Improvement of pasture biomass modelling using high-resolution satellite imagery and machine learning.

Robust quantification of vegetative biomass using satellite imagery using one or more forms of machine learning (ML) has hitherto been hindered by the extent and quality of training data. Here, we showcase how ML predictive demonstrably improves when additional training data is used. We collated field datasets of pasture biomass obtained via destructive sampling, 'C-Dax' reflective measurements and rising plate meters (RPM) from ten livestock farms across four States in Australia. Remotely sensed data from the Sentinel-2 constellation was used to retrieve aboveground biomass using a novel machine learning paradigm hereafter termed "SPECTRA-FOR" (Spectral Pasture Estimation using Combined Techniques of Random-forest Algorithm for Features Optimisation and Retrieval). Using this framework, we show that the low temporal resolution of Sentinel-2 in high latitude regions with persistent cloud cover leads to extensive gaps between cloud-free images, hindering model performance and, thus, contemporaneous ability to forecast real-time pasture biomass. By leveraging the spectral consistency between Sentinel-2 and Planet Lab SuperDove to overcome this limitation, we used ten spectral bands of Sentinel-2, four bands of Sentinel-2 as a proxy for pre-2022 SuperDove (referred to as synthetic SuperDove or SSD), and the actual SuperDove (ASD), given that SuperDove imagery has a higher resolution and more frequent passage compared with Sentinel-2. Using their respective bands as input features to SPECRA-FOR, model performance for the ten bands of Sentinel-2 were R2 = 0.87, root mean squared error (RMSE) of 439 kg DM/ha and mean absolute error (MAE) of 255 kg DM/ha, while that for SSD increased to an R2 of 0.92, RMSE of 346 kg DM/ha and MAE = 208 kg DM/ha. The study revealed the importance of robust data mining, imagery harmonisation and model validation for accurate real-time modelling of pasture biomass with ML.

Density independent decline from an environmentally transmitted parasite.

Invasive environmentally transmitted parasites have the potential to cause declines in host populations independent of host density, but this is rarely characterized in naturally occurring populations. We investigated (1) epidemiological features of a declining bare-nosed wombat (Vombatus ursinus) population in central Tasmania owing to a sarcoptic mange (agent Sarcoptes scabiei) outbreak, and (2) reviewed all longitudinal wombat-mange studies to improve our understanding of when host population declines may occur. Over a 7-year period, the wombat population declined 80% (95% CI 77-86%) and experienced a 55% range contraction. The average apparent prevalence of mange was high 27% (95% CI 21-34), increased slightly over our study period, and the population decline continued unabated, independent of declining host abundance. Combined with other longitudinal studies, our research indicated wombat populations may be at risk of decline when apparent prevalence exceeds 25%. This empirical study supports the capacity of environmentally transmitted parasites to cause density independent host population declines and suggests prevalence limits may be an indicator of impending decline-causing epizootics in bare-nosed wombats. This research is the first to test effects of density in mange epizootics where transmission is environmental and may provide a guide for when apparent prevalence indicates a local conservation threat.

Implementation of dedicated social worker coaching for emergency medicine residents - Lessons learned.

Emergency medicine training is associated with high levels of stress and burnout, which were exacerbated by the COVID-19 pandemic. The pandemic further exposed a mismatch between trainees' mental health needs and timely support services; therefore, the objective of our innovation was to create an opportunity for residents to access a social worker who could provide consistent coaching. The residency leadership team partnered with our graduate medical education (GME) office to identify a clinical social worker and professionally-trained coach to lead sessions. The project was budgeted at an initial cost of $15,000 over 1 year. Residents participated in 49 group and 73 individual sessions. Post implementation in 2021, we compared this intervention to all other wellness initiatives. Resident response rate was 80.88% (n = 55/68) and median interquartile range (IQR) score of the initiative was 2 (1 = detrimental and 4 = beneficial) versus 3.79 (3.69-3.88) the median IQR of all wellness initiatives. A notable number, 22%, rated the program as detrimental, which could be related to summary comments regarding ability to attend sessions, lack of session structure, loss of personal/educational time, and capacity of the social worker to relate with them. Summary comments also revealed the innovation was useful, with individual sessions preferred to group sessions. Application of a social worker coaching program in an emergency medicine residency program appears to be a feasible novel intervention. Lessons learned after implementation include the importance of recruiting someone with emergency department/GME experience, orienting them to culture before implementation and framing coaching as an integrated residency resource.

Successful use of veno-venous extracorporeal membrane oxygenation for acute chest syndrome in a child with sickle cell disease and SARS-CoV-2.

Children with sickle cell disease (SCD) are at increased risk for severe illness due to severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2). We describe the successful native lung recovery of a child with SCD referred for lung transplant (LTx) evaluation who was on prolonged veno-venous extracorporeal membrane oxygenation (VV-ECMO). He initially presented with acute chest syndrome complicated by SARS-CoV-2 infection that ultimately required dual-lumen, single bicaval VV-ECMO cannulation for respiratory support. Despite the increased risk of hemolysis and thrombosis from SCD and SARS-CoV-2 infection, he was successfully supported on VV-ECMO for 71 days without complications leading to native lung recovery with meticulous management of his SCD therapy. This report provides new insight on our approach to VV-ECMO support in a child with SCD and SARS-CoV-2 infection. With a successful outcome, the patient has returned home but still on mechanical ventilation with LTx still an option if he is not eventually liberated from invasive respiratory support.

Metal ion complexing properties of dipyridoacridine, a highly preorganized tridentate homologue of 1,10-phenanthroline.

DPA (dipyrido[4,3-b;5,6-b]acridine) may be considered as a tridentate homologue of phen (1,10-phenanthroline). In this paper some of the metal ion complexing properties of DPA in aqueous solution are reported. Using UV-visible spectroscopy to follow the intense π-π* transitions of DPA as a function of pH gave protonation constants at ionic strength (µ) = 0 and 25 °C of pK(1) = 4.57(3) and pK(2) = 2.90(3). Titration of 10(-5) M solutions of DPA with a variety of metal ions gave log K(1) values as follows: Zn(II), 7.9(1); Cd(II), 8.1(1); Pb(II), 8.3(1); La(III), 5.23(7); Gd(III), 5.7(1); Ca(II), 3.68; all at 25 °C and µ = 0. Log K(1) values at µ = 0.1 were obtained for Mg(II), 0.7(1); Sr(II), 2.20(1); Ba(II), 1.5(1). The log K(1) values show that the high level of preorganization of DPA leads to complexes 3 log units more stable than the corresponding terpyridyl complexes for large metal ions such as La(III) or Ca(II), but that for small metal ions such as Mg(II) and Zn(II) such stabilization is minimal. Molecular mechanics calculations (MM) are used to show that the best-fit M-N length for coordination with DPA is 2.60 Å, accounting for the high stability of Ca(II) or La(III) complexes of DPA, which are found to have close to this M-N bond length in their phen complexes.

Single-Molecule Force Spectroscopy of DNA-Based Reversible Polymer Bridges: Surface Robustness and Homogeneity.

Single-molecule force spectroscopy, as implemented in an atomic force microscope, provides a rarely-used method by which to monitor dynamic processes that occur near surfaces. Here, a methodology is presented and characterized that facilitates the study of polymer bridging across nanometer-sized gaps. The model system employed is that of DNA-based reversible polymers, and an automated procedure is introduced that allows the AFM tip-surface contact point to be automatically determined, and the distance d between opposing surfaces to be actively controlled. Using this methodology, the importance of several experimental parameters was systematically studied, e.g. the frequency of repeated tip/surface contacts, the area of the substrate surface sampled by the AFM, and the use of multiple AFM tips and substrates. Experiments revealed the surfaces to be robust throughout pulling experiments, so that multiple touches and pulls could be carried out on a single spot with no measurable affect on the results. Differences in observed bridging probabilities were observed, both on different spots on the same surface and, more dramatically, from one day to another. Data normalization via a reference measurement allows data from multiple days to be directly compared.

Effects of steric constraint on chromium(III) complexes of tetraazamacrocycles, 2. Comparison of the chemistry and photobehavior of the trans-dichloro- and trans-dicyano- complexes of cyclam, 1,4-C2-cyclam, and 1,11-C3-cyclam.

The synthesis and characterization of several Cr(III) complexes of the constrained macrocyclic ligand 1,11-C3-cyclam (1,4,8,11-tetraazabicyclo[9.3.3]heptadecane) is reported. Only trans complexes are formed, and the structure of trans-[Cr(1,11-C3-cyclam)Cl2]PF6 is presented. The chemical and photophysical behavior of the 1,11-C3-cyclam complexes are compared with those of the corresponding cyclam (1,4,8,11 tetraazacyclotetradecane) and 1,4-C2-cyclam (1,4,8,11-tetraazabicyclo[10.2.2]hexadecane) complexes. The aquation rate of trans-[Cr(1,11-C3-cyclam)Cl2]+ is similar to that of the corresponding 1,4-C2-cyclam complex and is more than 5 orders of magnitude faster than the cyclam counterpart. A monotonic increase in the extinction coefficient is observed on going from the cyclam complexes to the 1,11-C3-cyclam complexes to the 1,4-C2-cyclam complexes, and this is related to the degree of centrosymmetry in each complex. The trans-[Cr(1,11-C3-cyclam)(CN)2]+ complex is a weak emitter in aqueous solution with a room-temperature emission maximum at 724 nm (tau=23 micros). Like the corresponding 1,4-C2-cyclam complex (tau=0.24 micros), the 1,11-C3-cyclam complex shows no deuterium-isotope effect in room-temperature solution. This is in marked contrast to the corresponding cyclam complex which has an emission lifetime of 335 micros and a significant deuterium isotope effect in room-temperature solution. Low temperature (77K) data are also presented in an attempt to understand the differences in photophysical behavior.

Factors controlling metal-ion selectivity in the binding sites of calcium-binding proteins. The metal-binding properties of amide donors. A crystallographic and thermodynamic study.

The metal-ion complexing properties of the ligand EDTAM (ethylenediamine-N,N,N',N'-tetraacetamide) are investigated as a model for the role of amide oxygen donors in the binding sites of Ca-binding proteins. The structures of the complexes [Ca(EDTAM)NO3]NO3 (1), [La(EDTAM)(H2O)4](NO3)3.H2O (2), and [Cd(EDTAM)(NO3)]NO3 (3) are reported: 1 monoclinic, P2(1)/c, a = 10.853(2) angstroms, b = 12.893(3) angstroms, c = 13.407(3) angstroms, beta = 103.28(3) degrees, Z = 4, R = 0.0281; 2 triclinic, P, a = 8.695(2) angstroms, b = 9.960(2) angstroms, c = 16.136(3) angstroms, alpha = 95.57(3) degrees, beta = 94.84(3) degrees, gamma = 98.72(3) degrees, Z = 2, R = 0.0394; 3 monoclinic, P2(1)/c, a = 10.767(2) angstroms, b = 12.952(2) angstroms, c = 13.273(2) angstroms, beta = 103.572(3) degrees, Z = 4, R = 0.0167. Compounds 1 and 3 are isostructural, and the EDTAM binds to the metal ion through its two N-donors and four O-donors from the amide groups. Ca(II) in 1 is 8-coordinate with a chelating NO3- group, while Cd(II) in 3 may possibly be 7-coordinate, with an asymmetrically coordinated NO3- that is best regarded as unidentate. The La(III) in 2 is coordinated to the EDTAM in a manner similar to that of 1 and 3, but it is 10-coordinate with four water molecules coordinated to the La(III). The formation constants (log K1) for complexes of a variety of metal ions with EDTAM are reported in 0.1 M NaNO3 at 25.0 +/- 0.1 degrees C. These are compared to the log K1 values for en (ethylenediamine) and THPED (N,N,N',N'-tetrakis(2-hydroxypropyl)-ethylenediamine). For large metal ions, such as Ca2+ or La3+, log K1 increases strongly when the four acetamide groups are added to en to give EDTAM, whereas for a small metal ion, such as Mg2+, this increase is small. The log K1 values for EDTAM compared to THPED suggest that the amide oxygen is a much stronger base than the alcoholic oxygen. Structures of binding sites in 40 Ca-binding proteins are examined. It is shown that the Ca-O=C bond angles involving coordinated amides in these sites are large, commonly being in the 150-180 degrees range. This is discussed in terms of the idea that for purely ionic bonding the M-O=C bond angle will approach 180 degrees, while for covalent bonding the angle should be closer to 120 degrees. How this fact might be used by the proteins to control selectivity for different metal ions is discussed.