Amazon forest structure generates diurnal and seasonal variability in light utilization.

The complex three-dimensional (3-D) structure of tropical forests generates a diversity of light environments for canopy and understory trees. Understanding diurnal and seasonal changes in light availability is critical for interpreting measurements of net ecosystem exchange and improving ecosystem models. Here, we used the Discrete Anisotropic Radiative Transfer (DART) model to simulate leaf absorption of photosynthetically active radiation (lAPAR) for an Amazon forest. The 3-D model scene was developed from airborne lidar data, and local measurements of leaf reflectance, aerosols, and PAR were used to model lAPAR under direct and diffuse illumination conditions. Simulated lAPAR under clear-sky and cloudy conditions was corrected for light saturation effects to estimate light utilization, the fraction of lAPAR available for photosynthesis. Although the fraction of incoming PAR absorbed by leaves was consistent throughout the year (0.80?0.82), light utilization varied seasonally (0.67?0.74), with minimum values during the Amazon dry season. Shadowing and light saturation effects moderated potential gains in forest productivity from increasing PAR during dry-season months when the diffuse fraction from clouds and aerosols was low. Comparisons between DART and other models highlighted the role of 3-D forest structure to account for seasonal changes in light utilization. Our findings highlight how directional illumination and forest 3-D structure combine to influence diurnal and seasonal variability in light utilization, independent of further changes in leaf area, leaf age, or environmental controls on canopy photosynthesis. Changing illumination geometry constitutes an alternative biophysical explanation for observed seasonality in Amazon forest productivity without changes in canopy phenology.

Predicting water permeability in sedimentary rocks from capillary imbibition and pore structure

In this paper, absolute water permeability is estimated from capillary imbibition and pore structure for 15 sedimentary rock types. They present a wide range of petrographic characteristics that provide degrees of connectivity, porosities, pore size distributions, water absorption coefficients by capillarity and water permeabilities. A statistical analysis shows strong correlations among the petrophysical parameters of the studied rocks. Several fundamental properties are fitted into different linear and multiple expressions where water permeability is expressed as a generalized function of the properties. Some practical aspects of these correlations are highlighted in order to use capillary imbibition tests to estimate permeability. The permeability–porosity relation is discussed in the context of the influence of pore connectivity and wettability. As a consequence, we propose a generalized model for permeability that includes information about water fluid rate (water absorption coefficient by capillarity), water properties (density and viscosity), wetting (interfacial tension and contact angle) and pore structure (pore radius and porosity). Its application is examined in terms of the type of pores that contribute to water transport and wettability. The results indicate that the threshold pore radius, in which water percolates through rock, achieves the best description of the pore system. The proposed equation is compared against Carman–Kozeny's and Katz–Thompson's equations. The proposed equation achieves very accurate predictions of the water permeability in the range of 0.01 to 1000 mD.

Size effect on the tensile strength of fine-grained copper

We considered the effect of the thickness of copper sheet on its tensile strength. A model in which the strength of surface grains is governed by dislocation image forces, while that of interior grains is determined by dislocation cell structure, was proposed. Using a rule of mixtures, the dependence of strength on the specimen thickness was calculated. A master curve representing the calculated dependence of normalized strength on the ratio of sheet thickness to grain size was confirmed by experiment.

Synthesis, structure and spectral properties of dithiocarbamato bridged dirhenium(III,II) complexes: a combined experimental and theoretical study

Sodium salts of dimethyldithiocarbamate, diethyldithiocarbamate and pyrrolidinedithiocarbamate react with the multiply bonded paramagnetic dirhenium(III,II) complex Re₂(μ-O₂CCH₃)Cl₄(μ-dppm)₂, 1 (dppm = Ph₂PCH₂PPh₂) in refluxing ethanol to afford the paramagnetic substitution products of the type Re₂(η²-S,S)₂(μ-S,S)(μ-Cl)₂(μ-dppm), where S,S represents the dithiocarbamato ligands [S,S = S₂CNMe₂, 4(L_Me); S₂CNEt₂, 4(L_Et) and S₂CN(CH₂)₄, 4(L_Pyr)]. These are the first examples of dirhenium complexes that contain bridging dithiocarbamato ligand along with the dppm ligand. These complexes have very similar spectral (UV-Vis, IR, EPR) and electrochemical properties which are also reported. The identity of 4(L_Et) has been established by single-crystal X-ray structure determination (Re-Re distance 2.6385 (9) Å) and is shown to have edge-shared bioctahedral structure. The electronic structure and the absorption spectra of the complexes are scrutinized by the density functional theory (DFT) and time-dependent density functional theory (TD-DFT) analyses.

Mechanisms of Chloroperoxidase-catalyzed Enantioselective Reactions as Probed by Site-directed Mutagenesis and Isotopic Labeling

Chloroperoxidase (CPO) is a heme-containing glycoprotein secreted by the marine fungus Caldariomyces fumago. Chloroperoxidase contains one ferriprotoporphyrin IX prosthetic group per molecule and catalyzes a variety of reactions, such as halogenation, peroxidation and epoxidation. The versatile catalytic activities of CPO coupled with the increasing demands for chiral synthesis have attracted an escalating interest in understanding the mechanistic and structural properties of this enzyme. In order to better understand the mechanisms of CPO-catalyzed enantioselective reactions and to fine-tune the catalytic properties of chloroperoxidase, asparagine 74 (N74) located in the narrow substrate access channel of CPO was replaced by a bulky, nonpolar valine and a polar glutamine using site-directed mutagenesis. The CPO N74 mutants displayed significantly enhanced activity toward nonpolar substrates compared to wild-type CPO as a result of changes in space and polarity of the heme distal environment. More interestingly, N74 mutants showed dramatically decreased chlorination and catalase activity but significantly enhanced epoxidation activity as a consequence of improved kinetic perfection introduced by the mutation as reflected by the favorable changes in kcat and kcat/KM of these reactions. It is also noted that the N74V mutant is capable of decomposing cyanide, the most notorious poison for many hemoproteins, as judged by the unique binding behavior of N74V with potassium cyanide. Histidine 105 (H105) was replaced by a nonpolar amino acid alanine using site-directed mutagenesis. The CPO H105 mutant (H105A) displayed dramatically decreased chlorination and catalase activity possibly because of the decreased polarity in the heme distal environment and loss of the hydrogen bonds between histidine 105 and glutamic acid 183. However, significantly increased enantioselectivity was observed for the epoxidation of bulky styrene derivatives. Furthermore, my study provides strong evidence for the proposed histidine/cysteine ligand switch in chloroperoxidase, providing experimental support for the structure of the 420-nm absorption maximum for a number of carbon monoxide complexes of heme-thiolate proteins. For the NMR study, [dCPO(heme)] was produced using 90% deuterated growth medium with excess heme precursors and [dCPO(Phe)] was grown in the same highly deuterated medium that had been supplemented with excess natural phenylalanine. To make complete heme proton assignments, NMR spectroscopy has been performed for high-resolution structural characterization of [dCPO(heme)] and [dCPO(Phe)] to achieve unambiguous and complete heme proton assignments, which also allows important amino acids close to the heme active center to be determined.

Structure–property relationships of elementary bamboo fibers

Natural fibers are promising alternatives to synthetic fibers because of their sustainability, low environmental footprint and specific properties desirable for a wide range of technical engineering applications. The industrial implementation of fine grade natural bamboo fibers, including technical (100–200 microns) and elementary fibers (<30 microns) has been of increasing interest in recent times because these fibers offer a unique set of properties including high tensile strength, antibacterial and UV absorption. However to date, very little scientific effort has been devoted to fully understand the inter-correlation between their mechanical, physico-chemical, microstructural and morphological properties. In this paper, we report for the first time the structure–property relationship of elementary bamboo fibers. The impact of the inner microstructural organization of fibers (including the micro-fibrils angle) and physico-chemical factors such as the cellulose content and crystallinity index, on the tensile performance of these fibers is discussed in detail. This work also provides an insight into the application of bamboo fibers as natural and low-cost sorbent material for the removal of Cu2+ metal ions from model industrial wastewater. The metal ion adsorption properties of the fibers are correlated to surface energy analysis obtained from inverse gas chromatography.

Genetic structure and sex-biased dispersal of a declining cooperative-breeder, the Grey-crowned Babbler, Pomatostomus temporalis, at the southern edge of its range

Loss and fragmentation of habitat can disrupt genetic exchange between populations, which is reflected in changes to the genetic structure of populations. The Grey-crowned Babbler (Pomatostomus temporalis) is a cooperatively breeding woodland bird, once common and widespread in south-eastern Australia. The species has suffered population declines of >90% across its southern distribution as a result of loss and fragmentation of habitat. We investigated patterns of genetic diversity and population structure of Grey-crowned Babblers in fragmented habitats at the southernmost extent of its range. We sampled blood from 135 individual Babblers from 39 groups stratified into six subpopulations in three regions. Genotypic data were used to estimate genetic diversity, population substructure, local relatedness and dispersal patterns. Individuals showed high heterozygosity within regions, and varying numbers of private alleles among regions suggested differences in levels of connectivity between regions. Four genetic clusters revealed population substructure consistent with treeless landscapes acting as strong barriers to gene flow. In contrast to previous studies,we identified a male-biased dispersal pattern and significant isolation-by-distance patterns for females at fine spatial scales. We recommend that conservation plans for this species incorporate opportunities to increase and enhance corridor areas to facilitate genetic exchange among subpopulations.

Thermal Treatments of Fe—Mn Alkoxide of Glycerol: Infrared absorption and emission

Synthetic Fe—Mn alkoxide of glycerol samples are submitted to controlled heating conditions and examined by IR absorption spectroscopy. On the other hand, the same sample is studied by infrared emission spectroscopy (IRES), upon heating in situ from 100 to 600°C. The spectral techniques employed in this contribution, especially IRES, show that as a result of the thermal treatments ferromagnetic oxides (manganese ferrite) are formed between 350 and 400°C. Some further spectral changes are seen at higher temperatures.

The Behavior of Hydroxyl Units of Synthetic Goethite and its Dehydroxylated Product Hematite

The behavior of the hydroxyl units of synthetic goethite and its dehydroxylated product hematite was characterized using a combination of Fourier transform infrared (FTIR) spectroscopy and X-ray diffraction (XRD) during the thermal transformation over a temperature range of 180-270 degrees C. Hematite was detected at temperatures above 200 degrees C by XRD while goethite was not observed above 230 degrees C. Five intense OH vibrations at 3212-3194, 1687-1674, 1643-1640, 888-884 and 800-798 cm(-1), and a H2O vibration at 3450-3445 cm(-1) were observed for goethite. The intensity of hydroxyl stretching and bending vibrations decreased with the extent of dehydroxylation of goethite. Infrared absorption bands clearly show the phase transformation between goethite and hematite: in particular. the migration of excess hydroxyl units from goethite to hematite. Two bands at 536-533 and 454-452 cm(-1) are the low wavenumber vibrations of Fe-O in the hematite structure. Band component analysis data of FTIR spectra support the fact that the hydroxyl units mainly affect the a plane in goethite and the equivalent c plane in hematite.

Tuning the valence of the cerium center in (Na)phthalocyaninato and porphyrinato cerium double-deckers by changing the nature of the tetrapyrrole ligands

A series of 7 cerium double-decker complexes with various tetrapyrrole ligands including porphyrinates, phthalocyaninates, and 2,3-naphthalocyaninates have been prepared by previously described methodologies and characterized with elemental analysis and a range of spectroscopic methods. The molecular structures of two heteroleptic \[(na)phthalocyaninato](porphyrinato) complexes have also been determined by X-ray diffraction analysis which exhibit a slightly distorted square antiprismatic geometry with two domed ligands. Having a range of tetrapyrrole ligands with very different electronic properties, these compounds have been systematically investigated for the effects of ligands on the valence of the cerium center. On the basis of the spectroscopic (UV−vis, near-IR, IR, and Raman), electrochemical, and structural data of these compounds and compared with those of the other rare earth(III) counterparts reported earlier, it has been found that the cerium center adopts an intermediate valence in these complexes. It assumes a virtually trivalent state in cerium bis(tetra-tert-butylnaphthalocyaninate) as a result of the two electron rich naphthalocyaninato ligands, which facilitate the delocalization of electron from the ligands to the metal center. For the rest of the cerium double-deckers, the cerium center is predominantly tetravalent. The valences (3.59−3.68) have been quantified according to their LIII-edge X-ray absorption near-edge structure (XANES) profiles.