Modeling Lanthanide Complexes: Towards the Theoretical Design of Light Conversion Molecular Devices

Theoretical techniques have been developed and/or improved to predict the molecular structure of lanthanide complexes which were used to calculate their electronic properties, in particular, their electronic spectra and energy levels necessary to calculate the rates of energy transfer from the ligands to the metal ion. The molecular structure has been obtained by the SMLC/AM1 (Sparkle Model for the Calculation of Lanthanide Complexes – Austin Model 1) model where the lanthanide ion is simulated by a sparkle implemented into the AM1 Hamiltonian used to perform a HF-SCF (Hartree-Fock Self-Consistent Field) calculation. The previous implementation of the SMLC/AM1 model (sparkle/1) involving only two parameters has been generalized to be consistent with the AM1 Hamiltonian and the new model (sparkle/2) significantly improved the prediction of molecular structures of Eu(III) complexes. For the electronic spectra and energy level calculations of the lanthanide complexes the model replaces the metal ion by a point charge with the ligands held in their positions as determined by the SMLC/AM1 model, and uses a INDO/S-CI (intermediate neglect of differential overlap/spectroscopic-configuration interaction) model. A preliminary study of the solvent effects on the absorption spectra of the free ligand is also presented. For the ligand-lanthanide ion energy transfer Fermi's golden rule is used with the multipolar and exchange mechanisms being implemented and tested for several complexes. These theoretical techniques have been applied to several complexes yielding very good results when compared to experimental data as well as predictions for the molecular and electronic structures and the relative contributions of the mechanisms for the energy transfer rates. This revised version was published online in June 2006 with corrections to the Cover Date.     

The role of the nicotinamide and adenine subsites in the negative co-operativity of coenzyme binding to glyceraldehyde-3-phosphate dehydrogenase.

The interaction of 3-aminopyridine-adenine dinucleotide, an NAD ⁺ 2 analogue which is fluorescent at the pyridine end of the molecule, with rabbit muscle glyceraldehyde-3-phosphate dehydrogenase was investigated. The fluorescence properties of the AAD⁺ molecule were used to monitor the nicotinamide subsites ou the GPDHase tetramer, the fluorescent aminopyridine moiety of the molecule serving as an intrinsic probe. Although the binding of AAD⁺ wag found to be negatively co-operative, no conformational changes induced at the nicotinamide subsite upon coenzyme binding were found to be transmitted to neighboring subunits. These findings, in conjunction with our earlier findings and with the observation that different NAD⁺ analogues which differ in the chemistry of the pyridine moiety bind with different extents of co-operativity, enable us to offer specific roles for the nicotinamide and the adenine subsites in generating the negative co-operativity.It is suggested that the structure of the pyridine moiety of the coenzyme controls the mode of binding of the pyridine moiety to the nicotinamide subsite. This, in turn, controls the orientation of the adenine moiety with respect to its subsite, thereby determining the mode of the interactions between the adenine and its binding domain. As the propagation of conformational changes caused by these interactions to neighboring subunits is believed to be the cause of the negative co-operativity exhibited by this enzyme towards coenzyme binding, the structure of the pyridine moiety controls this phenomenon.     

涉及光疗机制的生物光化学

本文对光生物和光化学的定义,反应机制的类型和光敏化作用等做了阐述。下面例举几个光疗的成果 1.光疗牛皮癣 经常使用的8-甲氧基补骨脂素在UVA的照射下,从基态被激发到三重态。它主要和DNA中的胸腺嘧啶,其次和色氨酸进行光环合加成,形成交联,阻止DNA和RNA的合成,抑制具过度增生 2.血卟啉衍生物(HPD)治癌 HPD有定位于癌组织的能力和光动力作用,可推断病人体内癌部位。 讨论了HPD的光疗机制,和酞菁相比,有各自的优缺点。 3.竹红菌素 主要治疗妇女外阴白色病变和疤痕疙瘩,抑制癌细胞生长。 讨论了竹红菌甲素和乙素及它们的氧化物的结构和活性。 在大于510nm的光照射下,也可抑制癌细胞的生长。列举了竹红菌素的优缺点。     

Extraction and analysis of superoxide free radicals (·O−2) from whole mammalian liver

Extraction of whole lobes of normal rat liver with dimethyl sulphoxide (DMSO) under N₂ gives extracts which contain 5—10 μmol/l·O^?₂ (50-100 nmol·O^?₂ per 10 ml extract per 4 g liver; 1.25-2.50 nmol·O^?₂ per millilitre per gram liver). Evidence for ·O^?₂ in the extracts is given by: (1) electron spin resonance signals (ESR), (2) differential pulse polarography (DPP), (3) chemiluminescence (CL), and (4) nitroblue tetrazolium reduction (NBT). All tests yield results identical with those obtained with authentic ·O^?₂. Extraction of ·O^?₂ is enhanced by tetrabutyl ammonium ion, and is maximal at 1-3 min. These results raise the possibility that substantial amounts of ·O^?₂ are normally sequestered in protective membranous sites in vivo.     

Cone penetrometer testing,hydropunch®, and borehole geophysics applications for environmental investigations

An effective groundwater monitoring system can be implemented by the combined utilization of cone penetrometer (CPT), HydroPunch^® sampling, and borehole geophysical methods. The combined techniques provide a cost‐effective method for the design of a groundwater monitoring system for geologists or hydrogeologists assessing a site. With the relatively high costs associated with determining groundwater quality for site assessments, coupled with regulatory agency compliance, these combined methods can provide an effective edge in an increasingly competitive environmental industry. CPT combined with HydroPunch sampling can delineate the horizontal and vertical extent and concentration of a contaminant plume, define the extent and thickness of a free product plume, define soil and aquifer characteristics, and aid in the proper selection of well location and screen placement. The use of borehole geophysics further enhances the interpretation provided from the CPT. The interpretation of borehole geophysics provides additional information about the deposition regime of the area of investigation and a more detailed investigation of the stratigraphy. The CPT and HydroPunch can be used in unconsolidated sediments, and HydroPunch sampling can be combined with a hollow‐stem auger system. Borehole geophysics can be run in almost any environment. CPT and borehole geophysics provide information on specific lithologic characteristics necessary to obtain a groundwater sample from vertically separated aquifers. The HydroPunch can obtain a discrete, chemically representative groundwater sample from the targeted aquifer. CPT and borehole geophysics can also be used to determine lithology and for correlation of equivalent stratas from one borehole or well to the next. Borehole geophysical interpretation also provides a means of determining not only the stratigraphy and lithology but also the aquifer parameters and the type of fluids in the aquifer. Hydrogeologic and geologic data obtained from using these three methods can be employed to maximize the cost‐effectiveness and design efficiency of a groundwater monitoring system. Proper location of wells and screened interval placements are determined by a coherent design process rather than by random chance. Two studies demonstrating the combined applications of CPT, HydroPunch, and borehole geophysics for the design and placement of groundwater monitoring wells are presented in the following discussion.     

Community structure and abundance of insects in response to early‐season aphid infestation in wild cabbage populations

1. Changes in the arthropod community structure can be attributed to differences in constitutively expressed plant traits or those that change depending on environmental conditions such as herbivory. Early‐season herbivory may have community‐wide effects on successive insect colonisation of host plants and the identity of the initially inducing insect may determine the direction and strength of the effects on the dynamics and composition of the associated insect community. 2. Previous studies have addressed the effect of early infestation with a chewing herbivore. In the present study, the effect of early infestation was investigated with a phloem‐feeding aphid [Brevicoryne brassicae L. (Hemiptera, Aphididae)] on the insect community associated with three wild cabbage (Brassica oleracea L.) populations, which are known to differ in defence chemistry, throughout the season in field experiments. 3. Aphid infestation had asymmetric effects on the associated insect community and only influenced the abundance of the natural enemies of aphids, but not that of chewing herbivores and their natural enemies. The effect size of aphid infestation further depended on the cabbage population. 4. Aphid feeding has been previously reported to promote host‐plant quality for chewing herbivores, which has been attributed to antagonism between the two major defence signalling pathways controlled by the hormones salicylic acid (SA) and jasmonic acid (JA), respectively. Our results show no effects of early infestation by aphids on chewing herbivores, suggesting the absence of long‐term JA–SA antagonism. 5. Investigating the effects of the identity of an early‐season coloniser and genotypic variation among plant populations on insect community dynamics are important in understanding insect–plant community ecology.     

Positive indirect effect of aquatic insects on terrestrial prey is not offset by increased predator density

1. Changes in one prey species' density can indirectly affect the abundance of another prey species if a shared predator eats both species. Sometimes, indirect effects occur when prey straddle habitats, including when riparian predator populations grow in response to emergent aquatic insects and increase predation on terrestrial prey. However, predators may largely switch to aquatic insects or become satiated, reducing predation on terrestrial prey. 2. To determine the net indirect effect of aquatic insects on terrestrial arthropods via generalist spider predators, a field experiment was conducted mimicking midge influx and a wolf spider numerical response inside enclosures near an Icelandic lake. Lab mesocosms were also used to assess per capita rates of spider predation u nder differing levels of midge abundance. 3. Midges always decreased sentinel prey predation, but this effect increased with predator density. When midges were absent, predation increased 30% at a high spider density, but predation was equal between spider treatments when midges were present. In situ arthropods showed no effect of midge or spider treatments, although non‐significant abundance patterns were observed congruent with sentinel prey results. 4. In lab mesocosms, prey survivorship increased ≥50% where midges were present and rapidly saturated; the addition of 5, 20, 50, and 100 midges equivalently reduced spider predation, supporting predator distraction rather than satiation as the root cause. 5. The present results demonstrate a strong positive indirect effect of midges and broadly support the concept that predator responses to alternative prey are a major influence on the magnitude and direction of predator‐mediated indirect effects.     

Characterization of six microsatellite markers in Trillium camschatcense using a dual‐suppression‐polymerase chain reaction technique

Trillium camschatcense is a herbaceous perennial plant distributed in Hokkaido and northern Honshu, Japan. Geographical variations in the breeding system (partial selfing or obligate outcrossing) are reported in the populations of Hokkaido. We isolated six polymorphic microsatellite loci from this species. The number of allele per locus ranged from four to 12, whereas the expected heterozygosities ranged from 0.69 to 0.83. These markers may allow further investigations to reveal the evolutionary and ecological processes of mating system in T. camschatcense.