Optimizing energy costs in a zinc and lead mine

Boliden Tara Mines Ltd. consumed 184.7 GWh of electricity in 2014, equating to over 1% of the national demand of Ireland or approximately 35,000 homes. Ireland's industrial electricity prices, at an average of 13 c/KWh in 2014, are amongst the most expensive in Europe. Cost effective electricity procurement is ever more pressing for businesses to remain competitive. In parallel, the proliferation of intelligent devices has led to the industrial Internet of Things paradigm becoming mainstream. As more and more devices become equipped with network connectivity, smart metering is fast becoming a means of giving energy users access to a rich array of consumption data. These modern sensor networks have facilitated the development of applications to process, analyse, and react to continuous data streams in real-time. Subsequently, future procurement and consumption decisions can be informed by a highly detailed evaluation of energy usage. With these considerations in mind, this paper uses variable energy prices from Ireland’s Single Electricity Market, along with smart meter sensor data, to simulate the scheduling of an industrial-sized underground pump station in Tara Mines. The objective is to reduce the overall energy costs whilst still functioning within the system's operational constraints. An evaluation using real-world electricity prices and detailed sensor data for 2014 demonstrates significant savings of up to 10.72% over the year compared to the existing control systems

Multimodal switching of a redox-active macrocycle

Molecules that can switch between multiple stable states in response to stimuli are promising for many applications, but are challenging to construct. Here, the authors design a resorcinarene switching manifold with multiple oxidation states and coupled charge-transfer states, which can access up to five distinct switch-states with unique optical outputs

Nanomolecular singlet oxygen photosensitizers based on hemiquinonoid-resorcinarenes, the fuchsonarenes

Singlet oxygen sensitization involving a class of hemiquinonoid-substituted resorcinarenes prepared from the corresponding 3,5-di-t-butyl-4-hydroxyphenyl-substituted resorcinarenes is reported. Based on variation in the molecular structures, quantum yields comparable with that of the well-known photosensitizing compound meso-tetraphenylporphyrin were obtained for the octabenzyloxy-substituted double hemiquinonoid resorcinarene reported herein. The following classes of compounds were studied: benzyloxy-substituted resorcinarenes, acetyloxy-substituted resorcinarenes and acetyloxy-substituted pyrogallarenes. Single crystal X-ray crystallographic analyses revealed structural variations in the compounds with conformation (i.e., rctt, rccc, rcct) having some influence on the identity of hemiquinonoid product available. Multiplicity of hemiquinonoid group affects singlet oxygen quantum yield with those doubly substituted being more active than those containing a single hemiquinone. Compounds reported here lacking hemiquinonoid groups are inactive as photosensitizers. The term ‘fuchsonarene’ (fuchson + arene of resorcinarene) is proposed for use to classify the compounds

Increasing the complexity of oxoporphyrinogen colorimetric sensing chromophores: N-alkylation and β-substitution

Meso-5,10,15,20-tetrakis-3,5-di-tert-butyl-4-oxocyclohexadienylideneporphyrinogen, OxP, is a versatile, highly colored chromophore derived from meso-5,10,15,20-tetrakis(3,5-di-tert-butyl-4-hydroxyphenyl)porphyrin. It exhibits a wide range of chromogenic responses to solvents (solvatochromism), anions and acidic media (halochromism) making it potentially useful as an analytical reagent. The chromogenic responses of OxP can be modulated by varying its chemical structure, and this is reviewed here based on the introduction of substituents at central nitrogen atoms or pyrrolic β -positions. OxP and its N-alkylated derivates Bn2OxP and Bn4OxP have been used to estimate acidity in non-polar solvents. Bn2OxP can also be used to determine enantiomeric excesses of chiral substances. N-alkylation has also been used to introduce higher functional groups such as porphyrins to prepare self-assembling systems. β-Substitution has been used to introduce selectivity of anion interactions including towards basic anions (fluoride, cyanide) and polyoxoanions (nitrate, perchlorate, etc.). These aspects make OxP a highly adaptable tetrapyrrole molecule for sensing and other applications

Electron and energy transfer in a porphyrin–oxoporphyrinogen–fullerene triad, ZnP–OxP–C₆₀

A multichromophoric triad, ZnP–OxP–C60 containing porphyrin (ZnTPP hereafter ZnP), oxoporphyrinogen (OxP) and fullerene (C60) has been synthesized to probe the intramolecular dynamics of its electron and energy transfer in relation to the presence of the closely linked electron deficient OxP–C60 ‘special pair’, constructed as a mimic of the naturally occurring photosynthetic antenna-reaction center. The DFT optimized structure of the triad reveals the relative spatial remoteness of the ZnP entity with proximal OxP/C60 entities. Free-energetics of different energy and electron transfer events were estimated using spectral, computational and electrochemical studies, according to the Rehm–Weller approach. Femtosecond transient absorption spectral studies revealed energy transfer from 1ZnP* to OxP to yield ZnP–1OxP*–C60, and electron transfer to yield ZnP˙+–OxP–C60˙− and/or ZnP–OxP˙+–C60˙− charge seperated states. That is, the ZnP entity in the triad operates as both antenna and electron donor to generate relatively long-lived charge separated states thus mimicking the early photoevents of natural photosynthesis

Diporphyrin tweezer for multichannel spectroscopic analysis of enantiomeric excess

Chiral 1,1’-binaphthyl-linked diporphyrin ‘tweezers’ (R)-1/(S)-1 and the corresponding zinc(II) complexes (R)-2(S)-2 were prepared as chiral host molecules, and their utility for chiral analyses (especially enantiomeric excess (ee) determinations) were evaluated. Tris(1-n-dodecyl)porphyrins were used for the first time as the interacting units. Host capabilities of the diporphyrin tweezers were investigated by titrations with (R,R)- and (S,S)-cyclohexane-1,2-diamine (CHDA). The host molecules could be used as multichannel probes of ee by using UV-vis, circular dichroism (CD), fluorescence emission and 1H nuclear magnetic resonance (1H-NMR) methods. Chiral configurations could also be differentiated using CD or 1H-NMR spectroscopy. All three optical techniques give good resolution of ee with reasonable sensitivity considering the low concentrations used (ca. 10−6 mol·L−1). The ee determination of CHDA enantiomers using NMR spectroscopy is also possible because of the reasonably well separated resonances in the case of (R,R)- and (S,S)-CHDA. Non-metallated (R)-1/(S)-1 hosts could not be used to detect chiral information in a strongly acidic chiral guest. This work demonstrates the utility of 1,1’-binapthyl-linked chiral hosts for chiral analysis of ditopically interacting enantiomers

Knock-on synthesis of tritopic calix[4]pyrrole host for enhanced anion interactions

Interactions of anionic guests with a tritopic peripherally functionalized conjugated calix[4]pyrrole host (1) prepared using a regioselective synthetic method is reported. The regioselectivity of synthesis relies on selective N-alkylation of the calix[4]pyrrole caused by peripheral substitution of one pyrrole group with subsequent N-alkylation at the opposing pyrrole group termed by us ‘knock-on’ regioselectivity. The resulting host molecule exhibits anion interactions with common chloride and nitrate anions enhanced by an order of magnitude over the parent conjugated calix[4]pyrrole. Combined analysis of 1H NMR and UV-vis spectroscopic titration data enabled an evaluation of binding strengths of anions with the host KA in a binding model where the salt dissociation process is also incorporated in the form of its dissociation constant Kd. Anions could be classified as two types based on their interactions with 1: Type A anions (chloride, nitrate, perchlorate, hydrogensulphate) associate as 1 : 1 complexes through hydrogen bonding while interactions involving Type B anions (acetate, fluoride, dihydrogenphosphate) are complicated by host deprotonation and/or countercation association. Hosts based on rim-functionalized calix[4]pyrroles such as 1 represent a promising new family of chromophores for estimation of biologically relevant anions or other species

Amphiprotism-Coupled Near-Infrared Emission in Extended Pyrazinacenes Containing Seven Linearly Fused Pyrazine Units

International audiencePeripherally substituted tetradecaazaheptacene (NHp) compounds, exhibiting amphiprotism-coupled emission, have been synthesized. X-ray crystallography reveals a planar acene-like chromophore, and electronic absorption and emission occur in the near-infrared biological transparency window (650-900 nm). The compounds exhibit long-wavelength emission with photoluminescence quantum yields Φ up to ∼0.61 at 686 nm, with the monodeprotonated state Φ ≈ 0.58 at 712 nm. This unprecedented highly nitrogenous chromophore illustrates the stability and utility of the pyrazinacenes for different applications based on their photophysical properties and chemical structures