Short chains of porphyrin molecules can mediate electron transport over distances as long as 5-10 nm with low attenuation. This means that porphyrin-based molecular wires could be useful in nanoelectronic and photovoltaic devices, but the mechanisms responsible for charge transport in single oligo-porphyrin wires have not yet been established. Here, based on electrical measurements of single-molecule junctions, we show that the conductance of the oligo-porphyrin wires has a strong dependence on temperature, and a weak dependence on the length of the wire. Although it is widely accepted that such behaviour is a signature of a thermally assisted incoherent (hopping) mechanism, density functional theory calculations and an accompanying analytical model strongly suggest that the observed temperature and length dependence is consistent with phase-coherent tunnelling through the whole molecular junction.
A series of thioacetate-terminated butadiyne-linked porphyrin oligomers have been synthesized with one to three porphyrin repeat units. Single molecule electrical scanning tunneling microscopy measurements using the I(s) and I(t) methods were used to determine the molecule conductances for this series of oligomers. The molecular conductance shows an exponential falloff with sulfur-sulfur distance with a remarkably low attenuation factor of beta = (0.04 +/- 0.006) A-1.
Mercury‐dependent artisanal and small‐scale gold mining (ASGM) is the largest source of mercury pollution on Earth. In this practice, elemental mercury is used to extract gold from ore as an amalgam. The amalgam is typically isolated by hand and then heated—often with a torch or over a stove—to distill the mercury and isolate the gold. Mercury release from tailings and vaporized mercury exceed 1000 tonnes each year from ASGM. The health effects on the miners are dire, with inhaled mercury leading to neurological damage and other health issues. The communities near these mines are also affected due to mercury contamination of water and soil and subsequent accumulation in food staples, such as fish—a major source of dietary protein in many ASGM regions. The risks to children are also substantial, with mercury emissions from ASGM resulting in both physical and mental disabilities and compromised development. Between 10 and 19 million people use mercury to mine for gold in more than 70 countries, making mercury pollution from ASGM a global issue. With the Minamata Convention on Mercury entering force this year, there is political motivation to help overcome the problem of mercury in ASGM. In this effort, chemists can play a central role. Here, the problem of mercury in ASGM is reviewed with a discussion on how the chemistry community can contribute solutions. Introducing portable and low‐cost mercury sensors, inexpensive and scalable remediation technologies, novel methods to prevent mercury uptake in fish and food crops, and efficient and easy‐to‐use mercury‐free mining techniques are all ways in which the chemistry community can help. To meet these challenges, it is critical that new technologies or techniques are low‐cost and adaptable to the remote and under‐resourced areas in which ASGM is most common. The problem of mercury pollution in ASGM is inherently a chemistry problem. We therefore encourage the chemistry community to consider and address this issue that affects the health of millions of people.
A key goal in molecular electronics has been to find molecules that facilitate efficient charge transport over long distances. Normally, molecular wires become less conductive with increasing length. Here, we report a series of fused porphyrin oligomers for which the conductance increases substantially with length by >10-fold at a bias of 0.7 V. This exceptional behavior can be attributed to the rapid decrease of the HOMO-LUMO gap with the length of fused porphyrins. In contrast, for butadiyne-linked porphyrin oligomers with moderate inter-ring coupling, a normal conductance decrease with length is found for all bias voltages explored (±1 V), although the attenuation factor (β) decreases from ca. 2 nm at low bias to <1 nm at 0.9 V, highlighting that β is not an intrinsic molecular property. Further theoretical analysis using density functional theory underlines the role of intersite coupling and indicates that this large increase in conductance with length at increasing voltages can be generalized to other molecular oligomers.
Crude oil and hydrocarbon fuel spills are a perennial threat to aquatic environments. Inexpensive and sustainable sorbents are needed to mitigate the ecological harm of this pollution. To address this need, this study features a low‐density polysulfide polymer that is prepared by the direct reaction of sulfur and used cooking oils. Because both sulfur and cooking oils are hydrophobic, the polymer has an affinity for hydrocarbons such as crude oil and diesel fuel and can rapidly remove them from seawater. Through simple mechanical compression, the oil can be recovered and the polymer can be reused in oil spill remediation. The polysulfide is unique because it is prepared entirely from repurposed waste: sulfur is a by‐product of the petroleum industry and used cooking oil can be used as a comonomer. In this way, sulfur waste from the oil industry is used to make an effective sorbent for combatting pollution from that same sector.
The length dependence of charge transport is evaluated in three families of porphyrin-based wires. Planar edge-fused tapes and alkyne-linked oligomers mediate efficient charge transport with exceptionally shallow distance dependence, whereas the conductances of the twisted singly linked chains decrease steeply with increasing oligomer length. The planar tapes are more conjugated than the alkyne-linked oligomers, but these two types of wires have similar conductance attenuation factors.
Inverse vulcanization provides dynamic and responsive materials made from elemental sulfur and unsaturated cross-linkers. These polymers have been used in av ariety of applicationss uch as energy storage, infrared optics, repairable materials, environmental remediation, and precision fertilizers. In spite of thesea dvances, there is an eed for methods to recycle and reprocess these polymers. In this study,p olymers prepared by inverse vulcanization are shown to undergo reactive compression molding. In this process, the reactive interfaces of sulfur polymers are brought into contact by mechanicalc ompression.U pon heating these molds at relatively low temperatures (% 100 8C), chemical bonding occurs at the polymer interfaces by SÀSm etathesis. This method of processing is distinct from previouss tudies on inverse vulcanization because the polymers examined in this study do not form al iquid phase when heated. Neither compression nor heatinga lone was sufficient to mold these polymers into new architectures, so this is an ew concept in the manipulation of sulfur polymers. Additionally,h igh-level ab initio calculations revealed that the weakest SÀSb ond in organic polysulfides decreases linearly in strength from as ulfur rank of 2t o4 ,b ut then remains constant at about 100kJmol À1 for highers ulfur rank. This is criticali nformation in engineering these polymers for SÀSm etathesis. Guidedb yt his insight, polymer repair,r ecycling, and repurposingi nto new composites was demonstrated.
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