Cationic induced assembly of two 2D zinc-terephthalate polymeric networks

Based on templates of [Ph₃PCH₂Ph]Cl and [Ph₄P]Cl ([Ph₃PCH₂Ph] = benzyltriphenylphosphonium, [Ph₄] = tetraphenylphosphonium), the hydrothermal reactions of zinc acetate dihydrate, H₂tp (tp = terephthalate) and water give rise to two new zinc-terephthalate coordination polymers, [Ph₃PCH₂Ph][Zn(tp)Cl] (1) and [Ph₄P][Zn(tp)(H₂O)₂·0.5tp] (2). X-ray single-crystal structural analysis reveals that both 1 (C₃₃H₂₆ClO₄PZn) and 2 (C₃₆H₃₀O₈PZn) crystallize in the 2D non-interpenetrating layered supramolecular networks with guest organophosphonium cations. Due to template effect of different guest cations, 1 presents an interesting 2D smectite-like lamellar framework that formed by the 4-linked (4,4) anionic zinc-terephthalate polymeric network and the interlayer [Ph₃PCH₂Ph]⁺ exchangeable cations, while 2 shows a 2D 3-linked (6,3) H-bonded anionic zinc-terephthalate polymeric brickwall network with encapsulated guest [Ph₄P]⁺ cations. Both compounds are stable up to about 300 °C, and exhibit intense fluorescent emission band at 446 nm (λ_exc = 328 nm) for 1 and 420 nm (λ_exc = 340 nm) for 2 in the solid state at room temperature.     

Microwave synthesis, spectroscopy, thermal analysis and crystal structure of an one-dimensional polymeric {[Cu(4,4′-bipy)(H2O)3(SO4)] · 2H2O}n complex

A metal organic-inorganic coordination framework formulated as {[Cu(4,4′-bipy)(H₂O)₃(SO₄)] · 2H₂O}_n (1) (where 4,4′-bipy = 4,4′-bipyridine) has been successfully prepared by microwave synthesis. The title complex has been characterized by single crystal X-ray crystallography, FT-IR spectroscopy and thermal analysis. Complex (1) is an one-dimensional (1D) polymer in which 4,4′-bipy acts as a bridging ligand supporting the formation of infinite [Cu(4,4′-bipy)(H₂O)₃(SO₄)] chains. The packing diagram shows that a 3D network is formed via hydrogen bonds. The infrared spectra and thermographic data are consistent with the chemical formula.     

Self-assembly of 2D zinc metal-organic frameworks based on mixed organic ligands

Self-assembly of Zn(NO₃)₂·6H₂O, 5-amino-2,4,6-triiodoisophthalic acid (H₂atiip) and 4,4′-bipyridine (bpy) or 1,3-di(4-pyridyl)propane (dpp) gave rise to three unusual zinc metal-organic frameworks, Zn₂(bpy)₂(atiip)₂·3H₂O·2dmf (1), Zn₈(dpp)₈(atiip)₈·4H₂O (2), Zn(dpp)(atiip)·(dmf)·(H₂O) (3). All complexes possess 2D layer frameworks constructed from 1D Zn-carboxylate tubular unit for 1, 1D Zn-carboxylate helical chain for 2 and 3. In 1 and 2, the bpy or dpp act as both bridging and blocking ligands and the blocking ligands play an important role in the formation of the 2D layer frameworks. Both 2 and 3 contain two different large metallomacrocycles. Photoluminescence measurements of 1-3 in the solid state at room temperature show that all complexes exhibit luminescence, which can be assigned to an intraligand π → π^∗ transition or ligand-to-metal charge transfer (LMCT).     

Bottom-up derivation of discrete-time population models with the Allee effect

This paper presents a framework in which various single-species discrete-time population models exhibiting the Allee effect are derived from first principles. Here, the Allee effect means a reduction in individual fitness at low population sizes. The derivation is based on the distribution of female and male individuals among discrete resource sites, in addition to competitive and cooperative interaction among individuals. These derivations show how the derived population models depend on the type and the intensity of competition, and the degree of clustering of individuals. Along with these models exhibiting the Allee effect, this paper also presents first-principles derivation of population models without the Allee effect which include a parameter relating to the intensity of competition.     

中国旧石器文化的“西方元素”与早期人类文化进化格局

本文回顾和分析中国旧石器研究史上有关"西方元素"即西方旧石器文化标志性技术和工具问题的争论,得出三点结论:1)"西方元素"在中国旧石器文化中是与西方同类技术和工具大体同步出现的客观现象,两者无本质差别;2)和西方一样,中国旧石器的"西方元素"也有重叠与穿时性.这使得旧大陆两侧的旧石器文化连成一体,难分东西;3)基于以上事实,本文作者倾向于认为:迄今已知的旧大陆旧石器文化是过去200多万年间早期人类在进化过程中应对全球气候波动引起的生态环境变迁而反复进行的横贯大陆的双向迁移、交流与融合的结果.     

Long-term recovery of macroinvertebrate biota in grossly polluted streams: Re-colonisation as a constraint to ecological quality

To meet targets imposed by the European Water Framework Directive (2000/60/EC) it is vital that measures to improve the status of rivers are both effective and economically viable. Achievement of such aims needs robust understanding of biological responses to changes in water quality vis-à-vis mechanisms of and constraints to the colonization of previously polluted sites. This study therefore examined the long-term chemical and biological changes in historically polluted rivers to elucidate the responses of macroinvertebrate biota to improvements in chemical water quality. For three historically polluted sites in the English Midlands, data from surveys over a period of ca. 50 years were analysed. Ammonia (NH₃) and 5-day biochemical oxygen demand (BOD₅) were used as chemical water quality indicators. Variations in the ecological recovery of the study sites were assessed using an average pollution sensitivity score (Average Score Per Taxon) and the number of taxa present (usually to family level) present in hand-net samples. Ecological recovery varied widely and was influenced by the intensity and spatial extent of the pollution and the proximity of available sources of potential colonisers. At the site most isolated from potential sources of colonizing taxa, no clean-water macroinvertebrate taxa were recorded 30 years after the major sources of pollution ceased. Where clean-water colonisers were more readily available, significant improvements in ecological quality followed within 2–5 years of the improvements in chemical quality. Macroinvertebrate communities and hence monitoring data may thus be indicative of long past conditions or of biological isolation rather than contemporaneous chemical conditions. Combined chemical and biological data were used to explore a generic model for predicting recovery rates and success. Neither BOD₅ nor NH₃ were found to provide a consistent and meaningful prediction of either average pollution tolerance of macroinvertebrate taxa or of the number of taxa present. Long-term relationships between macroinvertebrate variables and chemical water quality variables, however, were non-linear, suggesting that water quality thresholds may have to be exceeded before biological recovery can occur. Even when chemical water quality has been improved substantially, the apparent ecological status of macroinvertebrate communities may not reflect reduced pollution levels attained until adequate time to allow for re-colonisation (possibly decades) has elapsed.     

Can we measure ecological sustainability? Landscape pattern as an indicator for naturalness and land use intensity at regional,national and European level

European landscapes have been shaped over the centuries by processes related to human land use, which are reflected in regionally distinct landscape patterns. Since landscape pattern has been linked to biodiversity and other ecological values of the landscapes, this paper explores landscape pattern as a tool for ecological sustainability assessments at the regional (Austrian Cultural Landscapes), national (Austria) and European (European Union + Norway, Switzerland) level with focus on agricultural landscapes. A set of landscape metrics served as a basis to assess naturalness and geometrisation of Austrian and European landscapes as a proxy for their sustainability. To achieve an accurate spatially explicit assessment, we applied a spatial reference framework consisting in units that are homogeneous in biophysical and socio-economic contexts, adapted the regional approach for its application at European level, and developed relative sustainability thresholds for the landscape metrics. The analyses revealed that several landscape metrics, particularly the “Number of Shape Characterising Points” showed a high correlation with the degree of naturalness. The sustainability map of Austria based on an ordinal regression model revealed well-known problem regions of ecological sustainability. At the European level, the relative deviation from the average pattern showed clearly the simplification processes in the landscapes. However, a better spatial resolution of land cover data would add to the refinement of pattern analysis in regions and therefore the assessment of sustainability. We recommend the combination of information of different scales for the formulation and implementation of sustainability policies.     

Impacts of human activity on environment in the high-cold pasturing area: A case of Gannan pasturing area

Identifying the specific forces driving environmental impact is a hot topic in the field of sustainable development in the pasturing area. In the paper, the ecological footprint was taken as the index of environmental impact, and a series of index like population quality, prosperous, using intensity, livelihood tactics are considered as the main human factors. Using the STIRPAT model and temporal series data from 1980 to 2007, the author analyzes the effects of the human driving forces of environmental impact.
The ecological footprint method presents a simple framework for national natural capital accounting, and it has been used as a comprehensive index of human activity impact, which indirectly reflect human activity’s pressure on the environment. Our analyses showed that the ecological footprint increased from 238736.9 to 877716.1 ha and per capital ecological footprint also increased from 0.854 to 1.961 ha/per during 1980–2007 in Gannan pasturing area. However, in the meantime, the ecological footprint intensity was inclined from 25.396 to 3.025 ha/ten thousand yuan.
With a view of dismantling the human driving forces of ecological footprint, the modified IPAT-called STIRPAT has been employed as a common analytic framework. Our analyses showed that population quantity and using intensity was a major driver of ecological footprint, their coefficients were greater than 1.0 in model (1); In addition, promoting the prosperous lever and the primary industry proportion, the impact of environment will be increased, but their coefficients are less than 1.0 in model (1). At the same time, the technological eco-efficiency of sample regions was discussed in details, the range ability of the technological eco-efficiency was wider, and 15 years went beyond the average level, but the other was less than the average level. Another important finding in the empirical study is that there are some evidences of an environmental Kuznets curve for ecological footprint within the range of calculated data. Some potential improvements in some further researches and suggestions to alleviate the environment pressure, and it is put forward in the last section.     

New yttrium(III) and copper(II) coordination polymers with partially protonated cyclohexane-1,2,3,4,5,6-hexacarboxylato ligands: Synthesis, crystal structures and properties

Two coordination polymers, [Y(H₂O)₄(H₃chhc)]·6H₂O (1) and [Cu₅(H₂O)₁₀(Hchhc)₂]·4H₂O (2) with H₆chhc = cyclohexane-1,2,3,4,5,6-hexacarboxylic acid) represent rare examples of metal complexes with partially protonated cyclohexane-1,2,3,4,5,6-hexacarboxylato ligands. The [Y(H₂O)₄]³⁺ units in 1 are interlinked by the triprotonated (H₃chhc)³⁻ anions in a η⁵μ₄ bridging mode to form 2D (4³)₂(4⁶·6⁶·8³) topological networks, which are stacked along [0 1 0] direction in ···ABAB··· fashion with the lattice H₂O molecules sandwiched between layers. The pentameric [Cu₅(H₂O)₁₀]¹⁰⁺ units in 2 are bridged by monoprotonated (Hchhc)⁵⁻ anions in a η⁸μ₆ fashion to generate a 3D MOF of an unprecendented (4³)(4⁵·6⁷·8³) topology with the lattice H₂O molecules in channels. The temperature-dependent magnetic susceptibility data of 2 could be modeled to a combination of a linear chain of equally-spaced Cu(II) ions (J₁ = 1.86 cm⁻¹) with an isosceles triangular Cu₃ unit (J₂ = 5.86 cm⁻¹).