Studies of carbohydrate derivatives having the -CH2F function

The following primary sulphonates have been converted into the corresponding deoxyfluoro derivatives by reaction with potassium fluoride in ethylene glycol:1,2:3,4-di-O-isopropylidene-6-O-tosyl α-D-galactopyranose (1), methyl 2,3-O2-isopropyliden-5-O-tosyl-α,β-D-ribofuranoside (2), 1,2:3,4-di-O-methylene-6-O-tosyl-α-D-glucofuranose (3), 3,5-di-O-benzylidene-1,2-O-isopropylidene-6-O-tosyl-α-D-glucofuranose (4), and 1,2:3,5-di-O-isopropylidene-6-O-tosyl-α-D-glucofuranose (5). The yields were generally poor; in the reaction of 1, a major by-product was 6-O-(2-hydroxyethyl)-1,2:3,4-di-O-isopropylidene-α-D-galactopyranose (11). The reaction of the primary hydroxyl precursor of each of the above tosylates with N2-(2-chloro- 1,1,2-trifluoroethyl)-N,N-diethylamine generally yielded the O-chlorofluoroacetyl derivative; however, 1,2:3,5-di-O-methylene-α-D-glucofuranose (12) was converted into the 6-deoxy-6-fluoro derivative (8). The ¹⁹F resonances of compounds containing the CH₂F moiety fall between φ_C +213 and φ_C +235 p.p.m. The differences between the vicinal¹⁹F-¹H couplings of compounds having the D-gluco and D-galacto configurations clearly reflect the influence of the C-4O-4 substitutents on the populations of the C-5C-6 rotamers. A novel type of noise-modulated, heteronuclear decoupling experiment is described.     

Ouabain-insensitive salt and water movements in duck red cells. II. The role of chloride in the volume response

This paper describes the effect of external chloride on the typical swelling response induced in duck red cells by hypertonicity or norepinephrine. Lowering chloride inhibits swelling and produces concomitant changes in net movements of sodium and potassium in ouabain-treated cells, which resemble the effect of lowering external sodium or potassium. Inhibition is the same whether chloride is replaced with gluconate or with an osmotic equivalent of sucrose. Since changes in external chloride also cause predictable changes in cell chloride, pH, and water, these variables were systematically investigated by varying external pH along with chloride. Lowering pH to 6.60 does not abolish the response if external chloride levels are normal, although the cells are initially swollen due to the increased acidity. Cells deliberately preswollen in hypotonic solutions with appropriate ionic composition can also respond to norepinephrine by further swelling. These results rule out initial values of cell water, chloride, and pH as significant variables affecting the response. Initial values of the chloride equilibrium potential do have marked effect on the direction and rate of net water movement. If chloride is lowered by replacement with the permeant anion, acetate, E(Cl) is unchanged and a normal response to norepinephrine, which is inhibited by furosemide, is observed. Increasing internal sodium by the nystatin technique also inhibits the response. A theory is developed which depicts that the cotransport carrier proposed in the previous paper (W.F. Schmidt and T.J. McManus. 1977b. J. Gen. Physiol. 70:81-97) moves in response to the net electrochemical potential difference driving sodium and potassium across the membrane. Predictions of this theory fit the data for both cations and anions.     

Defining a functional unit for dairy production LCA that reflects the transaction between the farmer and the dairy processor

Purpose

The two main functions of dairy farming are to produce raw milk and to generate an economic income for the farmer (Powell et al. in Nutr Cycl Agroecosyst 82:107–115, 2008), both of which drive the downstream value chain. Farm profit is mainly determined by the quantity and quality of milk, and at the same time, dairy farmers have a responsibility for animal welfare and the protection of human health through milk hygiene. When dairy farmers supply milk to a processor, the payment is based on both the quantity and the quality in terms of composition (fat and protein) and hygiene (total bacterial count and somatic cell count). Somatic cell count reflects the health status of the mammary gland and contributes to reduced shelf life and reduced cheese yield and quality, whilst total bacterial count reflects herd health and farm sanitation. The objective of this work was to create a new functional unit for raw milk at the farm gate/ processor gate, which could be used to better capture the economic function of milk, while still reflecting the quality criteria captured by energy corrected milk and fat and protein corrected milk.

Materials and methods

Base price-adjusted milk (BPAM) is proposed as a functional unit to capture more of the functions of the transaction between the farmer and the processor. It expresses the volume of milk delivered as the equivalent volume at base price, such that greater milk solids increase the volume and poor hygiene decreases the volume. The BPAM was compared with energy-corrected milk and was tested using a survey of 54 farms in Ireland and eight scenarios compared with the observed values and an “ideal” scenario with no hygiene penalty imposed.

Results and discussion

It was found that kg BPAM for the sample of farms was strongly correlated with kg ECM because of the overall hygiene standard from the sample of farms available. For specific farms at specific times, the hygiene properties contributed to the economic function of the milk in a way that could not be captured using energy-corrected milk. The scenario analysis indicated that high levels of biological contamination, if captured in the raw milk functional unit, could increase carbon footprint by >?200%.

Conclusions

It was concluded that BPAM may not be a necessary functional unit for all studies, but those that focused on the farmer and processor perspectives should consider using BPAM because it captures more of the obligatory properties of raw milk than just quality expressed in terms of milk solids.

     

Liana cover in the canopies of rainforest trees is not predicted by local ground‐based measures

Lianas (woody climbers) are structural parasites of trees that compete with them for light and below‐ground resources. Most studies of liana–tree interactions are based on ground‐level observations of liana stem density and size, with these assessments generally assumed to reflect the amount of liana canopy cover and overall burden to the tree. We tested this assumption in a 1‐ha plot of lowland rainforest in tropical Australia. We recorded 1072 liana stems (≥1 cm diameter at breast height {dbh}) ha^?1 across all trees (≥10 cm dbh) on the plot and selected 58 trees for detailed study. We estimated liana canopy cover on selected trees that hosted 0–15 liana individuals, using a 47‐m‐tall canopy crane. Notably, we found no significant correlations between liana canopy cover and three commonly used ground‐based measurements of liana abundance as follows: liana stem counts per tree, liana above‐ground biomass per tree and liana basal area per tree. We also explored the role of tree size and liana infestation and found that larger trees (≥20 cm dbh) were more likely to support lianas and to host more liana stems than smaller trees (≤20 cm dbh). This pattern of liana stem density, however, did not correlate with greater liana coverage in the canopy. Tree family was also found to have a significant effect on likelihood of hosting lianas, with trees in some families 3–4 times more likely to host a liana than other families. We suggest that local ground‐based measures of liana–tree infestation may not accurately reflect liana canopy cover for individual trees because they were frequently observed spreading through neighbouring trees at our site. We believe that future liana research will benefit from new technologies such as high‐quality aerial photography taken from drones when the aim is to detect the relative burden of lianas on individual trees.     

The discovery of biaryl acids and amides exhibiting antibacterial activity against Gram-positive bacteria

Solid-phase synthetic methods for biaryl-based compounds were developed resulting in the construction of two 1000-member libraries. Numerous compounds were identified by high-throughput screening using whole cell screens to exhibit anti-microbial activity against Gram-positive bacteria. A series of biaryl compounds containing natural and unnatural amino acids were made to explore the SAR of the amino acid functionality.     

Interacting Factors Driving a Major Loss of Large Trees with Cavities in a Forest Ecosystem

Large trees with cavities provide critical ecological functions in forests worldwide, including vital nesting and denning resources for many species. However, many ecosystems are experiencing increasingly rapid loss of large trees or a failure to recruit new large trees or both. We quantify this problem in a globally iconic ecosystem in southeastern Australia – forests dominated by the world''s tallest angiosperms, Mountain Ash (Eucalyptus regnans). Tree, stand and landscape-level factors influencing the death and collapse of large living cavity trees and the decay and collapse of dead trees with cavities are documented using a suite of long-term datasets gathered between 1983 and 2011. The historical rate of tree mortality on unburned sites between 1997 and 2011 was >14% with a mortality spike in the driest period (2006–2009). Following a major wildfire in 2009, 79% of large living trees with cavities died and 57–100% of large dead trees were destroyed on burned sites. Repeated measurements between 1997 and 2011 revealed no recruitment of any new large trees with cavities on any of our unburned or burned sites. Transition probability matrices of large trees with cavities through increasingly decayed condition states projects a severe shortage of large trees with cavities by 2039 that will continue until at least 2067. This large cavity tree crisis in Mountain Ash forests is a product of: (1) the prolonged time required (>120 years) for initiation of cavities; and (2) repeated past wildfires and widespread logging operations. These latter factors have resulted in all landscapes being dominated by stands ≤72 years and just 1.16% of forest being unburned and unlogged. We discuss how the features that make Mountain Ash forests vulnerable to a decline in large tree abundance are shared with many forest types worldwide.     

Avian ecological succession in the Amazon: A long‐term case study following experimental deforestation

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Detecting anthropogenic disturbance in tropical forests

Tropical forests are beleaguered by an array of threats driven by different scales of anthropogenic perturbations, which vary in the degree to which they can be detected by remote sensing. The extent of different patterns of cryptic disturbance often far exceeds the total area deforested, as shown by two recent studies on selective logging in Amazonia. Here, we discuss different forms of disturbance in Amazonian forests and question how much of the apparently intact forest in this region remains relatively undisturbed.