Oxoiron(IV) in chloroperoxidase compound II is basic: implications for P450 chemistry

With the use of x-ray absorption spectroscopy, we have found that the Fe-O bond in chloroperoxidase compound II (CPO-II) is much longer than expected for an oxoiron(IV) (ferryl) unit; notably, the experimentally determined bond length of 1.82(1) A accords closely with density functional calculations on a protonated ferryl (Fe(IV)-OH, 1.81 A). The basicity of the CPO-II ferryl [pKa > 8.2 (where Ka is the acid dissociation constant)] is attributable to strong electron donation by the axial thiolate. We suggest that the CPO-II protonated ferryl is a good model for the rebound intermediate in the P450 oxygenation cycle;with elevated pKa values after one-electron reduction, thiolate-ligated ferryl radicals are competent to oxygenate saturated hydrocarbons at potentials that can be tolerated by folded polypeptide hosts.     

Hemoglobins A and A2 in New World primates: comparative variation and its evolutionary implications

Hemoglobin A(2) (alpha(2)delta(2)) in New World primates represents about 1/160 to 1/16 of total hemoglobin and, by virtue of this low proportion, is presumed to be functionally unimportant. Nonetheless, A(2) exhibits genetic polymorphism by electrophoresis in three out of five genera, whereas the major component, hemoglobin A (alpha(2)beta(2)), is electrophoretically invariant. Moreover, in four genera, including man, the evolutionary accumulation of mutations has been greater in delta than in beta Such findings suggest that both polymorphism and evolutionary changes can accrue to an effectively functionless and thus selectively nearly netutral gene.     

Buffered tree population changes in a quaternary refugium: evolutionary implications

A high-resolution pollen record from western Greece shows that the amplitude of millennial-scale oscillations in tree abundance during the last glacial period was subdued, with temperate tree populations surviving throughout the interval. This provides evidence for the existence of an area of relative ecological stability, reflecting the influence of continued moisture availability and varied topography. Long-term buffering of populations from climatic extremes, together with genetic isolation at such refugial sites, may have allowed lineage divergence to proceed through the Quaternary. Such ecologically stable areas may be critical not only for the long-term survival of species, but also for the emergence of new ones.     

A stable silicon(0) compound with a Si=Si double bond

Dative, or nonoxidative, ligand coordination is common in transition metal complexes; however, this bonding motif is rare in compounds of main group elements in the formal oxidation state of zero. Here, we report that the potassium graphite reduction of the neutral hypervalent silicon-carbene complex L:SiCl4 {where L: is:C[N(2,6-Pri2-C6H3)CH]2 and Pri is isopropyl} produces L:(Cl)Si-Si(Cl):L, a carbene-stabilized bis-silylene, and L:Si=Si:L, a carbene-stabilized diatomic silicon molecule with the Si atoms in the formal oxidation state of zero. The Si-Si bond distance of 2.2294 +/- 0.0011 (standard deviation) angstroms in L:Si=Si:L is consistent with a Si=Si double bond. Complementary computational studies confirm the nature of the bonding in L:(Cl)Si-Si(Cl):L and L:Si=Si:L.     

Hydrocarbon separations in a metal-organic framework with open iron(II) coordination sites

The energy costs associated with large-scale industrial separation of light hydrocarbons by cryogenic distillation could potentially be lowered through development of selective solid adsorbents that operate at higher temperatures. Here, the metal-organic framework Fe(2)(dobdc) (dobdc(4-) : 2,5-dioxido-1,4-benzenedicarboxylate) is demonstrated to exhibit excellent performance characteristics for separation of ethylene/ethane and propylene/propane mixtures at 318 kelvin. Breakthrough data obtained for these mixtures provide experimental validation of simulations, which in turn predict high selectivities and capacities of this material for the fractionation of methane/ethane/ethylene/acetylene mixtures, removal of acetylene impurities from ethylene, and membrane-based olefin/paraffin separations. Neutron powder diffraction data confirm a side-on coordination of acetylene, ethylene, and propylene at the iron(II) centers, while also providing solid-state structural characterization of the much weaker interactions of ethane and propane with the metal.     

Lower pH limit for the existence of blue-green algae: evolutionary and ecological implications

Observations on a wide variety of acidic environments, both natural and man-made, reveal that blue-green algae (Cyanophyta) are completely absent from habitats in which the pH is less than 4 or 5, whereas eukaryotic algae flourish. By using enrichment cultures with inocula from habitats of various pH values, the absence of blue-green algae at low pH was confirmed.     

Decamethyldizincocene, a stable compound of Zn(I) with a Zn-Zn bond

Unlike mercury, which has an extensive +1 oxidation state chemistry, zinc usually adopts the +2 oxidation state. Decamethyldizincocene, Zn2(eta5-C5Me5)2, an organometallic compound of Zn(I) formally derived from the dimetallic [Zn-Zn]2+ unit, has been isolated from the low-temperature (-10 degrees C) reaction of Zn(C5Me5)2 and Zn(C2H5)2 in diethyl ether. X-ray studies show that it contains two eclipsed Zn(eta5-C5Me5) fragments with a Zn-Zn distance (+/- standard deviation) of 2.305(+/-3) angstroms, indicative of a metal-metal bonding interaction.     

Synthesis of a stable compound with fivefold bonding between two chromium(I) centers

Although in principle transition metals can form bonds with six shared electron pairs, only quadruply bonded compounds can be isolated as stable species at room temperature. Here we show that the reduction of {Cr(mu-Cl)Ar'}2 [where Ar' indicates C6H3-2,6(C6H3-2,6-Pri2)2 and Pr indicates isopropyl] with a slight excess of potassium graphite has produced a stable compound with fivefold chromium-chromium (Cr-Cr) bonding. The very air- and moisture-sensitive dark red crystals of Ar'CrCrAr' were isolated with greater than 40% yield. X-ray diffraction revealed a Cr-Cr bond length of 1.8351(4) angstroms (where the number in parentheses indicates the standard deviation) and a planar transbent core geometry. These data, the structure's temperature-independent paramagnetism, and computational studies support the sharing of five electron pairs in five bonding molecular orbitals between two 3d5 chromium(I) ions.     

虾夷扇贝卵巢酶水解产物抗氧化性的研究

利用耐热蛋白酶水解虾夷扇贝Patinopecten yessoensis卵巢,加水分解得到富含多肽的蛋白粉末,测定酶水解产物中残存氧的浓度和对DPPH自由基活性消去的能力。结果表明,酶水解物的产率为17.8%,酶水解物中蛋白质的含量为87.92%;10 g/L虾夷扇贝卵巢酶水解产物能消去DPPH自由基61.68%的活性。试验表明,虾夷扇贝卵巢酶水解物有较好的抗氧化性。     

Spectral sensitivity of the compound eyes of Anomala corpulenta motschulsky(Coleoptera:Scarabaeoidea)

The scarab beetle, Anomala corpulenta Motschulsky(Coleoptera: Scarabaeoidea), is a widespread and destructive pest in China. Vision is one of the most important means of acquiring information about the external environment. In order to contribute to the understanding of the perception of visual stimuli in this species, the light sensitivity and spectral responses of the scarab beetle, A. corpulenta, were measured by using an electroretinogram(ERG) technique. In total, 14 monochromatic light intensities, between 340 and 605 nm, were applied to the compound eyes of A. corpulenta under varying levels of adaptation to dark and light conditions. The results showed that all light stimuli induced an ERG response, with varied amplitudes. The spectral sensitivity curve of dark-adapted eyes showed one major peak(~400 nm; near-ultraviolet), a secondary peak(from 498 to 562 nm; yellow-green) and the third peakat 460 nm. By contrast, in light-adapted eyes, only a near-UV peak was observed. From these results, we conclude that the compound eye of A. corpulenta is likely to have at least three spectral types of photoreceptor. Significance of differences were also recorded in the responses of male and female compound eyes, as well as diurnally and nocturnally. The amplitude of ERG in response to white-light stimuli varied with the light intensity: The stronger the luminance, the higher the ERG value. This suggests that the compound eye of A. corpulenta adapts quickly to changing light conditions, enabling A. corpulenta to maintain nocturnal activities.     

Spectral sensitivity of the compound eyes of Anomala corpulenta motschulsky (Coleoptera: Scarabaeoidea)

The scarab beetle, Anomala corpulenta Motschulsky (Coleoptera: Scarabaeoidea), is a widespread and destructive pest in China. Vision is one of the most important means of acquiring information about the external environment. In order to contribute to the understanding of the perception of visual stimuli in this species, the light sensitivity and spectral responses of the scarab beetle, A. corpulenta, were measured by using an electroretinogram (ERG) technique. In total, 14 monochromatic light intensities, between 340 and 605 nm, were applied to the compound eyes of A. corpulenta under varying levels of adaptation to dark and light conditions. The results showed that all light stimuli induced an ERG response, with varied amplitudes. The spectral sensitivity curve of dark-adapted eyes showed one major peak (~400 nm; near-ultraviolet), a secondary peak (from 498 to 562 nm; yellow-green) and the third peakat 460 nm. By contrast, in light-adapted eyes, only a near-UV peak was observed. From these results, we conclude that the compound eye of A. corpulenta is likely to have at least three spectral types of photoreceptor. Significance of differences were also recorded in the responses of male and female compound eyes, as well as diurnally and nocturnally. The amplitude of ERG in response to white-light stimuli varied with the light intensity: The stronger the luminance, the higher the ERG value. This suggests that the compound eye of A. corpulenta adapts quickly to changing light conditions, enabling A. corpulenta to maintain nocturnal activities.     

Reaction of monosaccharides with proteins: possible evolutionary significance

Measurements were made of the rate of condensation of various monosaccharides with amino groups of hemoglobin to form Schiff base linkages. The reactivity of each sugar was dependent on the extent to which it exists in the open (carbonyl) structure rather than in the ring (hemiacetal or hemiketal) structure. Among the 15 monosaccharides tested, aldoses showed higher reactivities than ketoses. Glucose was the least reactive of the aldohexoses. The emergence of glucose as the primary metabolic fuel may be due in part to the high stability of its ring structure which limits potentially deleterious nonenzymatic glycosylation of proteins.     

Isotope fractionation and atmospheric oxygen: implications for phanerozoic O(2) evolution

Models describing the evolution of the partial pressure of atmospheric oxygen over Phanerozoic time are constrained by the mass balances required between the inputs and outputs of carbon and sulfur to the oceans. This constraint has limited the applicability of proposed negative feedback mechanisms for maintaining levels of atmospheric O(2) at biologically permissable levels. Here we describe a modeling approach that incorporates O(2)-dependent carbon and sulfur isotope fractionation using data obtained from laboratory experiments on carbon-13 discrimination by vascular land plants and marine plankton. The model allows us to calculate a Phanerozoic O(2) history that agrees with independent models and with biological and physical constraints and supports the hypothesis of a high atmospheric O(2) content during the Carboniferous (300 million years ago), a time when insect gigantism was widespread.     

印度谷螟成虫复眼的外部形态及显微结构观察

利用扫描电镜和石蜡切片技术观察研究了印度谷螟[Plodia interpunctella(Hübener)]成虫复眼的外部形态和明暗适应对其内部显微结构的影响.结果显示:(1)该蛾复眼半球形,位于头部两侧,略成“八”字形排列,单个复眼的小眼数约为1 950;(2)每个小眼主要由角膜、晶锥、小网膜细胞柱、视杆和基膜组成,其中角膜、晶锥、小网膜细胞周围环绕着由初级虹膜色素细胞分泌的初级虹膜色素颗粒和由6个次级虹膜色素细胞分泌的次级虹膜色素颗粒,基膜处分布有基膜色素颗粒,且密集的气管穿过基膜进入网膜区;(3)明适应时,大部分次级虹膜色素颗粒向视杆远心端移动,覆盖整个小网膜细胞柱区域;暗适应时,次级虹膜色素颗粒逐渐向晶锥方向聚集,分布在各晶锥周围和小网膜细胞柱的远心端.结果表明:印度谷螟成虫复眼为典型的重叠像眼,其主要通过色素颗粒发生纵向位移来调节对光的吸收,以适应外界光环境的变化.     

乙酰水杨酸稀土在银杏上的应用研究初报

研究结果表明：乙酰水杨酸可使银杏出苗率提高１０个百分点，使幼苗中过氧化物酶、超氧化物歧化酶活性明显提高，丙二醛含量下降，使幼苗株高，茎粗，侧根数和叶片数明显增加，幼苗茎腐病发病率和病情指数降低；产量提高，品质得到明显改善。     

高效液相色谱法测定中西复方制剂中甲砜霉素含量

采用Waters HPLC系统，WatersCl8柱，甲醇：水(30：70)为流动相，检测波长为226nm，对中西复方制剂中的甲砜霉素含量进行测定，该方法快速、简便，分离效果好，中药对甲砜霉素的测定无任何干扰；在5～30μg／ml范围内线性关系良好(r=0．9999)；平均回收率可达99．6％。     

优释多（包膜复合微量）对养殖端的影响及其效果评估

文章阐述优释多(包膜复合微量)在蛋鸡、肉鸡和畜禽养殖中的应用,延长产蛋高峰期,缓解产蛋后期因生理性衰退而出现的蛋壳颜色差、蛋壳质量下降,解决无机矿自身不足等问题,对肉鸡和畜禽具体保健作用,并对产品特点、功效、论证及试验数据进行了全方位的剖析,以期为更好地认识、了解和评估该产品的使用效果提供依据。     

Rapid extinction of the moas (Aves: Dinornithiformes): model, test, and implications

A Leslie matrix population model supported by carbon-14 dating of early occupation layers lacking moa remains suggests that human hunting and habitat destruction drove the 11 species of moa to extinction less than 100 years after Polynesian settlement of New Zealand. The rapid extinction contrasts with models that envisage several centuries of exploitation.