Elucidating the Mechanism of Efficient Eu(III) and Yb(III) Sensitisation from a Re(I) Tetrazolato Triangular Assembly.

The reaction of Re(CO)5Br with deprotonated 1H-(5-(2,2':6',2''-terpyridine)pyrid-2-yl)tetrazole yields a triangular assembly formed by tricarbonyl Re(I) vertices. Photophysical measurements reveal blue-green emission with a maximum at 520 nm, 32% quantum yield, and 2430 ns long-lived excited state decay lifetime in deaerated dichloromethane solution. Coordination of lanthanoid ions to the terpyridine units red-shifts the emission to 570 nm and also reveals efficient (90%) and fast sensitisation to both Eu(III) and Yb(III) at room temperature, with a similar rate constant kET of the order of 107 s-1. Efficient sensitisation of Eu(III) from Re(I) is unprecedented, especially when considering the close proximity in energy between the donor and acceptor excited states. On the other hand, comparative measurements at 77 K reveal that energy transfer to Yb(III) is two orders of magnitude slower than that to Eu(III). A two-step mechanism of sensitisation is therefore proposed, whereby the rate-determining step is a thermally activated energy transfer step between the Re(I) centre and the terpyridine functionality, followed by rapid energy transfer to the respective Ln(III) excited states. At 77 K, the direct Re(I) to Eu(III) energy transfer seems to proceed via a ligand-mediated superexchange Dexter-type mechanism.

On-Surface Molecular Recognition Driven by Chalcogen Bonding.

Chalcogen bonding interactions (ChBIs) have been widely employed to create ordered noncovalent assemblies in solids and liquids. Yet, their ability to engineer molecular self-assembly on surfaces has not been demonstrated. Here, we report the first demonstration of on-surface molecular recognition solely governed by ChBIs. Scanning tunneling microscopy and ab initio calculations reveal that a pyrenyl derivative can undergo noncovalent chiral dimerization on the Au(111) surface through double Ch···N interactions involving Te- or Se-containing chalcogenazolo pyridine motifs. In contrast, reference chalcogenazole counterparts lacking the pyridyl moiety fail to form regular self-assemblies on Au, resulting in disordered assemblies.

An extremely electron poor Au(III) trication bearing acetonitrile ligands.

The synthesis and structural characterization of an electron poor Au(III) trication bearing 2 imidazole and 2 acetonitrile ligands is described. The new complex is capable of aryl C-H metalation with the formation of a monomesitylene complex and also demonstrated to be highly oxidizing in the rapid room temperature conversion of cyclohexene to benzene.

Aggregation-Induced Emission of Naphthalene Diimides: Effect of Chain Length on Liquid and Solid-Phase Emissive Properties.

The aggregation-induced emission (AIE) properties of a systematic series of naphthalene diimides (NDIs) varying the chain length at the imide positions have been studied. A solvophobic collapse of NDI units through the flash injection of THF NDI solutions in sonicating water triggers the formation of stable suspensions with enhanced fluorescence emissions. Shorter chains favor the π-π stacking of NDI units through H-aggregation producing a strong AIE effect showing remarkably high quantum yields that have not been observed for non core-substitued NDIs previously. On the other hand, NDIs functionalized with longer chains lead to more disordered domains where π-π stacking between NDI units is mainly given by J-aggregation unfavoring the AIE effect.

More Accurate Measurement of Return Peak Current in Cyclic Voltammetry Using Diffusional Baseline Fitting.

The difficulty associated with accurately measuring the height of the back peak (Ipb) in cyclic voltammetry (CV) has long plagued electrochemists. Most commonly, Ipb is measured by extrapolating a linear fit from a selected region of a voltammogram after the switching potential (Eλ), but without substantial separation between the peak potential (Ep) and Eλ, this approach always overestimates the background current and so underestimates Ipb. Moreover, experimental conditions can present challenges for this method as an appropriate region for linear fitting is often lacking due to neighboring peaks or solvent electrolysis current. Here, we present a new method for finding the baseline current for the back peak in CV experiments. By examining the CV data as a function of time rather than potential, it is possible to fit a generalized Cottrell or Shoup-Szabo equation to the current decay of the forward peak and extrapolate this function as a baseline for the return peak. This approach was tested by using simulated and experimental data in a variety of conditions, including data demonstrating linear and radial diffusional control. We found that the method allows for more accurate determination of back peak currents, especially when linear fits are complicated by narrow electrochemical windows or radial diffusion. A user-friendly Python program was written to automatically find an appropriate fitting range for this analysis and measure peak currents. We have made this program available to the electrochemical community at large.

N-Heterocyclic Olefins on a Silicon Surface.

The adsorption of N-heterocyclic olefins (NHOs) on silicon is investigated in a combined scanning tunneling microscopy, X-ray photoelectron spectroscopy, and density functional theory study. We find that both of the studied NHOs bind covalently, with ylidic character, to the silicon adatoms of the substrate and exhibit good thermal stability. The adsorption geometry strongly depends on the N-substituents: for large N-substituents, an upright adsorption geometry is favored, while a flat-lying geometry is found for the NHO with smaller wingtips. These different geometries strongly influence the quality and properties of the obtained monolayers. The upright geometry leads to the formation of ordered monolayers, whereas the flat-lying NHOs yield a mostly disordered, but denser, monolayer. The obtained monolayers both show large work function reductions, as the higher density of the flat-lying monolayer is found to compensate for the smaller vertical dipole moments. Our findings offer new prospects in the design of tailor-made ligand structures in organic electronics and optoelectronics, catalysis, and material science.

Giant and Tunable Out-of-Plane Spin Polarization of Topological Antimonene.

Topological insulators are bulk insulators with metallic and fully spin-polarized surface states displaying Dirac-like band dispersion. Due to spin-momentum locking, these topological surface states (TSSs) have a predominant in-plane spin polarization in the bulk fundamental gap. Here, we show by spin-resolved photoemission spectroscopy that the TSS of a topological insulator interfaced with an antimonene bilayer exhibits nearly full out-of-plane spin polarization within the substrate gap. We connect this phenomenon to a symmetry-protected band crossing of the spin-polarized surface states. The nearly full out-of-plane spin polarization of the TSS occurs along a continuous path in the energy-momentum space, and the spin polarization within the gap can be reversibly tuned from nearly full out-of-plane to nearly full in-plane by electron doping. These findings pave the way to advanced spintronics applications that exploit the giant out-of-plane spin polarization of TSSs.

Structural verification and new reactivity for Stang's reagent, [PhI(CN)][OTf].

The structure of Stang's reagent [PhI(CN)][OTf] is confirmed by X-ray crystallography and is determined to be best described as an ion-pair in organic solution. It is found to be a strong Lewis acid, but reaction with pyridine ligands gives [Pyr-CN][OTf] salts via oxidation of pyridine giving a new derivative of the CDAP reagent widely used as an activation agent for polysaccharides.

Longitudinal measures of labour time-use on pasture-based dairy farms, incorporating the impact of specific facilities and technologies.

The seasonal workload on pasture-based dairy farms, combined with increased herd sizes, have led to an increased focus on farm labour time-use and techniques that can reduce farm labour demand. The objective of this study was to measure labour time-use over time on a sample of pasture-based dairy farms and examine the impact that specific facilities and technologies could have on labour demand in real farm situations. Fifty-seven farms completed two labour time-use studies in spring 2019 and 2021 (1st February to 30th April). Farm labour input was recorded on one day each week during the study period. Results showed that farm labour input increased by 3% (1 364 to 1 403 h) between spring 2019 and 2021 and farm labour efficiency improved by 7% (10.7 to 10.0 h/cow), while herd size increased by 10% (145 to 160 cows). Case study farms that made substantial changes to the milking and calf care facilities and practices (between 2019 and 2021) were selected to examine the impact of these changes on labour demand and efficiency. The four case study farms that implemented new milking parlours or added additional milking units improved their milking efficiency by 15% (2.89 to 2.45 h/cow per farm) and reduced milking labour input by 15% (402 to 342 h per farm). Seventeen farms made substantial calf care changes such as constructing a new calf shed, installing an automatic calf feeder, selling male calves and contract rearing heifer calves preweaning. These farms had on average 26 more cows per farm in 2021 than in 2019 (increasing from 137 to 163 cows), but calf care labour input declined by 5% (240 to 228 h per farm) and calf care labour efficiency improved by 16% (1.83 to 1.53 h/cow per farm). Of these farms, the largest improvement was observed on the eight farms that installed automatic calf feeders, where calf care labour efficiency improved by 23% (1.76 to 1.36 h/cow). Results of this study contribute to our understanding of labour use on pasture-based dairy farms and how it can change over time. The real-time on-farm case studies can reassure farmers of the positive benefits that the facilities and technologies outlined in this study can have on labour efficiency.

Electrochemiluminescence Amplification in Bead-Based Assays Induced by a Freely Diffusing Iridium(III) Complex.

Heterogeneous electrochemiluminescence (ECL) assays employing tri-n-propylamine as a co-reactant and a tris(2,2'-bipyridine)ruthenium(II) ([Ru(bpy)3]2+) derivative as an emissive label are integral to the majority of academic and commercial applications of ECL sensing. This model system is an active research area and constitutes the basis of successfully commercialized bead-based ECL immunoassays. Herein, we propose a novel approach to the enhancement of such conventional ECL assays via the incorporation of a second metal coordination complex, [Ir(sppy)3]3- (where sppy = 5'-sulfo-2-phenylpyridinato-C2,N), to the experimental system. By employing ECL microscopy, we are able to map the spatial distribution of ECL emission at the surface of the bead, from [Ru(bpy)3]2+ labels, and solution-phase emission, from [Ir(sppy)3]3-. The developed [Ir(sppy)3]3--mediated enhancement approach elicited a significant improvement (70.9-fold at 0.9 V and 2.9-fold at 1.2 V vs Ag/AgCl) of the ECL signal from [Ru(bpy)3]2+ labels immobilized on the surface of a polystyrene bead. This dramatic enhancement in ECL signal, particularly at low oxidation potentials, has important implications for the improvement of existing heterogeneous ECL assays and ECL-based microscopy, by amplifying the signal, opening new bioanalytical detection schemes, and reducing both electrode surface passivation and deleterious side reactions.

The impact of work organisation on the work life of people on pasture-based dairy farms.

The seasonal workload combined with increased dairy herd sizes and a declining workforce have created social sustainability challenges for pasture-based dairy farms. Effective work organisation can build productive capacity that may have a positive impact on this scenario. Our objective was to develop a framework to characterise and examine the effect of work organisation on the working situations of the people involved in a sample of 55 pasture-based dairy farms in Ireland. We conceptualised that effective work organisation on a dairy farm could be considered as a system that is efficient from a labour input perspective, resulting in a profitable farming system with outcomes of good operator well-being, health and safety, and quality of life. A literature review established efficiency & productivity, flexibility and standardisation as our three characteristics of work organisation. Using data from an existing labour time-use study completed from the 1st February to 30th June 2019, we aimed to test the veracity of these work organisation characteristics in the Irish pasture-based dairy system. Two proxy indicators were selected to represent each of the three work organisation characteristics, and each of the 55 farms were categorised into quartiles based on their ranking for these six indicators (1 = most effective quartile to 4 = least effective quartile). The most and least effective quartiles of farms for work organisation showed similar levels of farm labour input and labour efficiency. Farmers in the most effective work organisation quartile were working 51.2 h/week from February to June compared with 70.0 h/week for farmers in the least effective quartile, which was attributed to later start times, earlier finish times, and more time at non-farm activity. Farms achieving effective work organisation had a labour-efficient system with relatively low farmer working hours. Extension of the work organisation concept to other farms could improve their labour situation and aid in alleviating some of the key quality of life challenges faced by dairy farmers.

A simple, low-cost instrument for electrochemiluminescence immunoassays based on a Raspberry Pi and screen-printed electrodes.

A powerful, yet low-cost and semi-portable electrochemiluminescence (ECL) biosensing device is described. It is constructed around a Raspberry Pi single-board computer, which serves as the controller and user interface. The Pi is interfaced with an expansion board that controls the potential applied to a disposable screen-printed electrode and facilitates data acquisition from a photomultiplier tube (PMT), which detects the ECL emission from the sensor surface. As proof-of-concept, we demonstrate that this arrangement can quantitate tris(2,2'-bipyridine)ruthenium(II) ([Ru(bpy)3]2+]) with an estimated limit of detection (LOD) of 20 pM, and C-reactive protein with an LOD of 50 fg mL-1. The analytical performance of the Raspberry Pi-based setup is comparable to a conventional ECL configuration (computer, potentiostat and photodetector). The Raspberry Pi-based setup can replace a conventional ECL setup, at a fraction of the cost, without sacrificing sensitivity or versatility. The combination of a single-board computer and a sensitive light detector represents a significant step towards translating ECL instruments into mobile, point-of-care diagnostic platforms.

A redox-mediator pathway for enhanced multi-colour electrochemiluminescence in aqueous solution.

The classic and most widely used co-reactant electrochemiluminescence (ECL) reaction of tris(2,2'-bipyridine)ruthenium(ii) ([Ru(bpy)3]2+) and tri-n-propylamine is enhanced by an order of magnitude by fac-[Ir(sppy)3]3- (where sppy = 5'-sulfo-2-phenylpyridinato-C 2,N), through a novel 'redox mediator' pathway. Moreover, the concomitant green emission of [Ir(sppy)3]3-* enables internal standardisation of the co-reactant ECL of [Ru(bpy)3]2+. This can be applied using a digital camera as the photodetector by exploiting the ratio of R and B values of the RGB colour data, providing superior sensitivity and precision for the development of low-cost, portable ECL-based analytical devices.

Construction of a Highly Sensitive Thiol-Reactive AIEgen-Peptide Conjugate for Monitoring Protein Unfolding and Aggregation in Cells.

Impairment of the protein quality control network leads to the accumulation of unfolded and aggregated proteins. Direct detection of unfolded protein accumulation in the cells may provide the possibility for early diagnosis of neurodegenerative diseases. Here a new platform based on a peptide-conjugated thiol-reactive aggregation-induced emission fluorogen (AIEgen), named MI-BTD-P (or D1), for labeling and tracking unfolded proteins in cells is reported. In vitro experiments with model proteins show that the non-fluorescent D1 only becomes highly fluorescent when reacted with the thiol group of free cysteine (Cys) residues on unfolded proteins but not glutathione or folded proteins with buried or surface exposed Cys. When the labeled unfolded proteins form aggregates, D1 fluorescence intensity is further increased, and fluorescence lifetime is prolonged. D1 is then used to measure unfolded protein loads in cells by flow cytometry and track the aggregate formation of the D1 labeled unfolded proteins using confocal microscopy. In combination with fluorescence lifetime imaging technique, the proteome at different folding statuses can be better differentiated, demonstrating the versatility of this new platform. The rational design of D1 demonstrates the outlook of incorporation of diverse functional groups to achieve maximal sensitivity and selectivity in biological samples.

Emission from the working and counter electrodes under co-reactant electrochemiluminescence conditions.

We present a new approach to explore the potential-dependent multi-colour co-reactant electrochemiluminescence (ECL) from multiple luminophores. The potentials at both the working and counter electrodes, the current between these electrodes, and the emission over cyclic voltammetric scans were simultaneously measured for the ECL reaction of Ir(ppy)3 and either [Ru(bpy)3]2+ or [Ir(df-ppy)2(ptb)]+, with tri-n-propylamine as the co-reactant. The counter electrode potential was monitored by adding a differential electrometer module to the potentiostat. Plotting the data against the applied working electrode potential and against time provided complementary depictions of their relationships. Photographs of the ECL at the surface of the two electrodes were taken to confirm the source of the emissions. This provided a new understanding of these multifaceted ECL systems, including the nature of the counter electrode potential and the possibility of eliciting ECL at this electrode, a mechanism-based rationalisation of the interactions of different metal-complex luminophores, and a previously unknown ECL pathway for the Ir(ppy)3 complex at negative potentials that was observed even in the absence of the co-reactant.

Wide-Bite-Angle Diphosphine Ligands in Thermally Activated Delayed Fluorescent Copper(I) Complexes: Impact on the Performance of Electroluminescence Applications.

We report a series of seven cationic heteroleptic copper(I) complexes of the form [Cu(P^P)(dmphen)]BF4, where dmphen is 2,9-dimethyl-1,10-phenanthroline and P^P is a diphosphine chelate, in which the effect of the bite angle of the diphosphine ligand on the photophysical properties of the complexes was studied. Several of the complexes exhibit moderately high photoluminescence quantum yields in the solid state, with ΦPL of up to 35%, and in solution, with ΦPL of up to 98%. We were able to correlate the powder photoluminescence quantum yields with the % Vbur of the P^P ligand. The most emissive complexes were used to fabricate both organic light-emitting diodes and light-emitting electrochemical cells (LECs), both of which showed moderate performance. Compared to the benchmark copper(I)-based LECs, [Cu(dnbp)(DPEPhos)]+ (maximum external quantum efficiency, EQEmax = 16%), complex 3 (EQEmax = 1.85%) showed a much longer device lifetime (t1/2 = 1.25 h and >16.5 h for [Cu(dnbp)(DPEPhos)]+ and complex 3, respectively). The electrochemiluminescence (ECL) properties of several complexes were also studied, which, to the best of our knowledge, constitutes the first ECL study for heteroleptic copper(I) complexes. Notably, complexes exhibiting more reversible electrochemistry were associated with higher annihilation ECL as well as better performance in a LEC.

Controlled growth of ordered monolayers of N-heterocyclic carbenes on silicon.

N-Heterocyclic carbenes (NHCs) are promising modifiers and anchors for surface functionalization and offer some advantages over thiol-based systems. Because of their strong binding affinity and high electron donation, NHCs can dramatically change the properties of the surfaces to which they are bonded. Highly ordered NHC monolayers have so far been limited to metal surfaces. Silicon, however, remains the element of choice in semiconductor devices and its modification is therefore of utmost importance for electronic industries. Here, a comprehensive study on the adsorption of NHCs on silicon is presented. We find covalently bound NHC molecules in an upright adsorption geometry and demonstrate the formation of highly ordered monolayers exhibiting good thermal stability and strong work function reductions. The structure and ordering of the monolayers is controlled by the substrate geometry and reactivity and in particular by the NHC side groups. These findings pave the way towards a tailor-made organic functionalization of silicon surfaces and, thanks to the high modularity of NHCs, new electronic and optoelectronic applications.

Evolution of Topological Surface States Following Sb Layer Adsorption on Bi2Se3.

Thin antimony layers adsorbed on bismuth selenide (Bi2Se3) present an exciting topological insulator system. Much recent effort has been made to understand the synthesis and electronic properties of the heterostructure, particularly the migration of the topological surface states under adsorption. However, the intertwinement of the topological surface states of the pristine Bi2Se3 substrate with the Sb adlayer remains unclear. In this theoretical work, we apply density functional theory (DFT) to model heterostructures of single and double atomic layers of Sb on a bismuth selenide substrate. We thereby discuss established and alternative structural models, as well as the hybridization of topological surface states with the Sb states. Concerning the geometry, we reveal the possibility of structures with inverted Sb layers which are energetically close to the established ones. The formation energy differences are below 10 meV/atom. Concerning the hybridization, we trace the band structure evolution as a function of the adlayer-substrate distance. By following changes in the connection between the Kramers pairs, we extract a series of topological phase transitions. This allows us to explain the origin of the complex band structure, and ultimately complete our knowledge about this peculiar system.

Nature of Optical Excitations in Porphyrin Crystals: A Joint Experimental and Theoretical Study.

The nature of optical excitations and the spatial extent of excitons in organic semiconductors, both of which determine exciton diffusion and carrier mobilities, are key factors for the proper understanding and tuning of material performances. Using a combined experimental and theoretical approach, we investigate the excitonic properties of meso-tetraphenyl porphyrin-Zn(II) crystals. We find that several bands contribute to the optical absorption spectra, beyond the four main ones considered here as the analogue to the four frontier molecular orbitals of the Gouterman model commonly adopted for the isolated molecule. By using many-body perturbation theory in the GW and Bethe-Salpeter equation approach, we interpret the experimental large optical anisotropy as being due to the interplay between long- and short-range intermolecular interactions. In addition, both localized and delocalized excitons in the π-stacking direction are demonstrated to determine the optical response, in agreement with recent experimental observations reported for organic crystals with similar molecular packing.

Luminescent iridium(iii)-boronic acid complexes for carbohydrate sensing.

A family of four Ir(iii) complexes of the form [Ir(ppy)2(L)]Cl (where ppy = 2-phenyl-pyridine and L = a pyridyl-1,2,4-triazole or pyridyl-1,3,4-oxadiazole ligand bearing a boronic acid group) have been prepared as potential luminescent sensors for carbohydrates. A modular eight step procedure was developed to synthesise the complexes, and this was initiated with the preparation of two benzhydrazide and three S-ethylated pyridine-2-thiocarboxamides precursors. Reaction of these precursors produced three new 1,2,4-triazole- and one 1,3,4-oxadiazole-based ligands substituted with boronic acid pinacol ester groups. The boronic acid pinacol esters were then converted to boronic acids in two steps via potassium trifluoroborate intermediates. The boronic acid substituted ligands and their Ir(iii) complexes were fully characterised using a range of techniques including X-ray crystallography in the case of the pyridyl-1,3,4-oxadiazole ligand and two of the Ir(iii) complexes. The capacity of the synthesised Ir(iii) complexes to form boronic acid cyclic esters with the simple sugars glucose and fructose was evaluated using high-resolution mass spectrometry (HRMS) and photoluminescence titration studies. These studies confirm that the Ir(iii) complexes form adducts with both glucose and fructose, with increased levels of boronic acid cyclic esters being formed with fructose at higher pHs. Theoretical calculations were used to gain insight into the nature of the electronic transitions involved in the electronic absorption and emission spectra.