Synthesis and crystal structure of a cis-oxime-oximate bridged tetra coordinated open-book shaped new dicopper(II/II) complex [Cu2(μ-Hdmg)2(Hdmg)]ClO4: First report of unusual oxime OH bridging

Reaction of Cu(ClO₄)₂ · 6H₂O with dimethylglyoxime (H₂dmg) and triethylamine (pH ∼ 4-5) at room temperature affords oxime bridged dicopper(II/II) complex of formula [Cu₂(μ-Hdmg)₂(Hdmg)]ClO₄ · H₂O (1) (H₂dmg = dimethylglyoxime). The complex has been characterized by single-crystal X-ray diffraction analysis. The structure consists of one dinuclear complex cation, [Cu₂(μ-Hdmg)₂(Hdmg)], and one anion. Two copper(II) ions at a distance of 3.558 Å are bridged by one oxime and one oximate groups in cis arrangement. The geometry around each copper atom is square planar with an overall open-book type arrangement of these planes. The average copper-oxygen distance is (1.953 Å) and the average copper-nitrogen distance is 2.003 Å. The Cu-O(oxime) distance (1.963 Å) is higher than the Cu-O(oximate) distance (1.942 Å) due to different protonation label. The room temperature value of χ_MT for the title complex (χ_M being the molar magnetic susceptibility for two copper atoms) is low (ca. 0.42 cm³ K mol⁻¹) (μ_eff = 1.52 μ_B). The UV-Vis spectrum of the complex shows a characteristic broad band at 470 nm.     

Dinuclear copper(II) complexes containing 6-(benzylamino)purines as bridging ligands: Synthesis, characterization, and in vitro and in vivo antioxidant activities

A series of dinuclear copper(II) complexes involving 6-(benzylamino)purine derivatives, (HL_n), as bridging ligands were synthesized, characterized and tested for both their in vitro and in vivo antioxidant activities. Based on results of elemental analyses, temperature dependence of magnetic susceptibility measurements, UV-vis, FTIR, EPR, NMR and MALDI-TOF mass spectroscopy, conductivity measurements and thermal analyses, the complexes with general compositions of [Cu₂(μ-HL_n)₄Cl₂]Cl₂ · 2H₂O (1-4) and [Cu₂(μ-HL_n)₂(μ-Cl)₂Cl₂] (5-7) were prepared {where n = 1-4; HL₁ = 6-[(2-methoxybenzyl)amino]purine, HL₂ = 6-[(4-methoxybenzyl)amino]purine, HL₃ = 6-[(2,3-dimethoxybenzyl)amino]purine and HL₄ = 6-[(3,4-dimethoxybenzyl)amino]purine}. In the case of complexes 2, 3, 5 and 7, the antioxidant activities were studied by both in vitro {superoxide dismutase-mimic (SOD-mimic) activity} and in vivo {cytoprotective effect against the alloxan-induced diabetes (antidiabetic activity)} methods. The obtained IC₅₀ value of the SOD-mimic activity for the complex 5 (IC₅₀ = 0.253 μM) was shown to be even better than that of the native bovine Cu,Zn-SOD enzyme (IC₅₀ = 0.480 μM), used as a standard. As for the antidiabetic activity, the pretreatment of mice with complexes 3 and 7 led to the complete elimination of cytotoxic attack of alloxan and its free radical metabolites, used as a diabetogenic agent. The cytoprotective effect of these compounds was proved by the preservation of the initial blood glucose levels of the pretreated animals, as against the untreated control group.     

Effects of Echinaforce treatment on ex vivo-stimulated blood cells

The herb Echinacea purpurea, also called purple coneflower, is regarded as an immune modulator. This study examined changes in cytokine production in blood samples from 30 volunteers before and during 8-day oral administration with an ethanolic extract of fresh Echinacea purpurea (Echinaforce^®). Daily blood samples were ex vivo stimulated by LPS/SEB or Zymosan and analysed for a series of cytokines and haematological and metabolic parameters. Treatment reduced the proinflammatory mediators TNF-α and IL-1β by up to 24% (p < 0.05) and increased anti-inflammatory IL-10 levels by 13% (p < 0.05) in comparison to baseline. This demonstrated a substantial overall anti-inflammatory effect of Echinaforce^® for the whole group (n = 28). Chemokines MCP-1 and IL-8 were upregulated by 15% in samples from subjects treated with Echinaforce^® (p < 0.05). An analysis of a subgroup of volunteers who showed low pre-treatment levels of the cytokines MCP-1, IL-8, IL-10 or IFN-γ (n = 8) showed significant stimulation of these factors upon Echinaforce^® treatment (30-49% increases; p < 0.05), whereas the levels in subjects with higher pre-treatment levels remained unaffected. We chose the term “adapted immune-modulation” to describe this observation. Volunteers who reported high stress levels (n = 7) and more than 2 colds per year experienced a significant transient increase in IFN-γ upon Echinaforce^® treatment (>50%). Subjects with low cortisol levels (n = 11) showed significant down-regulation of the acute-phase proteins IL1-β, IL-6, IL-12 and TNF-α by Echinaforce^® (range, 13-25%), while subjects with higher cortisol levels showed no such down-regulation. This is the first ex vivo study to demonstrate adapted immune-modulation by an Echinacea preparation. While Echinaforce^® did not affect leukocyte counts, we speculate that the underlying therapeutic mechanism is based on differential multi-level modulation of the responses of the different types of leukocytes. Echinaforce^® thus regulates the production of chemokines and cytokines according to current immune status, such as responsiveness to exogenous stimuli, susceptibility to viral infection and exposure to stress.     

Reactivity study of arene(azido)ruthenium N∩O-base complexes with activated alkynes

Substitution reaction of chloro η⁶-arene ruthenium N∩O-base complexes [(η⁶-arene)Ru(N∩O)Cl] [N∩O = pyrazine-2-carboxylic acid (pca-H), 8-hydroxyquinoline (hq-H); arene = p-ⁱPrC₆H₄Me, N∩O = hq (1); arene = C₆Me₆, N∩O = hq (2)] with NaN₃ yield the neutral arene ruthenium azido complexes of the general formula [(η⁶-arene)Ru(N∩O)N₃] [N∩O = pca, arene = p-ⁱPrC₆H₄Me (3), arene = C₆Me₆ (4); N∩O = hq, arene = p-ⁱPrC₆H₄Me (5), arene = C₆Me₆ (6)]. These complexes undergo [3 + 2] dipolar cycloaddition reaction with activated alkynes dimethyl and diethyl acetylenedicarboxylates to yield the arene triazole complexes [(η⁶-arene)Ru(N∩O){N₃C₂(CO₂R)₂}] [N∩O = pca, R = Me, arene = p-ⁱPrC₆H₄Me (7), C₆Me₆ (8); R = Et, arene = p-ⁱPrC₆H₄Me (9), C₆Me₆ (10); N∩O = hq, R = Me, arene = p-ⁱPrC₆H₄Me (11) C₆Me₆ (12); R = Et, arene = p-ⁱPrC₆H₄Me (13), C₆Me₆ (14)]. On the bases of proton NMR study, in the above triazole complexes N(2) isomers are assigned with dimethylacetylenedicarboxylate whereas N(1) isomers with diethylacetylenedicarboxylate. All complexes have been characterized by IR and NMR spectroscopy as well as by elemental analysis. The molecular structures of the azido complexes [(η⁶-p-ⁱPrC₆H₄Me)Ru(pca)N₃] (3), [(η⁶-p-ⁱPrC₆H₄Me)Ru(hq)N₃] (5) and [(η⁶-C₆Me₆)Ru(hq)N₃] (6) have been established by single crystal X-ray diffraction studies.     

Half-sandwich ruthenium–arene complexes with thiosemicarbazones: synthesis and biological evaluation of [(η⁶-p-cymene)Ru(piperonal thiosemicarbazones)Cl]Cl complexes

The synthesis and characterization of a number of organometallic ruthenium(II) complexes containing a series of bidentate thiosemicarbazone ligands derived from piperonal is reported. The structure of compounds have been confirmed by spectroscopic analysis (IR and NMR) as well as X-ray crystallographic analysis of [(η⁶-p-cymene)Ru(pPhTSC)Cl]Cl (4) (pPhTSC is piperonal-N(4)-phenylthiosemicarbazone). The interaction of the complexes ([(η⁶-p-cymene)Ru(pEtTSC)Cl]Cl) (3) (pEtTSC is piperonal-N(4)-ethylthiosemicarbazone) and 4 with calf thymus DNA, human serum albumin (HSA) and pBR322 plasmid DNA were studied by spectroscopic, gel electrophoresis and hydrodynamic methods. The apparent binding constant for the interaction with DNA was determined to be 3.97 × 10³ M^− 1 and 4.07 × 10³ M^− 1 at 293 K for 3 and 4 respectively. The complexes bind strongly to HSA with binding constants of 2.94 × 10⁴ M^− 1 and 12.2 × 10⁴ M^− 1 at 296 K for 3 and 4 respectively. The in vitro anticancer activity of 3 and 4 has been evaluated against two human colon cancer cell line (HCT-116 and Caco-2) with IC₅₀ values in the range of 26-150 μM. Both 3 and 4 show good activity as a catalytic inhibitor of human topoisomerase II at concentrations as low as 20 μM. The proficiency of 3 and 4 to act as antibacterial agents was also evaluated against six pathogenic bacterial strains with the best activity seen against Gram-positive strains.     

Rare earth complexation with 1,3,5-trideoxy-1,3,5-tris(2-hydroxybenzyl)amino-cis-inositol

The protonation constants of 1,3,5-trideoxy-1,3,5-tris(2-hydroxyl-benzyl)amino-cis-inositol (thci) in I = 1 M (NaClO₄) were determined to be: pK_a1 5.96 ± 0.03, pK_a2 7.21 ± 0.01, pK_a3 8.32 ± 0.07, pK_a4 8.95 ± 0.06. The solvent extraction studies were consistent with the formation of the Ln(thci)³⁺ and complexes. The log of the stability constants (log β₁ and log β₂) at 25 °C in 1 M (NaClO₄) at pH 4 for formation of these complexes are reported. Laser luminescence measurements of the ⁷F₀-⁵D₀ transition of Eu(III) complexed by thci indicated two species. The shifts in the peaks relative to that of Eu(aq)³⁺ were comparable to the values reported for other complexes of Eu(III) with organic ligands, but the intensities were greater. Luminescence lifetime measurements of the fluorescence spectra indicated that the complex has 5 inner sphere water molecules bound to the Eu(III) cation at pH 6.71-8.52. This was consistent with bidentate chelation of Eu(III) with each thci molecule. gaussian view energy calculations indicated bonding for M(III) to the amino and hydroxyl groups of the cyclohexanetriol and (2-hydroxybenzyl)amino moieties in the Ln(thci)³⁺ complex.     

Binuclear manganese(III) complexes of an unsymmetric pyrazolate-based compartmental ligand with hard donor set

The synthesis, crystal structure and magnetic properties of manganese(III) binuclear complexes [Mn^III₂(L-3Н)₂(CH₃ОH)₄]·2CH₃ОH (1) and [Mn^III₂(L-3Н)₂(Py)₄]·2Py (2) (L = 3-[(1E)-N-hydroxyethanimidoyl]-4-methyl-1H-pyrazole-5-carboxylic acid) are reported. The ligand contains two distinct donor compartments formed by the pyrazolate-N and the oxime or the carboxylic groups. The complexes were characterized by X-ray single crystal diffraction, revealing that both 1 and 2 consist of dinuclear units in which the two metal ions are linked by double pyrazolate bridges with a planar {Mn₂N₄} core. Cryomagnetic measurements show antiferromagnetic interaction with g = 1.99, J = −3.6 cm⁻¹, Θ = −2.02 K for 1 and g = 2.00, J = −3.7 cm⁻¹, Θ = 1.43 K for 2.     

Investigation of the MSO4 · xH2O (M = Zn, x = 7; M = Cd, x = 8/3)/methyl 2-pyridyl ketone oxime reaction system: A novel Cd(II) coordination polymer versus mononuclear and dinuclear Zn(II) complexes

The reactions of methyl 2-pyridyl ketone oxime, (py)C(Me)NOH, with MSO₄ · xH₂O (M = Zn, x = 7; M = Cd, x = 8/3), in the absence of an external base, have been investigated. The synthetic study has led to the two new complexes [Zn(SO₄){(py)C(Me)NOH}(H₂O)₃] · H₂O (1 · H₂O) and [Zn₂(SO₄)₂{(py)C(Me)NOH}₄] · (py)C(Me)NOH [2 · (py)C(Me)NOH], and the coordination polymer [Cd(SO₄){(py)C(Me)NOH}(H₂O)]_n · [Cd(SO₄){(py)C(Me)NOH}(H₂O)₂]_n (3). In the three complexes the organic ligand chelates through its nitrogen atoms. The sulfate anion in 1 · H₂O is monodentate; the complex molecule is the mer isomer considering the positions of the aqua ligands. The Zn^II centers in 2 · (py)C(Me)NOH are bridged by two syn, anti η¹:η¹:μ₂ ligands; each metal ion has the cis-cis-trans disposition of the coordinated sulfate oxygen, pyridyl nitrogen and oxime nitrogens, respectively. The molecular structure of 3 is unique consisting of two different linear and ladder - type chains. π-π stacking interactions and/or hydrogen bonds lead to the formation of interesting supramolecular architectures in the three complexes. The thermal decomposition of complex 3 has been studied. Characteristic vibrational (IR, Raman) bands are discussed in terms of the nature of bonding and the structures of the three complexes.     

Synthesis, structures and DNA binding of ternary transition metal complexes M(II)L with the 2,2-bipyridylamine (L = p-HB, M = Co, Ni, Cu and Zn)

New ternary transition metal complexes of formulations [Co(bpa)(p-HB)₂](bpa = 2,2′-bipyridylamine, p-HB = p-hydroxybenzenecarboxylic acid) (1), [Ni(bpa)(p-HB)(H₂O)₂]⁺(NO₃)⁻ · H₂O (2), , [Cu(bpa)(p-HB)Cl] (4) and [Zn(bpa)(p-HB)₂]₂ · 0.5H₂O (5) are prepared, their structural features are characterized by crystal structural studies, and their DNA binding propensity has been evaluated by fluorescence method. The molecular structure of complex 1 shows the six coordinate octahedral geometry with one bpa and two p-HB ligands, complex 2 is the cationic complex and has the six coordinate octahedral structure with one bpa, one p-HB and two aqua ligands, complex 3 is also the cationic complex of octahedral coordination with two bpa and one p-HB ligands, complex 4 is five coordinate distorted square pyramidal with one bpa, one p-HB and chloride ligands and complex 5 has the distorted octahedral coordination with two p-HB and one bpa ligands. In all of the complexes, both bpa and p-HB act as the bidentate N and O-donor ligands, respectively. The intermolecular H-bond networks, together with π-π interaction in their solid state are also described. The complexes show the competitive inhibition of ethidium binding to DNA, and the DNA binding propensity can be reflected as the relative order: 3 > 2 > 1 > 5 > 4, in which the cationic charged Ni(II) complexes 2 and 3 show the most effective inhibition ability.     

In vivo enzymatic activity of acetylCoA synthetase in skeletal muscle revealed by C turnover from hyperpolarized [1-C]acetate to [1-C]acetylcarnitine

Background

Acetate metabolism in skeletal muscle is regulated by acetylCoA synthetase (ACS). The main function of ACS is to provide cells with acetylCoA, a key molecule for numerous metabolic pathways including fatty acid and cholesterol synthesis and the Krebs cycle.

Methods

Hyperpolarized [1-¹³C]acetate prepared via dissolution dynamic nuclear polarization was injected intravenously at different concentrations into rats. The ¹³C magnetic resonance signals of [1-¹³C]acetate and [1-¹³C]acetylcarnitine were recorded in vivo for 1 min. The kinetic rate constants related to the transformation of acetate into acetylcarnitine were deduced from the 3 s time resolution measurements using two approaches, either mathematical modeling or relative metabolite ratios.

Results

Although separated by two biochemical transformations, a kinetic analysis of the ¹³C label flow from [1-¹³C]acetate to [1-¹³C]acetylcarnitine led to a unique determination of the activity of ACS. The in vivo Michaelis constants for ACS were K_M = 0.35 ± 0.13 mM and V_max = 0.199 ± 0.031 μmol/g/min.

Conclusions

The conversion rates from hyperpolarized acetate into acetylcarnitine were quantified in vivo and, although separated by two enzymatic reactions, these rates uniquely defined the activity of ACS. The conversion rates associated with ACS were obtained using two analytical approaches, both methods yielding similar results.

General significance

This study demonstrates the feasibility of directly measuring ACS activity in vivo and, since the activity of ACS can be affected by various pathological states such as cancer or diabetes, the proposed method could be used to non-invasively probe metabolic signatures of ACS in diseased tissue.     

Dinuclear triphenylphosphinegold(I) sulfanylcarboxylates: Synthesis, structure and cytotoxic activity against cancer cell lines

Compounds of the type [(AuPPh₃)₂(xspa)]; H₂xspa [x:p = 3-phenyl-, f = 3-(2-furyl)-, t = 3-(2-thienyl)-, -o-py = 3-(2-pyridyl)-, Clp = 3-(2-chlorophenyl)-, -o-mp = 3-(2-methoxyphenyl)-, -p-mp = 3-(4-methoxyphenyl)-, -o-hp = 3-(2-hydroxyphenyl)-, -p-hp = 3-(4-hydroxyphenyl)-, -diBr-o-hp = 3-(3,5-dibromo-2-hydroxyphenyl)-; spa = 2-sulfanyl propenoato] were synthesized and characterized by IR and NMR (¹H, ¹³C and ³¹P) spectroscopy and by FAB mass spectrometry. The structures of [(AuPPh₃)₂(Clpspa)], [(AuPPh₃)₂(o-hpspa)], [(AuPPh₃)₂(p-hpspa)]·MeOH and [(AuPPh₃)₂(diBr-o-hpspa)]·2Me₂CO show the dinuclear nature of the complexes with the two gold atoms, one of which is also O-bonded to an O atom of the carboxylate group, bonded to the S atom. The in vitro antitumor activities against the HeLa-229, A2780 and A2780cis cell lines were determined and the compounds were found to be highly effective, in particular against the A2780cis cell line, with eight of the nine compounds having IC₅₀ values better than that of cisplatin. This behavior is indicative of a high ability to circumvent the cellular resistance to this drug.     

Antihypertensive effect of insect cells: In vitro and in vivo evaluation

In this study, we investigated the in vitro ACE inhibitory and in vivo antihypertensive effect of insect cell extracts. The IC₅₀ of three insect cell lines from different type and insect species origin: S2 (embryo, Drosophila melanogaster), Sf21 (ovary, Spodoptera frugiperda) and Bm5 (ovary, Bombyx mori), were evaluated. Most interesting results were that the IC₅₀ values ranged between 0.4 and 0.9 mg/ml, and that an extra hydrolysis with gastrointestinal enzymes did not increase the ACE inhibitory activity conspicuously. Finally, a single oral administration with a gavage of 150 mg cell extract/kg BW to spontaneous hypertensive rats (SHR) significantly decreased (p < 0.05) their systolic blood pressure (SBP) with 5-6% (9-12 mm Hg) compared to the controls at 6 h post-administration. Here the undigested and digested insect S2 cell extracts were equal in activity to lower the SBP. To the best of our knowledge, this is the first report of in vivo antihypertensive activity of insect cell extracts and this without an extra digestion requirement.     

A new tetranuclear copper(II) complex with oximate bridges: Structure, magnetic properties and DFT study

A new tetranuclear complex, [Cu₄L₄](ClO₄)₄·2H₂O (1), has been synthesized from the self-assembly of copper(II) perchlorate and the tridentate Schiff base ligand (2E,3E)-3-(2-aminopropylimino) butan-2-one oxime (HL). Single-crystal X-ray diffraction studies reveal that complex 1 consists of a Cu₄(NO)₄ core where the four copper(II) centers having square pyramidal environment are arranged in a distorted tetrahedral geometry. They are linked together by a rare bridging mode (μ₃-η¹,η²,η¹) of oximato ligands. Analysis of magnetic susceptibility data indicates moderate antiferromagnetic (J₁ = −48 cm⁻¹, J₂ = −40 cm⁻¹ and J₃ = −52 cm⁻¹) exchange interaction through σ-superexchange pathways (in-plane bridging) of the oxime group. Theoretical calculations based on DFT technique have been used to obtain the energy states of different spin configurations and estimate the coupling constants and to understand the exact magnetic exchange pathways.     

Synthesis, structure and cytotoxicity studies of diisopropylammonium and triethylammonium salts of triphenylphosphinegold(I) sulfanylcarboxylates

Compounds of the type [HQ][Au(PPh₃)(xspa)] and [HP][Au(PPh₃)(xspa)] {HQ = diisopropylammonium; HP = triethylammonium; H₂xspa = 3-aryl-2-sulfanylpropenoic acids [x: p = 3-phenyl-, f = 3-(2-furyl)-, t = 3-(2-thienyl)-, -o-py = 3-(2-pyridyl)-, Clp = 3-(2-chlorophenyl)-, -o-mp = 3-(2-methoxyphenyl)-, -p-mp = 3-(4-methoxyphenyl)-, -o-hp = 3-(2-hydroxyphenyl)-, -p-hp = 3-(4-hydroxyphenyl)-, diBr-o-hp = 3-(3,5-dibromo-2-hydroxyphenyl]} were synthesized and characterized by IR and NMR (¹H, ¹³C and ³¹P) spectroscopy and by FAB mass spectrometry. The structures of [HQ][Au(PPh₃)(Clpspa)] and [HQ][Au(PPh₃)(-o-mpspa)] show that the crystal contains hydrogen-bonded diisopropylammonium cations and [Au(PPh₃)(xspa)]⁻ anions. The anions in the two compounds have different structures, with the carboxylate group either coordinated or not coordinated to the gold atom, respectively. The in vitro antitumour activities against the HeLa-229, A2780 and A2780cis cell lines were determined for all complexes. The diisopropylammonium derivatives were generally found to be more active, in particular against the A2780cis cell line, and showed a high ability to circumvent the cellular resistance to cisplatin.     

Evaluation of a diospyrin derivative as antileishmanial agent and potential modulator of ornithine decarboxylase of Leishmania donovani

World health organization has called for academic research and development of new chemotherapeutic strategies to overcome the emerging resistance and side effects exhibited by the drugs currently used against leishmaniasis. Diospyrin, a bis-naphthoquinone isolated from Diospyros montana Roxb., and its semi-synthetic derivatives, were reported for inhibitory activity against protozoan parasites including Leishmania. Presently, we have investigated the antileishmanial effect of a di-epoxide derivative of diospyrin (D17), both in vitro and in vivo. Further, the safety profile of D17 was established by testing its toxicity against normal macrophage cells (IC₅₀ ∼ 20.7 μM), and also against normal BALB/c mice in vivo. The compound showed enhanced activity (IC₅₀ ∼ 7.2 μM) as compared to diospyrin (IC₅₀ ∼ 12.6 μM) against Leishmania donovani promastigotes. Again, D17 was tested on L. donovani BHU1216 isolated from a sodium stibogluconate-unresponsive patient, and exhibited selective inhibition of the intracellular amastigotes (IC₅₀ ∼ 0.18 μM). Also, treatment of infected BALB/c mice with D17 at 2 mg/kg/day reduced the hepatic parasite load by about 38%. Subsequently, computational docking studies were undertaken on selected enzymes of trypanothione metabolism, viz. trypanothione reductase (TryR) and ornithine decarboxylase (ODC), followed by the enzyme kinetics, where D17 demonstrated non-competitive inhibition of the L. donovani ODC, but could not inhibit TryR.     

One-pot syntheses of alkenyl-phosphonio complexes of ruthenium(II), rhodium(III) and iridium(III) bearing p-cymene or pentamethylcyclopentadienyl groups

Reaction of [(p-cymene)RuCl₂(PPh₃)] (1) or [Cp^∗MCl₂(PPh₃)] (Cp^∗ = C₅Me₅) (3a: M = Rh; 4a: M = Ir) with 1-alkynes and PPh₃ were carried out in the presence of KPF₆, generating the corresponding alkenyl-phosphonio complexes, [(p-cymene)RuCl(PPh₃){CHCR(PPh₃)}](PF₆) (2a: R = Ph; 2b: R = p-tolyl) or [Cp^∗MCl(PPh₃){CHCPh(PPh₃)}](PF₆) (5: M = Rh; 6: M = Ir). Similar reactions of complexes [Cp^∗RhCl₂(L¹)] (3a: L¹ = PPh₃; 3c: L¹ = P(OMe)₃) with L² (L² = PPh₃, PMePh₂, P(OMe)₃) gave [Cp^∗RhCl(L¹)(L²)](PF₆) (7bb: L¹ = L² = PMePh₂; 7ca: L¹ = P(OMe)₃, L² = PPh₃; 7cc: L¹ = L² = P(OMe)₃). Alkenyl-phosphonio complex 5 was treated with P(OMe)₃ or 2,6-xylyl isocyanide, affording [Cp^∗RhCl(L){CHCPh(PPh₃)}](PF₆) (8a: L = P(OMe)₃; 8b: L = 2,6-xylNC). X-ray structural analyses of 2a, 6 and 8a revealed that the phosphonium moiety bonded to the C_β atom of the alkenyl group are E configuration.     

Accuracy of in vivo and ex vivo ultrasonographic evaluation of ovarian follicles and corpora lutea in sows

Current study determined, in sows, the accuracy of ultrasonography for in vivo (n = 8) and ex vivo (n = 7) evaluation of corpora lutea (CLs) and follicles ≥1.5 mm in size, by comparison with macroscopic findings in sliced ovaries. The accuracy for ex vivo detection of follicles increased with follicle size (P < 0.05), being low for 1.5-1.9 mm follicles (65.9%) and higher for ≥6 mm follicles (93.3%); differences between ultrasonographic and macroscopic observations were significant only for follicles smaller than 3.9 mm (P < 0.05), due to underestimation. Ex vivo observation succeeded to detect presence or absence of CLs in all the ovaries; the efficiency for determining the exact number of CLs being 94.4%. The accuracy for in vivo detection of follicles also increased with follicle size (P < 0.05), dropping to values lower than 40% for 1.5-1.9 mm follicles; therefore, there were significant differences between ultrasonographic and macroscopic observations (P < 0.05). On the other hand, accuracy remained around 92% for ≥6 mm follicles. Ultrasonography was useful again for detecting presence of CLs in all the ovaries; the efficiency for determining CLs number reached 86.7%, due to underestimation in ovaries with higher number of CLs (P < 0.05). Overall, there were no significant differences when comparing the accuracy of ex vivo and in vivo scannings for determination neither of the number of follicles in each size-category larger than 1.9 mm nor of the presence of ovulations or of the CLs number in each ovary. In conclusion, the use of ultrasonography allows an accurate detection of the presence and number of CLs and follicles ≥2 mm of diameter in sows, without significant differences between in vivo and ex vivo observations.     

Enzymatically derived aldouronic acids from Cryptomeria japonica arabinoglucuronoxylan

An arabinoglucuronoxylan was extracted from the holocellulose of sugi (Cryptomeria japonica) wood with 10% KOH and subjected to hydrolysis by partially purified xylanase fraction from a commercial cellulase preparation “Meicelase”. Neutral sugars liberated were analyzed by size exclusion chromatography showing the presence of xylooligosaccharides up to xylohexaose. Aldouronic acids liberated were purified by preparative anion exchange chromatography. Their structures were identified by monosaccharide analysis, comparison of their volume distribution coefficients (Dvs) with those of the authentic samples in anion exchange chromatography and ¹H and ¹³C NMR spectroscopy, resulting in the characterization of eight aldouronic acids including acids consisting of two 4-O-Me-α-D-GlcAp residues and 3-5 D-Xyl residues.

1.

Fr. 1-S1: (aldohexaouronic acid, MeGlcA³Xyl₅), O-β-Xylp-(1 → 4)-O-β-D-Xylp-(1 → 4)-[O-(4-O-Me-α-D-GlcAp)-(1 → 2)]-O-β-Xylp-(1 → 4)-O-β-D-Xylp-(1 → 4)-D-Xyl

2.

Fr. 1-S2: (aldopentaouronic acid, MeGlcA³Xyl₄), O-β-Xylp-(1 → 4)-[O-(4-O-Me-α-D-GlcAp)-(1 → 2)]-O-β-D-Xylp-(1 → 4)-O-β-Xylp-(1 → 4)-D-Xyl

3.

Fr. 2-S1: (aldotetraouronic acid, MeGlcA³Xyl₃), O-(4-O-Me-α-D-GlcAp)-(1 → 2)-O-β-D-Xylp-(1 → 4)-O-β-D-Xylp-(1 → 4)-D-Xyl

4.

Fr. 3-S1: (aldotetraouronic acid, GlcA³Xyl₃), O-(α-D-GlcAp)-(1 → 2)-O-β-D-Xylp-(1 → 4)-O-β-Xylp-(1 → 4)-D-Xyl,

5.

Fr. 4-S1: (aldotriouronic acid, GlcA²Xyl₂), O-(4-O-Me-α-D-GlcAp)-(1 → 2)-O-β-D-Xylp-(1 → 4)-D-Xyl

6.

Fr. 4-S2: (MeGlc⁴MeGlcA³Xyl₅), O-β-D-Xylp-(1 → 4)-[O-(4-O-Me-α-D-GlcAp)]-(1 → 2)-O-β-D-Xylp-(1 → 4)-[O-(4-O-Me-α-D-GlcAp)]-(1 → 2)-O-β-D-Xylp-(1 → 4)-O-β-D-Xylp-(1 → 4)-D-Xyl

7.

Fr. 6-S1: (MeGlcA⁴MeGlcA³Xyl₄), O-(4-O-Me-α-D-GlcAp)-(1 → 2)-O-β-D-Xylp-(1 → 4)-O-[(4-O-Me-α-D-GlcAp)]-(1 → 2)-O-β-D-Xylp-(1 → 4)-O-β-D-Xylp-(1 → 4)-D-Xyl

8.

Fr. 7-S1: (MeGlcA³MeGlc²Xyl₃), O-(4-O-Me-α-D-GlcAp)-(1 → 2)-O-β-D-Xylp-(1 → 4)-O-[(4-O-Me-α-D-GlcAp)]-(1 → 2)-O-β-D-Xylp-(1 → 4)-D-Xyl

Fr. 4-S2 was a new acidic oligosaccharide. The distribution pattern of these vicinal uronic acid units along the D-xylan chain was discussed.     

Human plasma phospholipid transfer protein specific activity is correlated with HDL size: Implications for lipoprotein physiology

To gain further insights into the relationship between plasma phospholipid transfer protein (PLTP) and lipoprotein particles, PLTP mass and phospholipid transfer activity were measured, and their associations with the level and size of lipoprotein particles examined in 39 healthy adult subjects. No bivariate correlation was observed between PLTP activity and mass. PLTP activity was positively associated with cholesterol, triglyceride, apo B and VLDL particle level (r_s = 0.40–0.56, p ≤ 0.01) while PLTP mass was positively associated with HDL-C, large HDL particles, and mean LDL and HDL particle sizes (r_s = 0.44–0.52, p < 0.01). Importantly, plasma PLTP specific activity (SA) was significantly associated with specific lipoprotein classes, positively with VLDL, IDL, and small LDL particles (r_s = 0.42–0.62, p ≤ 0.01) and inversely with large LDL, large HDL, and mean LDL and HDL particle size (r_s = − 0.42 to − 0.70, p ≤ 0.01). After controlling for triglyceride levels, the correlation between PLTP mass or SA and HDL size remained significant. In linear models, HDL size explained 45% of the variability of plasma PLTP SA while triglyceride explained 34% of the PLTP activity. Thus, in healthy adults a significant relationship exists between HDL size and plasma PLTP SA (r_s = − 0.70), implying that HDL particle size may modulate PLTP SA in the vascular compartment.