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.     

川中丘陵区冬灌田甲烷和氧化亚氮排放研究

采用静态暗箱/气相色谱法对川中丘陵区冬灌田CH₄和N₂O排放特征进行连续一年的田间原位测定.结果表明,种植水稻区(种植区)在水稻生长季平均CH₄排放速率为22.76±2.76 mg·m^-2·h^-1,休闲期平均为1.43±0.20 mg·m^-2·h^-1,全年平均为9.64±1.17 mg·m^-2·h^-1;全年CH₄排放主要集中在水稻生长季,其累计CH₄排放量占全年总CH₄排放量的91.2%未种植水稻区(对照区) 全年CH₄平均排放速率为2.03±0.18 mg·m^-2·h^-1,水稻生长季CH₄排放量占全年总排放量的86.2%.N₂O的排放在稻田落干时呈现脉冲排放.在水稻生长季,对照区CH₄和N₂O的季节排放速率分别为4.53±0.38mg·m^-2·h^-1和32.01±5.02 μg·m^-2·h^-1,而种植区则分别为22.76±2.76 mg·m^-2·h^-1和73.04±5.03 μg·m^-2·h^-1,植株参与导致CH₄和N₂O排放速率分别增加302%和128%.CH₄和N₂O的排放随土水分条件的变化呈互为消长关系.在冬灌田中,即使考虑500年的时间尺度,全年N₂O排放产生的全球增温潜势也只有CH₄的7.9%,与CH₄相比,冬灌田排放的N₂O所产生的温室效应很小.     

Overview of the biogenic sources of atmospheric trace compounds due to agricultural activities

All human activities profoundly affect the chemical composition and properties of the atmosphere. The present overview highlights the impact of agricultural practices, including livestock raising, on the biogeochemical cycles of carbon and nitrogen and discusses the relevant environmental issues. Emissions from agriculture significantly contribute to the atmospheric budget of methane and nitrous oxide, which in turn contribute to the greenhouse effect. Agricultural activities are also the predominant source of ammonia to the atmosphere, so affecting the acidity of atmospheric depositions. A minor role is expected from agriculture in the production of tropospheric ozone through nitrogen oxides and volatile organic compound emissions.     

Consequences of the Ban of By-Products from Terrestrial Animals in Livestock Feeding in Germany and The European Union: Alternatives,Nutrient and Energy Cycles,Plant Production,and Economic Aspects

Consequences of the ban of meat and bone meal (MBM) and animal fat with regard to livestock feeding, cropping, ecology and economy where investigated with an inter-disciplinary approach for Germany and the European Union. Calculations were made for different production systems with pigs and poultry on the basis of statistical data for the production and for the feed markets as well as from requirement data for the respective species and production system. (1.) The ban of MBM from feeding caused a need for alternative protein sources. If all the amount of protein from MBM is to be replaced by soybean meal, in Germany and the EU about 0.30 and 2.30 · 10⁶t would be needed each year (supplementary amino acids not considered). Alternatively, doubling the grain legume acreage in Germany to about 420,000ha would supply a similar amount of protein. A wider application of phase feeding with adjusted dietary amino acid concentrations, however, would allow for saving protein to an extent which is similar to the amount of protein that was contributed by MBM in recent years. Thus, the ban is a minor problem in terms of ensuring amino acid supply. (2.) However, alternative plant ingredients cannot compensate for the gap in P supply that is caused by the ban. An additional demand for inorganic feed phosphates of about 14,000 and 110,000t per year is given in Germany and the EU, respectively. So far, this gap is filled almost completely by increased mining of rock phosphates. Alternatively, a general application of microbial phytase to all diets would largely fill this gap. Until the ban, MBM contributed to 57% of the supplementation of P that was needed for pigs and poultry. The ban of MBM makes large amounts of P irreversibly disappearing from the food chain. (3.) Energy from slaughter offal and cadavers can be utilized in different technologies, in the course of which the efficiency of energy utilisation depends on the technology applied. It is efficient in the cement work or rotation furnace if heat is the main energy required. In contrast, the energetic efficiency of fermentation is low. (4.) Incineration or co-incineration of MBM and other by-products causes pollution gas emissions amounting to about 1.4kg CO₂ and 0.2kg NO_x per kg. The CO₂ production as such is hardly disadvantageous, because heat and electrical energy can be generated by the combustion process. The prevention of dangerous gaseous emissions from MBM burning is current standard in the incineration plants in Germany and does not affect the environment inadmissibly. (5.) The effects of the MBM ban on the price for compound feed is not very significant. Obviously, substitution possibilities between different feed ingredients helped to exchange MBM without large price distortions. However, with each kg MBM not used in pig and poultry feeding economic losses of about 0.14¢ have to considered. In conclusion, the by far highest proportion of raw materials for MBM comes as by-products from the slaughter process. Coming this way, and assuring that further treatment is safe from the hygienic point of view, MBM and animal fat can be regarded as valuable sources of amino acids, minerals and energy in feeding pigs and poultry. Using them as feedstuffs could considerably contribute to the goal of keeping limited nutrients, phosphorus in particular, within the nutrient cycle and dealing responsible with limited resources.     

Synthesis and properties of Asante Calcium Red—A novel family of long excitation wavelength calcium indicators

Although many synthetic calcium indicators are available, a search for compounds with improved characteristics continues. Here, we describe the synthesis and properties of Asante Calcium Red-1 (ACR-1) and its low affinity derivative (ACR-1-LA) created by linking BAPTA to seminaphthofluorescein. The indicators combine a visible light (450–540 nm) excitation with deep-red fluorescence (640 nm). Upon Ca²⁺ binding, the indicators raise their fluorescence with longer excitation wavelengths producing higher responses. Although the changes occur without any spectral shifts, it is possible to ratio Ca²⁺-dependent (640 nm) and quasi-independent (530 nm) emission when using visible (<490 nm) or multiphoton (∼780 nm) excitation. Therefore, both probes can be used as single wavelength or, less dynamic, ratiometric indicators. Long indicator emission might allow easy [Ca²⁺]_i measurement in GFP expressing cells. The indicators bind Ca²⁺ with either high (K_d = 0.49 ± 0.07 μM; ACR-1) or low affinity (K_d = 6.65 ± 0.13 μM; ACR-1-LA). Chelating Zn²⁺ (K_d = 0.38 ± 0.02 nM) or Mg²⁺ (K_d ∼ 5 mM) slightly raises and binding Co²⁺ quenches dye fluorescence. New indicators are somewhat pH-sensitive (pK_a = 6.31 ± 0.07), but fairly resistant to bleaching. The probes are rather dim, which combined with low AM ester loading efficiency, might complicate in situ imaging. Despite potential drawbacks, ACR-1 and ACR-1-LA are promising new calcium indicators.     

Overview of the biogenic sources of atmospheric trace compounds due to agricultural activities

All human activities profoundly affect the chemical composition and properties of the atmosphere. The present overview highlights the impact of agricultural practices, including livestock raising, on the biogeochemical cycles of carbon and nitrogen and discusses the relevant environmental issues. Emissions from agriculture significantly contribute to the atmospheric budget of methane and nitrous oxide, which in turn contribute to the greenhouse effect. Agricultural activities are also the predominant source of ammonia to the atmosphere, so affecting the acidity of atmospheric depositions. A minor role is expected from agriculture in the production of tropospheric ozone through nitrogen oxides and volatile organic compound emissions.     

Investigation on Emission of Nitrous Oxide by Aseptic Soybean Plant

The emission of nitrous oxide is not only a way of nitrogen loss in ecological system of agriculture, it is also a contamination source of increasing nitrogen oxide concentration in the atmosphere. This paper reports the analysis of gas chromatographic determination of N2O on the soybean plant and its different four organs-root, stem, leaf and cotyledon under strict aseptic condition. The results showed ,hat they all are able to emit nitrous oxide.     

Correlation of structure and emission in solid state copper(I) complexes; [Cu4I4(CH3CN)2(L)2], L = aniline derivative

Four complexes of the type [Cu₄I₄(CH₃CN)₂(L)₂], L = aniline derivative: Cu₄I₄(CH₃CN)₂(2,6-dimethylaniline)₂ (I), triclinic, , a = 12.449(3), B = 14.108(6), C = 10.606(4) Å, = 73.46(3), β = 95.00(2), γ = 73.42(3)°, V = 1682.3(10) ų; Cu₄I₄(CH₃CN)₂(o-ethylaniline)₂ (II), triclinic,

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, V = 1734.0(8) ų; Cu₄I₄(CH₃CN)₂(6-ethyl-o-toluidine)₂ (III), orthorhombic, Pnam, a = 14.976(6), b = 21.187(6), C = 12.545(2) Å, V = 3980.7(2) ų; Cu₄I₄(CH₃CN)₂(p-anisidine)₂ (IV), monoclinic, A2/a, A = 20.032(10), B = 7.863(1), C = 18.715(9) Å, β = 101.56(4)°, V = 2888.0(2) ų; were examined by single crystal X-ray diffraction. Complexes I and II have no internal symmetry elements, III has an internal mirror and IV has a two-fold axis. Ab initio calculations based on the atomic positional parameters of complexes containing the three types of symmetry elements reveal HOMO orbitals to be dominated by the p orbitals of the iodine atoms whereas the LUMO orbitals contain major contributions from copper based p orbitals.     

Melittin-phospholipid interaction studied by employing the single tryptophan residue as an intrinsic fluorescent probe

The rotational correlation time of melittin, obtained from the nanosecond anisotropy of the emission from its single tryptophan residue, has been found to increase considerably in phosphate solution relative to that in aqueous solution, consistent with protein aggregation. The steady-state fluorescence spectra as well as the absorption spectra in phosphate solution exhibit a very good degree of similarity with those of the protein bound to egg phosphatidylcholine (PC) and distearoylphosphatidylcholine (DSPC) bilayer liposomes. The value of the second-order rate constant for dynamic quenching, $\text{k}{}_{\mathrm{<mtext>q</mtext>}}\text{= 1.4·10}{}^9\text{M}{}^{\mathrm{?1}}\text{·}\text{s}{}^{\mathrm{?1}}$, by acrylamide in 0.5 M phosphate solution is comparable to those for the protein-phospholipids complexes (1·10⁹ and 0.7·10⁹ M^?1·s^?1 for egg PC and DSPC, respectively). Similarities are also found in the nanosecond properties. There is a much stronger and quite similar dependence of the fluorescence spectra on time in the nanosecond range and of the fluorescence decay times on the emission wavelength in both cases as compared to the case in aqueous solution. These observations support the notion that melittin binds to the phospholipids in an aggregated form. The results suggest that the reduction in the $\text{k}{}_{\mathrm{<mtext>q</mtext>}}$ values of bound melittin relative to that in aqueous solution and the blue shift of the fluorescence spectrum (from 352 to 337 nm) are brought about by shielding of the tryptophan residue from the solvent through a combination of protein aggregation and enhancement of its α-helical content (suggested by published CD data). The magnitude of the $\text{k}{}_{\mathrm{<mtext>q</mtext>}}$ values for bound melittin, however, is still relatively high implying the occurrence of rather frequent encounters between the tryptophan residue and the hydrophilic acrylamide molecules. Thus, the residue is found not to penetrate deep into the phospholipid bilayer.     

High resolution emission spectra of one second delayed fluorescence from chloroplasts

The first well resolved emission spectra of white light-illuminated spinach chloroplasts at room temperature show that one second delayed fluorescence occurs at 685 nm. We demonstrate that reabsorption of this delayed fluorescence induces the second (probably prompt) emission observed at 730 nm and which we identify with the photosystem I peripheral antenna system.