesized. The molecular formula of the complexes is Ln(C₁₅H₉O₇)₃ · nH₂O, where Ln is the cation of lanthanide and n = 6 for La(III), Sm(III), Gd(III) or n = 8 for Ce(III), Pr(III), Nd(III) and Eu(III). Thermogravimetric studies and the values of dehydration enthalpy indicate that water occurring in the compounds is not present in the inner coordination sphere of the complex. The structure of the complexes was determined on the basis of UV-visible, IR, MS, ¹H NMR and ¹³C NMR analyses. It was found that in binding the lanthanide ions the following groups of morin take part: 3OH and 4CO in the case of complexes of La, Pr, Nd, Sm and Eu, or 5OH and 4CO in the case of complexes of Ce and Gd. The complexes are five- and six-membered chelate compounds.     

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.     

Stereoselective synthesis of chirally deuterated (S)-D-(6-(2)H(1))glucose

Chirally deuterated (S)-D-(6-(2)H(1))glucose has been prepared in good overall yield from d-(6,6'-(2)H(2))glucose by a short, five-step synthesis from D-(6,6-(2)H(2))glucose utilizing (R)-(+)-Alpine-Borane [(R)-9-[(6,6-dimethylbicyclo[3.1.1]hept-2-yl)methyl]-9-borabicyclo[3.3.1]nonane]. Suitably protected methyl 2,3,4-tri-O-benzyl-D-(6,6-(2)H(2))glucopyranoside was prepared and the deuterated O-6 primary alcohol was oxidized to an aldehyde by Swern oxidation. Stereoselective reduction with nondeuterated (R)-(+)-Alpine-Borane gave methyl 2,3,4-tri-O-benzyl-(6S)-D-(6-(2)H(1))glucopyranoside, which was deprotected under standard conditions to afford the title compound. The key stereoselective reduction step was achieved in 90% yield. The preparation uses economical, commercially available starting materials and will be useful for elucidating biosynthetic mechanisms.     

Synthesis and characterisation of a series of 1,2-phenylenedioxoborylcyclopentadienyl-metal complexes [Ti(IV), Zr(IV), Hf(IV), La(III), Ce(III), Yb(III), Sn(II) and Fe(II)]

The preparation of a series of 1,2-phenylenedioxoborylcyclopentadienyl-metal complexes is described. These are of formula [M{η⁵-C₅H₄(BX)}Cl₃] [M = Ti and X = CAT (2a), CAT^t (2b) or CAT^tt (2c); X = CAT^tt and M = Zr (4a) or Hf (4b)], [M{η⁵-C₅H₄(BX)}₂Cl₂] [M = Zr, X = CAT (3a) or CAT^t (3c); or M = Hf, X = CAT (3b) or CAT^t (3d)], [M{(μ-η⁵-C₅H₃BCAT)₂ SiMe₂}Cl₂] [M = Zr (5a) or Hf (5b)], [M{η⁵-C₅H₃(BCAT)₂}Cl₃] [M = Zr (6a) or Hf (6b)], [M{η⁵-C₅H₄BCAT}₃(THF)] [M = La (7a), Ce (7b) or Yb (7c)], [Sn{η⁵-C₅ H₄(BCAT^t)}Cl](8) and [Fe{η⁵-C₅H₄(BCAT^t)}₂] (9). The abbreviations refer to BO₂C₆H₄-1,2 (BCAT) and the 4-Bu^t (BCAT^t) and the (BCAT^tt) analogues. The compounds 2a-9 have been characterised by microanalysis, multinuclear NMR and mass spectra. The single crystal X-ray structure of the lanthanum compound 7a is presented.     

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.