A Raman spectroscopic study of the antimonite mineral peretaite Ca(SbO)4(OH)2(SO4)2•2H2O

Raman spectra of mineral peretaite Ca(SbO)4(OH)2(SO4)2•2H2O were studied, and related to the structure of the mineral. Raman bands observed at 978 and 980 cm-1 and a series of overlapping bands observed at 1060, 1092, 1115, 1142 and 1152 cm-1 are assigned to the SO42- ν1 symmetric and ν3 antisymmetric stretching modes. Raman bands at 589 and 595 cm-1 are attributed to the SbO symmetric stretching vibrations. The low intensity Raman bands at 650 and 710 cm-1 may be attributed to SbO antisymmetric stretching modes. Raman bands at 610 cm-1 and at 417, 434 and 482 cm-1 are assigned to the SO42- 4 and 2 bending modes, respectively. Raman bands at 337 and 373 cm-1 are assigned to O-Sb-O bending modes. Multiple Raman bands for both SO42- and SbO stretching vibrations support the concept of the non-equivalence of these units in the coquandite structure.

One-dimensional hydrogen-bonded structures in the 1:1 proton-transfer salts of 4,5-dichlorophthalic acid with the aliphatic Lewis bases diisopropylamine and hexamethylenetetramine

The crystal structures of the 1:1 proton-transfer compounds of 4,5-dichlorophthalic acid with the aliphatic Lewis bases diisopropylamine and hexamethylenetetramine, viz. diisopropylaminium 2-carboxy-4,5-dichlorobenzoate (1) and hexamethylenetetraminium 2-carboxy-4,5-dichlorobenzoate hemihydrate (2), have been determined. Crystals of both 1 and 2 are triclinic, space group P-1, with Z = 2 in cells with a = 7.0299(5), b = 9.4712(7), c = 12.790(1)Å, α = 99.476(6), β = 100.843(6), γ = 97.578(6)o (1) and a = 7.5624(8), b = 9.8918(8), c = 11.5881(16)Å, α = 65.660(6), β = 86.583(4), γ = 86.987(8)o (2). In each, one-dimensional hydrogen-bonded chain structures are found: in 1 formed through aminium N+-H...Ocarboxyl cation-anion interactions. In 2, the chains are formed through anion carboxyl O...H-Obridging water interactions with the cations peripherally bound. In both structures, the hydrogen phthalate anions are essentially planar with short intra-species carboxylic acid O-H...Ocarboxyl hydrogen bonds [O…O, 2.381(3) Å (1) and 2.381(8) Å (2)].

Hydrogen bonding in the water stabilized structure of the modified unsymmetrically substituted viologen chromophore, N-ethyl-N'-(2-phosphonomethyl)-4,4'-bipyridylium dichloride

The crystal structure of the modified unsymmetrically N, N'-substituted viologen chromophore, N-ethyl- N'-(2-phosphonoethyl)-4, 4'-bipyridinium dichloride 0.75 hydrate. (1) has been determined. Crystals are triclinic, space group P-1 with Z = 2 in a cell with a = 7.2550(1), b = 13.2038(5), c = 18.5752(7) Å, α = 86.495(3), β = 83.527(2), γ = 88.921(2)o. The two independent but pseudo-symmetrically related cations in the asymmetric unit form one-dimensional hydrogen-bonded chains through short homomeric phosphonic acid O-H...O links [2.455(4), 2.464(4)A] while two of the chloride anions are similarly strongly linked to phosphonic acid groups [O-H…Cl, 2.889(4), 2.896(4)Å]. The other two chloride anions together with the two water molecules of solvation (one with partial occupancy) form unusual cyclic hydrogen-bonded bis(Cl...water) dianion units which lie between the layers of bipyridylium rings of the cation chain structures with which they are weakly associated.

Crystallographic characterization of the first reported crystalline form of the potent hallucinogen (R)-2-amino-1-(8-bromobenzo[1,2-b;5,4-b']difuran-4-yl)propane or `bromodragonfly': the 1:1 anhydrous proton-transfer compound with 3,5-dinitrosalicylic acid

The 1:1 proton-transfer compound of the potent substituted amphetamine hallucinogen (R)-1-(8-bromobenzo[1,2-b; 4,5-b']difuran-4-yl)-2-aminopropane (common trivial name 'bromodragonfly') with 3,5-dinitrosalicylic acid, 1-(8-bromobenzo[1,2-b;4,5-b']difuran-4-yl)-2-mmoniopropane 2-carboxy-4,6-dinitrophenolate, C13H13BrNO2+ C7H3N2O7- forms hydrogen-bonded cation-anion chain substructures comprising undulating head-to-tail anion chains formed through C(8) carboxyl O-H...O(nitro) associations and incorporating the aminium groups of the cations. The intra-chain cation-anion hydrogen-bonding associations feature proximal cyclic R33(8) interactions involving both a N+-H...O(phenolate) and the carboxyl O--H...O(nitro)associations. Also present are aromatic pi-pi ring interactions [minimum ring centroid separation, 3.566(2)A; inter-plane dihedral angle, 5.13(1)deg]. A lateral hydrogen-bonding interaction between the third aminium proton and a carboxyl O acceptor link the chain substructures giving a two-dimensional sheet structure. This determination represents the first of any form of this compound and confirms that it has the (R) absolute configuration. The atypical crystal stability is attributed both to the hydrogen-bonded chain substructures provided by the anions, which accommodate the aminium proton-donor groups of the cations and give cross-linking, and to the presence of cation--anion aromatic ring pi-pi interactions.

4-Methylpyridinium 2-carboxy-4,5-dichlorobenzoate

In the structure of the 1:1 proton-transfer compound of 4-methylpyridine (\g-picoline) with 4,5-dichlorophthalic acid, C6H8N+ C8H3Cl2O4- . H2O, determined at 200 K, the 4,5-dichlorophthalate anions are bridged by the water molecule through O--H...O~carboxyl~ hydrogen bonds, giving zig-zag chains which extend along the c axial direction of the unit cell. The 4-methylpyridine cations are linked to the chains through single N--H...O~water~ hydrogen bonds and occupy the voids within the chains in the one-dimensional structure. The anions have the common 'planar' conformation with the short intramolecular O--H...O(carboxyl) hydrogen bond.

Hydrate stabilization in the three-dimensional hydrogen-bonded structure of the brucinium compound, bis(2,3-dimethoxy-10-oxostrychnidinium) biphenyl-4,4'-disulfonate hexahydrate

The crystal structure of the 2:1 proton-transfer compound of brucine with biphenyl-4,4’-disulfonate, bis(2,3-dimethoxy-10-oxostrychnidinium) biphenyl-4,4'-disulfonate hexahydrate (1) has been determined at 173 K. Crystals are monoclinic, space group P21 with Z = 2 in a cell with a = 8.0314(2), b = 29.3062(9), c = 12.2625(3) Å, β = 101.331(2)o. The crystallographic asymmetric unit comprises two brucinium cations, a biphenyl-4,4'-disulfonate dianion and six water molecules of solvation. The brucinium cations form a variant of the common undulating and overlapping head-to-tail sheet sub-structure. The sulfonate dianions are also linked head-to-tail by hydrogen bonds into parallel zig-zag chains through clusters of six water molecules of which five are inter-associated, featuring conjoint cyclic eight-membered hydrogen-bonded rings [graph sets R33(8) and R34(8)], comprising four of the water molecules and closed by sulfonate O-acceptors. These chain structures occupy the cavities between the brucinium cation sheets and are linked to them peripherally through both brucine N+-H...Osulfonate and Ocarbonyl…H-Owater to sulfonate O bridging hydrogen bonds, forming an overall three-dimensional framework structure. This structure determination confirms the importance of water in the stabilization of certain brucine compounds which have inherent crystal instability.

Phenyl-ring disorder in the two-dimensional hydrogen-bonded structure of the 1:1 proton-transfer salt of the diazo-dye precursor 4-(phenyldiazenyl)aniline (aniline yellow) with L-tartaric acid

The structure of the 1:1 proton-transfer compound from the reaction of L-tartaric acid with the azo-dye precursor aniline yellow [4-(phenylazo)aniline], 4-(phenyldiazenyl)anilinium hydrogen 2R,3R-tartrate C12H12N3+ . C4H6O6- has been determined at 200 K. The asymmetric unit of the compound contains two independent phenylazoanilinium cations and two hydrogen L-tartrate anions. The structure is unusual in that all four phenyl rings of both cations have identical 50% rotational disorder. The two hydrogen L-tartrate anions form independent but similar chains through head-to-tail carboxylic O--H...O~carboxyl~ hydrogen bonds [graph set C7] which are then extended into a two-dimensional hydrogen-bonded sheet structure through hydroxyl O--H...O hydrogen-bonding links. The anilinium groups of the phenyldiazenyl cations are incorporated into the sheets and also provide internal hydrogen-bonding extensions while their aromatic tails layer in the structure without significant interaction except for weak \p--\p interactions [minimum ring centroid separation, 3.844(3) \%A]. The hydrogen L-tartrate residues of both anions have the common short intramolecular hydroxyl O--H...O~carboxyl~ hydogen bonds. This work has provided a solution to the unusual disorder problem inherent in the structure of this salt as well as giving another example of the utility of the hydrogen tartrate in the generation of sheet substructures in molecular assembly processes.

2-(2,4-dinitrobenzyl)pyridinium 2-hydroxy-3,5-dinitrobenzoate

In the structure of the title compound, the salt C12H10N3O4+ C7H3N2O72-, the cations and the anions are linked by a single N+-H...O(carboxyl) hydrogen bond, the discrete cation-anion unit having no intermolecular associations other than weak cation--anion aromatic ring pi--pi interactions [ring centroid separation, 3.7320(14)A] and a number of weak inter-unit aromatic C-H...O contacts.

Impacts of periodic tillage on soil C stocks : a synthesis

Long-term loss of soil C stocks under conventional tillage and accrual of soil C following adoption of no-tillage have been well documented. No-tillage use is spreading, but it is common to occasionally till within a no-till regime or to regularly alternate between till and no-till practices within a rotation of different crops. Short-term studies indicate that substantial amounts of C can be lost from the soil immediately following a tillage event, but there are few field studies that have investigated the impact of infrequent tillage on soil C stocks. How much of the C sequestered under no-tillage is likely to be lost if the soil is tilled? What are the longer-term impacts of continued infrequent no-tillage? If producers are to be compensated for sequestering C in soil following adoption of conservation tillage practices, the impacts of infrequent tillage need to be quantified. A few studies have examined the short-term impacts of tillage on soil C and several have investigated the impacts of adoption of continuous no-tillage. We present: (1) results from a modeling study carried out to address these questions more broadly than the published literature allows, (2) a review of the literature examining the short-term impacts of tillage on soil C, (3) a review of published studies on the physical impacts of tillage and (4) a synthesis of these components to assess how infrequent tillage impacts soil C stocks and how changes in tillage frequency could impact soil C stocks and C sequestration. Results indicate that soil C declines significantly following even one tillage event (1-11 % of soil C lost). Longer-term losses increase as frequency of tillage increases. Model analyses indicate that cultivating and ripping are less disruptive than moldboard plowing, and soil C for those treatments average just 6% less than continuous NT compared to 27% less for CT. Most (80%) of the soil C gains of NT can be realized with NT coupled with biannual cultivating or ripping. (C) 2007 Elsevier B.V. All rights reserved.

Validation of the Chinese version of the Problem Areas in Diabetes (PAID-C) scale

OBJECTIVE To examine the psychometric properties of a Chinese version of the Problem Areas In Diabetes (PAID-C) scale. RESEARCH DESIGN AND METHODS The reliability and validity of the PAID-C were evaluated in a convenience sample of 205 outpatients with type 2 diabetes. Confirmatory factor analysis, Bland-Altman analysis, and Spearman's correlations facilitated the psychometric evaluation. RESULTS Confirmatory factor analysis confirmed a one-factor structure of the PAID-C (χ2/df ratio = 1.894, goodness-of-fit index = 0.901, comparative fit index = 0.905, root mean square error of approximation = 0.066). The PAID-C was associated with A1C (rs = 0.15; P < 0.05) and diabetes self-care behaviors in general diet (rs = −0.17; P < 0.05) and exercise (rs = −0.17; P < 0.05). The 4-week test-retest reliability demonstrated satisfactory stability (rs = 0.83; P < 0.01). CONCLUSIONS The PAID-C is a reliable and valid measure to determine diabetes-related emotional distress in Chinese people with type 2 diabetes.

Anhydrous 1:1 proton-transfer compounds of isonipecotamide with picric acid and 3,5-dinitrosalicylic acid: 4-carbamoylpiperidinium 2,4,6-trinitrophenolate and two polymorphs of 4-carbamoylpiperidinium 2-carboxy-4,6-dinitrophenolate

The structures of the anhydrous 1:1 proton-transfer compounds of isonipecotamide (4-carbamoylpiperidine) with picric acid and 3,5-dinitrosalicylic acid, namely 4-carbamoylpiperidinium 2,4,6-trinitrophenolate, C6H13N2O8+ C6H2N3O7- (I) and 4-carbamoylpiperidinium 2-carboxy-4,6-dinitrophenolate, C6H13N2O8+ C7H3N2O7-: two forms, the monoclinic alpha-polymorph (II) and the triclinic beta-polymorph (III) have been determined at 200 K. All compounds form hydrogen-bonded structures, one-dimensional in (II), two-dimensional in (I) and three-dimensional in (III). In (I), the cations form centrosymmetric cyclic head-to-tail hydrogen-bonded homodimers [graph set R2/2(14)] through lateral duplex piperidinium N---H...O(amide) interactions. These dimers are extended into a two-dimensional network structure through further interactions with anion phenolate-O and nitro-O acceptors, including a direct symmetric piperidinium N-H...O(phenol),O(nitro) cation--anion association [graph set R2/1(6)]. The monoclinic polymorph (II) has a similar R2/1(6) cation-anion hydrogen-bonding interaction to (I) but with an additional conjoint symmetrical R1/2(4) interaction as well as head-to-tail piperidinium N-H...O(amide) O hydrogen bonds and amide N-H...O(carboxyl) hydrogen bonds, give a network structure which include large R3/4(20) rings. The hydrogen bonding in the triclinic polymorph (III) is markedly different from that of monoclinic (II). The asymmetric unit contains two independent cation-anion pairs which associate through cyclic piperidinium N-H...O,O'(carboxyl) interactions [graph set R2/1(4)]. The cations also show the zig-zag head-to-tail piperidinium N-H...O(amide) hydrogen-bonded chain substructures found in (II) but in addition feature amide N-H...O(nitro) and O(phenolate) and amide N-H...O(nitro) associations. As well there is a centrosymmetric double-amide N-H...O(carboxyl) bridged bis(cation-anion) ring system [graph set R2/4(8)] in the three-dimensional framework. The structures reported here demonstrate the utility of the isonipecotamide cation as a synthon with previously unrecognized potential for structure assembly applications. Furthermore, the structures of the two polymorphic 3,5-dinitrosalicylic acid salts show an unusual dissimilarity in hydrogen-bonding characteristics, considering that both were obtained from identical solvent systems.

Influence of historic land use change on the biosphere-atmosphere-exchange of C and N trace gases in the humid, subtropical region of Queensland

Increases in atmospheric concentrations of the greenhouse gases (GHGs) carbon dioxide (CO2), methane (CH4), and nitrous oxide (N2O) due to human activities have been linked to climate change. GHG emissions from land use change and agriculture have been identified as significant contributors to both Australia’s and the global GHG budget. This is expected to increase over the coming decades as rates of agriculture intensification and land use change accelerate to support population growth and food production. Limited data exists on CO2, CH4 and N2O trace gas fluxes from subtropical or tropical soils and land uses. To develop effective mitigation strategies a full global warming potential (GWP) accounting methodology is required that includes emissions of the three primary greenhouse gases. Mitigation strategies that focus on one gas only can inadvertently increase emissions of another. For this reason, detailed inventories of GHGs from soils and vegetation under individual land uses are urgently required for subtropical Australia. This study aimed to quantify GHG emissions over two consecutive years from three major land uses; a well-established, unfertilized subtropical grass-legume pasture, a 30 year (lychee) orchard and a remnant subtropical Gallery rainforest, all located near Mooloolah, Queensland. GHG fluxes were measured using a combination of high resolution automated sampling, coarser spatial manual sampling and laboratory incubations. Comparison between the land uses revealed that land use change can have a substantial impact on the GWP on a landscape long after the deforestation event. The conversion of rainforest to agricultural land resulted in as much as a 17 fold increase in GWP, from 251 kg CO2 eq. ha-1 yr-1 in the rainforest to 889 kg CO2 eq. ha-1 yr-1 in the pasture to 2538 kg CO2 eq. ha-1 yr-1 in the lychee plantation. This increase resulted from altered N cycling and a reduction in the aerobic capacity of the soil in the pasture and lychee systems, enhancing denitrification and nitrification events, and reducing atmospheric CH4 uptake in the soil. High infiltration, drainage and subsequent soil aeration under the rainforest limited N2O loss, as well as promoting CH4 uptake of 11.2 g CH4-C ha-1 day-1. This was among the highest reported for rainforest systems, indicating that aerated subtropical rainforests can act as substantial sink of CH4. Interannual climatic variation resulted in significantly higher N2O emission from the pasture during 2008 (5.7 g N2O-N ha day) compared to 2007 (3.9 g N2O-N ha day), despite receiving nearly 500 mm less rainfall. Nitrous oxide emissions from the pasture were highest during the summer months and were highly episodic, related more to the magnitude and distribution of rain events rather than soil moisture alone. Mean N2O emissions from the lychee plantation increased from an average of 4.0 g N2O-N ha-1 day-1, to 19.8 g N2O-N ha-1 day-1 following a split application of N fertilizer (560 kg N ha-1, equivalent to 1 kg N tree-1). The timing of the split application was found to be critical to N2O emissions, with over twice as much lost following an application in spring (emission factor (EF): 1.79%) compared to autumn (EF: 0.91%). This was attributed to the hot and moist climatic conditions and a reduction in plant N uptake during the spring creating conditions conducive to N2O loss. These findings demonstrate that land use change in subtropical Australia can be a significant source of GHGs. Moreover, the study shows that modifying the timing of fertilizer application can be an efficient way of reducing GHG emissions from subtropical horticulture.

Pseudo-merohedral twinning in the structure of the hydrated 1:1 proton-transfer compound of 5-sulfosalicylic acid with 4-aminopyridine

The structure of the pseudo-merohedrally twinned crystal of the 1:1 proton-transfer compound of 5-sulfosalicylic acid (3-carboxy-4-hydroxybenzenesulfonic acid) with 4-aminopyridine: 4-aminopyridinium 3-carboxy-4-hydroxybenzenesulfonate sesquihydrate has been determined at 180 K and the hydrogen-bonding pattern is described. Crystals of the compound are monoclinic with space group P21/c, with unit cell dimensions a = 35.2589(8), b = 7.1948(1), c = 24.5851(5) Å, β = 110.373(2)o, and Z = 16. The monoclinic asymmetric unit comprises four cation-anion pairs and six water molecules of solvation with only the pyridinium cations having pseudo-symmetry as a result of inter-cation aromatic ring π-π stacking effects. Extensive hydrogen bonding gives a three-dimensional framework structure.

TaNF-YC11, one of the light-upregulated NF-YC members in Triticum aestivum, is co-regulated with photosynthesis-related genes

NF-Y is a heterotrimeric transcription factor complex. Each of the NF-Y subunits (NF-YA, NF-YB and NF-YC) in plants is encoded by multiple genes. Quantitative RT-PCR analysis revealed that five wheat NF-YC members (TaNF-YC5, 8, 9, 11 & 12) were upregulated by light in both the leaf and seedling shoot. Co-expression analysis of Affymetrix wheat genome array datasets revealed that transcript levels of a large number of genes were consistently correlated with those of the TaNF-YC11 and TaNF-YC8 genes in 3-4 separate Affymetrix array datasets. TaNF-YC11-correlated transcripts were significantly enriched with the Gene Ontology term photosynthesis. Sequence analysis in the promoters of TaNF-YC11-correlated genes revealed the presence of putative NF-Y complex binding sites (CCAAT motifs). Quantitative RT-PCR analysis of a subset of potential TaNF-YC11 target genes showed that ten out of the thirteen genes were also light-upregulated in both the leaf and seedling shoot and had significantly correlated expression profiles with TaNF-YC11. The potential target genes for TaNF-YC11 include subunit members from all four thylakoid membrane bound complexes required for the conversion of solar energy into chemical energy and rate limiting enzymes in the Calvin cycle. These data indicate that TaNF-YC11 is potentially involved in regulation of photosynthesis-related genes.

A Raman spectroscopic study of M2+M3+ sulfate minerals, römerite Fe2+Fe23+ (SO4)4· 14H2O and botryogen Mg2+Fe3+ (SO4)2(OH)·7H2O

The mixed valency (M2+M3+) sulphate minerals, römerite Fe2+Fe23+(SO4)4•14H2O and botryogen Mg2+Fe3+(SO4)2(OH).7H2O have been studied by Raman spectroscopy. The Raman spectra of the two types of crystals proved very similar but not identical. The observation of two symmetric stretching modes confirmed the presence of the two non-equivalent sulphate units in the römerite structure. The observation of multiple bands in the antisymmetric stretching region and in the bending regions proves the symmetry of the sulphate anion is significantly reduced in the römerite structure. The number of Raman bands related to the (SO4)2- symmetric and antisymmetric vibrations support the X-ray single crystal structure conclusion that two symmetrically distinct S6+ are present in the structure of botryogen. Römerite is a mineral of environmental significance as it is commonly found in tailings and dumps.