N,N′-Ethylene-bis(3-methoxysalicylideneimine) mononuclear (4f) and heterodinuclear (3d–4f) metal complexes: Synthesis, crystal structure and luminescent properties

The stepwise synthesis of mononuclear (4f) and heterodinuclear (3d–4f) Salen-like complexes has been investigated through structural determination of the intermediate and final products occurring in the process. In the first step, reactions of ligand H₂L and Ln(NO₃)₃ · 6H₂O give rise to three mononuclear lanthanide complexes Ln(H₂L)(NO₃)₃ [H₂L = N,N′-ethylene-bis(3-methoxysalicylideneimine), Ln = Nd (1), Eu (2) and Tb (3)], in which N,N′-ethylene-bis(3-methoxysalicylideneimine) acts as tetradentate ligands with the O₂O₂ set of donor atoms capable of effective coordination. These species are fairly stable and have been isolated. Then, addition of Cu(Ac)₂ · H₂O to the mononuclear lanthanide complex yields expected heterodinuclear (3d–4f) complexes Cu(L)Ln(NO₃)₃ · H₂O [Ln = Nd (4) and Eu (5)] where the Cu(II) ion is inserted to the inner N₂O₂ cavity. Luminescent analysis reveals that complex 3 exhibits characteristic metal-centered fluorescence of Tb(III) ion. However, the characteristic luminescence of both Sm(III) and Eu(III) ions is not observed both in solution and solid state of the complexes.     

大气臭氧浓度升高对银杏叶片活性氧代谢及相关基因表达的影响

采用开顶式气室熏蒸法,设置自然条件下臭氧(O₃)浓度(对照,约40 nmol·mol^-1)、80、160及200 nmol·mol^-14个臭氧浓度,观测了不同浓度臭氧条件下银杏叶片可见伤害、活性氧生成量、抗氧化酶活性及相关基因表达变化情况,分析大气臭氧浓度升高对植物活性氧代谢的影响.结果表明: 160和200 nmol·mol^-1 O₃熏蒸明显伤害银杏叶片,80 nmol·mol^-1与对照无差异,无可见伤害.O₃处理20 d后,160和200 nmol·mol^-1条件下银杏叶片的超氧自由基(O₂^-·)产生速率显著高于80 nmol·mol^-1和对照,而80 nmol·mol^-1与对照无差异;O₃处理40 d后,160和200 nmol·mol^-1熏蒸下叶片过氧化氢(H₂O₂)含量显著高于80 nmol·mol^-1和对照,而过氧化氢酶(CAT)活性显著高于80 nmol·mol^-1和对照,各臭氧处理抗坏血酸过氧化物酶(APX)活性均低于对照.熏蒸40 d后,CAT、APX基因的转录表达持续加强;防御素(GbD)的表达强度则随着臭氧浓度的增加及熏蒸时间的延长而呈显著加强.高浓度臭氧胁迫可使银杏叶片活性氧生成量增加、抗氧化酶活性下降、相关基因表达水平上调,有明显可见叶片伤害.     

A new interpretation of eutectic behavior for distearoylphosphatidylcholine-cholesterol binary bilayer membrane

We investigated the thermotropic phase behavior of the distearoylphosphatidylcholine (DSPC)–cholesterol binary bilayer membrane as a function of the cholesterol composition (X_ch) by fluorescence spectroscopy using 6-propionyl-2-(dimethylamino)naphthalene (Prodan) and differential scanning calorimetry (DSC). The fluorescence spectra, each of which has a single maximum, showed that the wavelength at the maximum intensity (λ_max) changed depending on the bilayer state: ca. 440 nm for the lamellar gel (L_β′ or L_β) and the liquid ordered (L_o) phases, ca. 470 nm for the ripple gel (P_β′) phase and ca. 490 nm for the liquid crystalline (L) phase, respectively. The transition temperatures were determined from the temperature dependences of the λ_max and endothermic peaks of the DSC thermograms. Both measurements showed that the pretransition disappears around X_ch = 0.035. The constructed temperature–X_ch phase diagram indicated that the phase behavior of the binary bilayer membrane at X_ch ≤ 0.15 is similar to that of general liquid–solid equilibrium for a binary system where both components are completely miscible in the liquid phase and completely immiscible in the solid phase. It was also revealed that the diagram has two characteristic points: a congruent melting point at X_ch = 0.08 and a peritectic-like point at X_ch = 0.15. The hexagonal lattice model was used for the interpretation of the phase behavior of the binary bilayer membrane. These characteristic compositions well correspond to the bilayer states in each of which cholesterol molecules are regularly distributed in the hexagonal lattice in a different way. That is, each composition of 0.035, 0.08 and 0.15 is nearly equal to that for the binary bilayer membrane which is entirely occupied with units, each composed of a cholesterol and 30 surrounding DSPC molecules within the next-next-next nearest neighbor sites (Unit (1:30): L_β(1:30)), with units, each of a cholesterol and 12 surrounding DSPC molecules within the next nearest sites (Unit (1:12): L_β(1:12)) or with units, each of a cholesterol and 6 surrounding DSPC molecules at the nearest neighbor sites (Unit (1:6): L_β(1:6)), respectively. Therefore, the eutectic behavior observed in the phase diagram was fully explainable in terms of a kind of phase separation between two different types of regions with different types of regular distributions of cholesterol. Further, the L_o phase was found in the higher X_ch-region (X_ch > 0.15). No endothermic peak over the temperature range from 10 to 80 °C at X_ch = 0.50 suggested that the single L_o phase can exist at X_ch > 0.50.     

The reproduction, age and growth of the spotted rockling

Biology of the Macaronesian endemic rockling Gaidropsarus guttatus was studied in the Azores. The overall sex ratio from the samples was highly in favour of females (1 : 6·33). The growth parameters were L _∞ = 24·23, k  = 1·219 and t ₀ = −0·059. Fish matured at 15 cm L _T and the spawning season was strongly clustered in April.     

Antioxidant properties of violacein: possible relation on its biological function

Violacein, a violet pigment produced by Chromobacterium violaceum, has attracted much attention in recent literature due to its pharmacological properties. In this work, the antioxidant properties of violacein were investigated. The reactivity with oxygen and nitrogen reactive species and 1,1-diphenyl-2-picryl-hydrazyl (DPPH), a stable free radical, was evaluated. EPR studies were carried out to evaluate the reactivity with the hydroxyl radical. The action of violacein against lipid peroxidation in three models of lipid membranes, including rat liver microsomes, Egg and Soy bean phosphathidylcholine liposomes were also evaluated. The compound reacted with DPPH (IC₅₀ = 30 μM), nitric oxide (IC₅₀ = 21 μM), superoxide radicals (IC₅₀ = 125 μM) and decreased the hydroxyl radical EPR signal. The compound protected the studied membranes against peroxidation induced by reactive species in the micromolar range. The reconstitution of violacein into the membranes increased its antioxidant effect. These results indicate that the compound has strong antioxidant potential. Based on these results we suggest violacein plays an important role with the microorganism membrane in defense against oxidative stress.     

Structure-activity relationships of adenosines with heterocyclic N6-substituents

Two series of N⁶-substituted adenosines with monocyclic and bicyclic N⁶ substituents containing a heteroatom were synthesized in good yields. These derivatives were assessed for their affinity ([³H]CPX), potency, and intrinsic activity (cAMP accumulation) at the A₁ adenosine receptor in DDT₁ MF-2 cells. In the monocyclic series, the N⁶-tetrahydrofuran-3-yl and thiolan-3-yl adenosines (1 and 26, respectively) were found to possess similar activities, whereas the corresponding selenium analogue 27 was found to be more potent. A series of nitrogen containing analogues showed varying properties, N⁶-((3R)-1-benzyloxycarbonylpyrrolidin-3-yl)adenosine (30) was the most potent at the A₁AR; IC₅₀ = 3.2 nM. In the bicyclic series, the effect of a 7-azabicyclo[2.2.1]heptan-2-yl substituent in the N⁶-position was explored. N⁶-(7-Azabicyclo[2.2.1]heptan-2-yl)adenosine (38) proved to be a reasonably potent A₁ agonist (K_i = 51 nM, IC₅₀ = 35 nM) while further substitution on the 7″-nitrogen with tert-butoxycarbonyl (31, IC₅₀ = 2.5 nM) and 2-bromobenzyloxycarbonyl (34, IC₅₀ = 9.0 nM) gave highly potent A₁AR agonists.     

Synthesis and in vitro anti-hepatitis B and C virus activities of ring-expanded ('fat') nucleobase analogues containing the imidazo[4,5-e][1,3]diazepine-4,8-dione ring system

As part of our structure–activity relationship studies, we report here the synthesis and in vitro anti-HBV and anti-HCV activities of a number of ring-expanded (‘fat’) nucleobases containing the imidazo[4,5-e][1,3]diazepine-4,8-dione ring system. One of the compounds, ZP-88, exhibited a good activity/toxicity profile against HBV by inhibition of the synthesis of extracellular virion release (EC₅₀ = 1.7 μM, CC₅₀ = 286 μM, SI = 168) and intracellular HBV replication intermediates (EC₅₀ = 8.4 μM, CC₅₀ = 286 μM, SI = 34) in cultured human hepatoblastoma 2.2.15 cells. By contrast, most of the compounds tested against HCV had only marginal activity/toxicity profile, although that was still better than that of the reference compound ribavirin.     

Reproduction, age, growth and mortality of axillary seabream, Pagellus acarne (Sparidae), from the Canarian archipelago

Axillary seabream Pagellus acarne (Risso 1826) caught off the Canary Islands from January 1991 to December 1994 were studied. The length range of the catches was between 11 and 31 cm, with a modal distribution between 17 and 21 cm. The overall ratio of males to females was 1:1.74. Males were observed up to a length of 24 cm. Hermaphrodites were recorded at lengths between 15 and 23 cm. The species was characterized by protandric hermaphroditism. The reproductive season extended from October to March, with a peak in spawning activity in December–January. The size at sexual maturity was 15.8 cm total length (2 years old) for males and 19.4 cm total length (3 years old) for females. The total length–total weight relationship for the entire population is described by the parameters a = 0.0068, and b = 3.2401. Otolith age readings showed that the population exploited consisted of 10 age groups (1–10 years), including a very high proportion of individuals between 1 and 4 years old. The von Bertalanffy growth parameters for all individuals were L_∞ = 32.98 cm, k = 0.22 years⁻¹, and t₀ = −0.87 years. Males grew comparatively slower than females. The instantaneous rates of mortality for all fish were Z = 0.96 years⁻¹, M = 0.30 years⁻¹, and F = 0.66 years⁻¹. The exploitation ratio and the length at first capture were, respectively, E = 0.69 and LC₅₀ = 16.1 cm. The stock is overexploited, therefore measures such as closed seasons or changes in fishing patterns would be desirable to safeguard the spawning stock and recruits.     

Age and growth analysis of the central mudminnow, Umbra limi (Kirtland, 1840)

A rudimentary understanding of age, growth, and life-span is lacking for many non-game fishes. Growth characteristics of the central mudminnow ( Umbra limi ) have not yet been accurately described using reliable hard part analysis. The utility of scales and otoliths as ageing structures and quantified growth was examined in one lake and one stream population of central mudminnow. Scales were found to be of no utility in determining age due to inconsistent formation of yearly annuli and a high incidence of regenerated scales, while otoliths were easily extracted and considered to be an accurate ageing structure. Ages determined from scales were low compared to those from otoliths, and the difference in age interpreted from the two structures increased with fish age. A power function was fitted to describe the length-weight relationship for this species ( a  = 0.0069, b  = 3.175). Von Bertalanffy growth parameters were estimated and compared for each population (Lake: L _∞ = 114.20 mm, K  = 0.30, t ₀ = −0.93; Stream: L _∞ = 77.59 mm, K  = 0.63, t ₀ = −0.76). The lake population showed greater size at age compared to the stream population, especially at older ages, and achieved a larger maximum size. Growth rate was also greater in the lake population (Lake: 1.74; Stream: 1.09 g year⁻¹). Females were larger at age than males in both populations, however all individuals greater than age 3 were males. This work represents the first successful account of central mudminnow growth using hard part analysis.     

Biology of the salema, Sarpa salpa (L. 1758) (Pisces, Sparidae) from the middle-eastern Adriatic

Salema Sarpa salpa (Linnaeus, 1758), were caught in the middle-eastern Adriatic Sea from August to November 2004. Length range of the samples was between 10.3 and 43.9 cm, with mean values of 25.5 cm in males, 32.6 cm in females, and 11.4 and 20.2cm in immature and hermaphrodite specimens, respectively. Sex ratio (males : females) was 3.1 : 1. Males were observed up to 37 cm length. Hermaphrodites showed lengths between 18 and 21 cm. The species was characterized by protandric hermaphroditism. Size at sexual maturity was 20.6 cm (2 years old) for males. Total length-total weight relationship for the entire population is described by the parameters a  = 0.00893, and b  = 3.1055. Otolith age readings showed that the population consisted of 15 age groups (1–15 years), including a very high proportion of individuals 1–7 years old. The von Bertalanffy growth parameters were L _∞ = 33.11cm, k  = 0.514, and t ₀ = −0.392 years for males and L _∞ = 40.85cm, k  = 0.179, and t ₀ = −2.606 years for females. Survival rate of females ( S  = 0.870) was much greater than for males ( S  = 0.769).     

Cadmium biosorption on Spirulina platensis biomass

Dry biomass of Spirulina platensis re-hydrated for 48 h was employed as a biosorbent in tests of cadmium(II) removal from water. Various concentrations of biomass (from 1 to 4 g l⁻¹) and metal (from 100 to 800 mg l⁻¹) were tested. Low biomass levels (X_o  2 g l⁻¹) ensured metal removal up to 98% only at Cd₀= 100 and 200 mg l⁻¹, while X_o  2.0 g l⁻¹ were needed at Cd₀ = 400 mg l⁻¹ to achieve satisfactory results. Whereas X_o = 4.0 g l⁻¹ was effective to remove up to Cd₀ = 500 mg l⁻¹, a further increase in metal concentration (Cd₀ = 600 and 800 mg l⁻¹) led to progressive worsening of the system performance. At a given biomass levels, the kinetics of the process was better at low Cd²⁺ concentrations, while, raising the adsorbent level from 1.0 to 2.0 g l⁻¹ and then to 4.0 g l⁻¹, the rate constant of biosorption increased by about one order of magnitude in both cases and the adsorption capacity of the system progressively decreased from 357 to 149 mg g⁻¹.     

Ozone effects on high light-induced photoinhibition in Phaseolus vulgaris

In this study the response to photoinhibition of photosynthesis and subsequent recovery was examined in plants of Phaseolus vulgaris L. cultivar ‘Pinto’ exposed to charcoal-filtered air or to ozone (O₃) at 150 nL L⁻¹ either for 3 h, or for 5 h. The responses were analysed using chlorophyll fluorescence imaging and by conventional fluorometry. Compared to control plants maintained in charcoal-filtered air, in plants exposed for 3 h to O₃ and then subjected to high light treatment, the results show an increased tolerance to photoinhibition. Plants exposed to the same O₃ concentration but for the longer 5-h period, were not tolerant to the photoinhibition treatment and, instead showed visible symptoms of damage (chlorosis and necrosis) clearly attributable to the longer O₃ exposure. Here the detrimental effects of O₃ aggravated the effects of the high light photoinhibitory treatment. The leaves exposed to the shorter O₃ treatment (150 nL L⁻¹ for 3 h) developed an ability to counteract the negative effects of a high light exposure probably because the O₃ had activated an antioxidant system able to protect the photosynthetic machinery.     

Age, growth and feeding of the common stingray (Dasyatis pastinaca, L., 1758) in the Cilician coastal basin, northeastern Mediterranean Sea

Growth and feeding of stingray ( Dasyatis pastinaca ) were studied using 346 specimens from the Cilician Basin coastal area (northeastern Mediterranean). Age classes between 0 to XII were found. The total length of all specimens ranged from 14.6 to 100.9 cm, and total weight was between 22.5 and 6800 g. Total length (TL)-weight (W) and disc width (DW)-weight (W) relationships were W = 0.0033*L^3.1429 and W = 0.0039*DW^3.4914, respectively. The age data, derived from central readings, were used to estimate the von Bertalanffy length and weight growth parameters. The results were L_∞ = 294.9 cm, W_∞ = 198690.1 g, K = 0.029 year⁻¹; t₀ = −2.2 year. The D. pastinaca diet was composed mainly of crustaceans.     

Anti-allergic substances from the rhizomes of Dioscorea membranacea

Extracts of five species of Thai medicinal plants, locally known as Hua-Khao-Yen, were screened for anti-allergic activities using RBL-2H3 cells. Of the five species studied, the ethanolic extract of Dioscorea membranacea exhibited potent inhibitory activity against β-hexosaminidase release as a marker of degranulation in RBL-2H3 cells, with an IC₅₀ value of 37.5 μg/mL. Eight compounds were isolated from this crude ethanolic extract, [two naphthofuranoxepins (1, 2), one phenanthraquinone (3), three steroids (4–6), and two steroidal saponins (7, 8)], and tested for their anti-allergic activities. The results showed that dioscorealide B (2) possessed the highest activity with an IC₅₀ value of 5.7 μM, followed by dioscoreanone (3, IC₅₀ = 7.7 μM), dioscorealide A (1, IC₅₀ = 27.9 μM), and diosgenin (9, IC₅₀ = 29.9 μM). Structure–activity relationship studies of naphthofuranoxepins on anti-allergic activity revealed that the hydroxylation at position 8 conferred higher activity than methoxylation. For diosgenin derivatives, the aglycone was found to possess higher activity than the diglucosylated molecule; whereas substitution with rhamnoglucosides apparently results in loss of activity. Furthermore, effects of dioscorealide A, dioscorealide B, and dioscoreanone on antigen-induced release of TNF- and IL-4 in the late phase reaction were also examined.     

Variation of DNA photocleavage efficiency for [(TL)2Ru(dpp)]Cl2 complexes where TL=2,2'-bipyridine, 1,10-phenanthroline, or 4,7-diphenyl-1,10-phenanthroline

The complexes [(bpy)₂Ru(dpp)]Cl₂, [(phen)₂Ru(dpp)]Cl₂, and [(Ph₂phen)₂Ru(dpp)]Cl₂ (where dpp = 2,3-bis(2-pyridyl)pyrazine, bpy = 2,2′-bipyridine, phen = 1,10-phenanthroline, Ph₂phen = 4,7-diphenyl-1,10-phenanthroline) have been investigated and found to photocleave DNA via an oxygen-mediated pathway. These light absorbing complexes possess intense metal-to-ligand charge transfer (MLCT) transitions in the visible region of the spectrum. The [(TL)₂Ru(dpp)]²⁺ systems populate ³MLCT states after visible light excitation, giving rise to emissions in aqueous solution centered at 692, 690, and 698 nm for TL = bpy, phen, and Ph₂phen respectively. The ³MLCT states and emissions are quenched by O₂, producing a reactive oxygen species. These complexes photocleave DNA with varying efficiencies, [(Ph₂phen)₂Ru(dpp)]²⁺ > [(phen)₂Ru(dpp)]²⁺ > [(bpy)₂Ru(dpp)]²⁺. The presence of the polyazine bridging ligand will allow these chromophores to be incorporated into larger supramolecular assemblies.     

Growth and reproduction of Mesopotamian spiny eel (Mastacembelus mastacembelus Banks & Solander, 1794) in Ataturk Dam Lake (Şanliurfa), Turkey

Age at length, growth and reproduction of 220 Mastacembelus mastacembelus specimens from the Atatürk Dam Lake were studied from July 2005 to July 2006. Total lengths and weights ranged from 7.0 to 85.0 cm and from 6 to 1100 g, respectively. Maximum age was 13 years. The regression model fitted to length and weight data was W  =   0.0228  L ^2.43 for males and W  =   0.0029  L ^2.95 for females. The von Bertalaffy growth equations for males and females were L _t  = 99.2 [1−e^{−0.11 ( t −0.12)}] and L _t  = 69.2 [1−e^{−0.26 ( t −0.35)}], respectively. Males dominated especially at an older age; the overall sex ratio was 1 : 0.63 (M:F). The breeding period was from May to July. Fecundity ranged from 2540 to 24 000 eggs per female.     

Endogenous heptapeptide Met-enkephalin-Gly-Tyr binds differentially to duplicate delta opioid receptors from zebrafish

Met-enkephalin-Gly-Tyr (MEGY) is an endogenous peptide that binds to opioid sites in zebrafish and in rat brain homogenates. The aim of this work is to characterize the binding profile of this opioid ligand on two duplicate delta receptors from zebrafish, ZFOR1 and ZFOR4. Our results show that, while ZFOR1 presents one single binding site for [³H]-MEGY (K_D = 4.0 ± 0.4 nM), the experimental data from ZFOR4 fit better to the two-site binding model (K_D1 = 0.8 ± 0.2 nM and K_D2 = 30.2 ± 10.2 nM). Two other MEGY synthetic analogues, (D-Ala²)-MEGY and (D-Ala², Val⁵)-MEGY were also prepared and tested, together with the original peptide MEGY and other opioid ligands, in competition binding assays. While these peptides presented K_i values on the nanomolar range when using [³H]-MEGY as radioligand, these parameters were two orders higher in competition binding assays with the antagonist [³H]-diprenorphine. Functional [³⁵S]GTPγS stimulation analysis has revealed that these two receptors can be activated by several opioid agonists. Our results prove that although the MEGY peptide acts as an agonist on ZFOR1 and ZFOR4, there are subtle pharmacological differences between these two delta opioid receptors from zebrafish.     

The effect of anoxic treatment on the larvae of six species of dermestids (Coleoptera)

Abstract: Based on surveys of species of museum pest insects commonly found in Finland, Norway, Denmark and Sweden, six species were selected for a study of the effect of exposure to anoxic treatment on the larval stage. An oxygen level of 0.3% (the rest, nitrogen) was applied and lethal exposure times were determined. Anthrenus museorum L. was the most susceptible species (LT₉₉ = 32.2 h), while Attagenus woodroffei Halst. & Green and Attagenus smirnovi Zhantiev (LT₉₉ = 88.1 h) were the most tolerant species. The LT₉₉ value of At. woodroffei was not calculated, as only 50% of the larvae were killed by the treatment. The results indicate that large intraspecific variation is present in these two Attagenus species. Larvae of Anthrenus verbasci (L.) (LT₉₉ = 43.9 h), Reesa vespulae (Milliron) (LT₉₉ = 53.6 h), and Trogoderma angustum (Solier) (LT₉₉ = 57.2 h) showed intermediate tolerance.     

Metabolism and thermoregulation in Maximowiczi's voles (Microtus maximowiczii) and Djungarian hamsters (Phodopus campbelli)

1 Metabolic rates (Vo₂), body temperature (T_b), and thermal conductance (C) were first determined in newly captured Maximowiczi's voles (Microtus maximowiczii) and Djungarian hamsters (Phodopus campbelli) from the Inner Mongolian grasslands at a temperature range from 5 to 35 °C.

2 The thermal neutral zone (TNZ) was between 25 and 32.5 °C for Maximowiczi's voles and between 25 and 30 °C for Djungarian hamsters. Mean T_b was 37.0±0.1 °C for voles and 36.2±0.1 °C for hamsters. Minimum thermal conductance was 0.172±0.004 ml O₂/g h °C for voles and 0.148±0.003 ml O₂/g h °C for hamsters.

3 The mean resting metabolic rate within TNZ was 2.21±0.05 ml O₂/g h in voles and 2.01±0.07 ml O₂/g h in hamsters. Nonshivering thermogenesis was 5.36±0.30 ml O₂/g h for voles and 6.30±0.18 ml O₂/g h for hamsters.

4 All these thermal physiological properties are adaptive for each species and are shaped by both macroenvironmental and microenvironmental conditions, food habits, phylogeny and other factors.