Mid-infrared Gas Sensing Using Graphene Plasmons Tuned by Reversible Chemical Doping

Highly confined plasmon modes in nanostructured graphene can be used to detect tiny quantities of biological and gas molecules. In biosensing, a specific biomarker can be concentrated close to graphene, where the optical field is enhanced, by using an ad-hoc functional layer (e.g., antibodies). Inspired by this approach, in this paper we exploit the chemical and gas adsorption properties of an ultrathin polymer layer deposited on a nanostructured graphene surface to demonstrate a new gas sensing scheme. A proof-of-concept experiment using polyethylenimine (PEI) that is chemically reactive to CO2 molecules is presented. Upon CO2 adsorption, the sensor optical response changes because of PEI vibrational modes enhancement and shift in plasmon resonance, the latter related to polymer-induced doping of graphene. We show that the change in optical response is reversed during CO2 desorption. The demonstrated limit of detection (LOD) of 390 ppm corresponds to the lowest value detectable in ambient atmosphere, which can be lowered by operating in vacuum. By using specific adsorption polymers, the proposed sensing scheme can be easily extended to other relevant gases, for example, volatile organic compounds.Peer ReviewedPostprint (published version

Volatile Organic Compound Composition of Urban Air in Nairobi, Kenya and Lagos, Nigeria

Sub-Saharan Africa is seeing rapid urbanization, with the population of cities such as Lagos and Nairobi growing at a rate of 3–4% a year. The region is extremely under-sampled for all air pollutants, particularly VOCs, which are useful markers for source apportionment as well as toxic in their own right. There are many contributors to air pollution in the region, and studies examining fine particulate pollution implicate traffic as the primary source in urban areas. In this pilot study, VOCs were analysed at a selection of roadside and urban background locations in Nairobi and Lagos, and 74 VOCs were quantified. GC×GC–MS/FID analysis revealed all locations were dominated by hydrocarbons typical of vehicle emissions, with the aromatic hydrocarbons benzene and toluene among the most abundant VOCs. Typical personal exposure scenarios for citizens of the cities were calculated to far exceed those of a resident in a city in Europe/US. Finally, the calculated ozone forming potential of the VOCs measured was found to be similarly high to other large cities studied with similar air pollution problems. Further study is therefore essential to determine the full extent of VOC pollution in the region and its impact on tropospheric chemistry

The Exposure of Workers at a Busy Road Node to PM2.5: Occupational Risk Characterisation and Mitigation Measures

The link between air pollution and health burden in urban areas has been well researched. This has led to a plethora of effective policy-induced monitoring and interventions in the global south. However, the implication of pollutant species like PM2.5 in low middle income countries (LMIC) still remains a concern. By adopting a positivist philosophy and deductive reasoning, this research addresses the question, to what extent can we deliver effective interventions to improve air quality at a building structure located at a busy road node in a LMIC? This study assessed the temporal variability of pollutants around the university environment to provide a novel comparative evaluation of occupational shift patterns and the use of facemasks as risk control interventions. The findings indicate that the concentration of PM2.5, which can be as high as 300% compared to the WHO reference, was exacerbated by episodic events. With a notable decay period of approximately one-week, adequate protection and/or avoidance of hotspots are required for at-risk individuals within a busy road node. The use of masks with 80% efficiency provides sufficient mitigation against exposure risks to elevated PM2.5 concentrations without occupational shift, and 50% efficiency with at least ‘2 h ON, 2 h OFF’ occupational shift scenario

GAPS-megacities: A new global platform for investigating persistent organic pollutants and chemicals of emerging concern in urban air

A pilot study was initiated in 2018 under the Global Atmospheric Passive Sampling (GAPS) Network named GAPS-Megacities. This study included 20 megacities/major cities across the globe with the goal of better understanding and comparing ambient air levels of persistent organic pollutants and other chemicals of emerging concern, to which humans residing in large cities are exposed. The first results from the initial period of sampling are reported for 19 cities for several classes of flame retardants (FRs) including organophosphate esters (OPEs), polybrominated diphenyl ethers (PBDEs), and halogenated flame retardants (HFRs) including new flame retardants (NFRs), tetrabromobisphenol A (TBBPA) and hexabromocyclododecane (HBCDD). The two cities, New York (USA) and London (UK) stood out with ∼3.5 to 30 times higher total FR concentrations as compared to other major cities, with total concentrations of OPEs of 15,100 and 14,100 pg/m3, respectively. Atmospheric concentrations of OPEs significantly dominated the FR profile at all sites, with total concentrations in air that were 2-5 orders of magnitude higher compared to other targeted chemical classes. A moderately strong and significant correlation (r = 0.625, p < 0.001) was observed for Gross Domestic Product index of the cities with total OPEs levels. Although large differences in FR levels were observed between some cities, when averaged across the five United Nations regions, the FR classes were more evenly distributed and varied by less than a factor of five. Results for Toronto, which is a "reference city" for this study, agreed well with a more in-depth investigation of the level of FRs over different seasons and across eight sites representing different urban source sectors (e.g. traffic, industrial, residential and background). Future sampling periods under this project will investigate trace metals and other contaminant classes, linkages to toxicology, non-targeted analysis, and eventually temporal trends. The study provides a unique urban platform for evaluating global exposome.Fil: Saini, Amandeep. Environment and Climate Change; CanadáFil: Harner, Tom. Environment and Climate Change; CanadáFil: Chinnadhurai, Sita. Environment and Climate Change; CanadáFil: Schuster, Jasmin K.. Environment and Climate Change; CanadáFil: Yates, Alan. Environment and Climate Change; CanadáFil: Sweetman, Andrew. Lancaster Environment Centre; Reino UnidoFil: Aristizabal Zuluaga, Beatriz H.. Universidad Nacional de Colombia; ColombiaFil: Jiménez, Begoña. Consejo Superior de Investigaciones Científicas; EspañaFil: Manzano, Carlos A.. Universidad de Chile; ChileFil: Gaga, Eftade O.. Eskisehir Technical University; TurquíaFil: Stevenson, Gavin. National Measurement Institute; AustraliaFil: Falandysz, Jerzy. Uniwersytet Gdanski; PoloniaFil: Ma, Jianmin. Peking University; ChinaFil: Miglioranza, Karina Silvia Beatriz. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mar del Plata. Instituto de Investigaciones Marinas y Costeras. Universidad Nacional de Mar del Plata. Facultad de Ciencias Exactas y Naturales. Instituto de Investigaciones Marinas y Costeras; ArgentinaFil: Kannan, Kurunthachalam. Nyu Grossman School Of Medicine; Estados UnidosFil: Tominaga, Maria. Sao Paulo State Environmental Company; BrasilFil: Jariyasopit, Narumol. No especifíca;Fil: Rojas, Nestor Y.. Universidad Nacional de Colombia; ColombiaFil: Amador-Muñoz, Omar. Universidad Nacional Autónoma de México; MéxicoFil: Sinha, Ravindra. Patna University; IndiaFil: Alani, Rose. University of Lagos; NigeriaFil: Suresh, R.. No especifíca;Fil: Nishino, Takahiro. Tokyo Metropolitan Research Institute for Environmental Protection; JapónFil: Shoeib, Tamer. American University In Cairo; Egipt

The pch2Δ Mutation in Baker's Yeast Alters Meiotic Crossover Levels and Confers a Defect in Crossover Interference

Pch2 is a widely conserved protein that is required in baker's yeast for the organization of meiotic chromosome axes into specific domains. We provide four lines of evidence suggesting that it regulates the formation and distribution of crossover events required to promote chromosome segregation at Meiosis I. First, pch2Δ mutants display wild-type crossover levels on a small (III) chromosome, but increased levels on larger (VII, VIII, XV) chromosomes. Second, pch2Δ mutants show defects in crossover interference. Third, crossovers observed in pch2Δ require both Msh4-Msh5 and Mms4-Mus81 functions. Lastly, the pch2Δ mutation decreases spore viability and disrupts crossover interference in spo11 hypomorph strains that have reduced levels of meiosis-induced double-strand breaks. Based on these and previous observations, we propose a model in which Pch2 functions at an early step in crossover control to ensure that every homolog pair receives an obligate crossover

Incompatibilities Involving Yeast Mismatch Repair Genes: A Role for Genetic Modifiers and Implications for Disease Penetrance and Variation in Genomic Mutation Rates

Genetic background effects underlie the penetrance of most genetically determined phenotypes, including human diseases. To explore how such effects can modify a mutant phenotype in a genetically tractable system, we examined an incompatibility involving the MLH1 and PMS1 mismatch repair genes using a large population sample of geographically and ecologically diverse Saccharomyces cerevisiae strains. The mismatch repair incompatibility segregates into naturally occurring yeast strains, with no strain bearing the deleterious combination. In assays measuring the mutator phenotype conferred by different combinations of MLH1 and PMS1 from these strains, we observed a mutator phenotype only in combinations predicted to be incompatible. Surprisingly, intragenic modifiers could be mapped that specifically altered the strength of the incompatibility over a 20-fold range. Together, these observations provide a powerful model in which to understand the basis of disease penetrance and how such genetic variation, created through mating, could result in new mutations that could be the raw material of adaptive evolution in yeast populations

Mutator dynamics in sexual and asexual experimental populations of yeast

<p>Abstract</p> <p>Background</p> <p>In asexual populations, mutators may be expected to hitchhike with associated beneficial mutations. In sexual populations, recombination is predicted to erode such associations, inhibiting mutator hitchhiking. To investigate the effect of recombination on mutators experimentally, we compared the frequency dynamics of a mutator allele (<it>msh2</it>Δ) in sexual and asexual populations of <it>Saccharomyces cerevisiae</it>.</p> <p>Results</p> <p>Mutator strains increased in frequency at the expense of wild-type strains in all asexual diploid populations, with some approaching fixation in 150 generations of propagation. Over the same period of time, mutators declined toward loss in all corresponding sexual diploid populations as well as in haploid populations propagated asexually.</p> <p>Conclusions</p> <p>We report the first experimental investigation of mutator dynamics in sexual populations. We show that a strong mutator quickly declines in sexual populations while hitchhiking to high frequency in asexual diploid populations, as predicted by theory. We also show that the <it>msh2Δ </it>mutator has a high and immediate realized cost that is alone sufficient to explain its decline in sexual populations. We postulate that this cost is indirect; namely, that it is due to a very high rate of recessive lethal or strongly deleterious mutation. However, we cannot rule out the possibility that <it>msh2</it>Δ also has unknown directly deleterious effects on fitness, and that these effects may differ between haploid asexual and sexual populations. Despite these reservations, our results prompt us to speculate that the short-term cost of highly deleterious recessive mutations can be as important as recombination in preventing mutator hitchhiking in sexual populations.</p

Methylated H3K4, a Transcription-Associated Histone Modification, Is Involved in the DNA Damage Response Pathway

Eukaryotic genomes are associated with a number of proteins such as histones that constitute chromatin. Post-translational histone modifications are associated with regulatory aspects executed by chromatin and all transactions on genomic DNA are dependent on them. Thus, it will be relevant to understand how histone modifications affect genome functions. Here we show that the mono ubiquitylation of histone H2B and the tri-methylation of histone H3 on lysine 4 (H3K4me3), both known for their involvement in transcription, are also important for a proper response of budding yeast cells to DNA damaging agents and the passage through S-phase. Cells that cannot methylate H3K4 display a defect in double-strand break (DSB) repair by non-homologous end joining. Furthermore, if such cells incur DNA damage or encounter a stress during replication, they very rapidly lose viability, underscoring the functional importance of the modification. Remarkably, the Set1p methyltransferase as well as the H3K4me3 mark become detectable on a newly created DSB. This recruitment of Set1p to the DSB is dependent on the presence of the RSC complex, arguing for a contribution in the ensuing DNA damage repair process. Taken together, our results demonstrate that Set1p and its substrate H3K4me3, which has been reported to be important for the transcription of active genes, also plays an important role in genome stability of yeast cells. Given the high degree of conservation for the methyltransferase and the histone mark in a broad variety of organisms, these results could have similar implications for genome stability mechanisms in vertebrate and mammalian cells

The Baker's Yeast Diploid Genome Is Remarkably Stable in Vegetative Growth and Meiosis

Accurate estimates of mutation rates provide critical information to analyze genome evolution and organism fitness. We used whole-genome DNA sequencing, pulse-field gel electrophoresis, and comparative genome hybridization to determine mutation rates in diploid vegetative and meiotic mutation accumulation lines of Saccharomyces cerevisiae. The vegetative lines underwent only mitotic divisions while the meiotic lines underwent a meiotic cycle every ∼20 vegetative divisions. Similar base substitution rates were estimated for both lines. Given our experimental design, these measures indicated that the meiotic mutation rate is within the range of being equal to zero to being 55-fold higher than the vegetative rate. Mutations detected in vegetative lines were all heterozygous while those in meiotic lines were homozygous. A quantitative analysis of intra-tetrad mating events in the meiotic lines showed that inter-spore mating is primarily responsible for rapidly fixing mutations to homozygosity as well as for removing mutations. We did not observe 1–2 nt insertion/deletion (in-del) mutations in any of the sequenced lines and only one structural variant in a non-telomeric location was found. However, a large number of structural variations in subtelomeric sequences were seen in both vegetative and meiotic lines that did not affect viability. Our results indicate that the diploid yeast nuclear genome is remarkably stable during the vegetative and meiotic cell cycles and support the hypothesis that peripheral regions of chromosomes are more dynamic than gene-rich central sections where structural rearrangements could be deleterious. This work also provides an improved estimate for the mutational load carried by diploid organisms

Molecular analysis of Saccharomyces cerevisiae chromosome I : On the number of genes and the identification of essential genes using temperature-sensitive-lethal mutations

Previous analyses of Saccharomyces cerevisiae chromosome I have suggested that the majority (&gt;75%) of single-copy essential genes on this chromosome are difficult or impossible to identify using temperature-sensitive (Ts-) lethal mutations. To investigate whether this situation reflects intrinsic difficulties in generating temperature-sensitive proteins or constraints on mutagenesis in yeast, we subjected three cloned essential genes from chromosome I to mutagenesis in an Escherichia coli mutator strain and screened for Ts- lethal mutations in yeast using the "plasmid-shuffle" technique. We failed to obtain Ts- lethal mutations in two of the genes (FUN12 and FUN20), while the third gene yielded such mutations, but only at a low frequency. DNA sequence analysis of these mutant alleles and of the corresponding wild-type region revealed that each mutation was a single substitution not in the previously identified gene FUN19, but in the adjacent, newly identified essential gene FUN53. FUN19 itself proved to be non-essential. These results suggest that many essential proteins encoded by genes on chromosome I cannot be rendered thermolabile by single mutations. However, the results obtained with FUN53 suggest that there may also be significant constraints on mutagenesis in yeast. The 5046 base-pair interval sequenced contains the complete FUN19, FUN53 and FUN20 coding regions, as well as a portion of the adjacent non-essential FUN21 coding region. In all, 68 to 75% of this interval is open reading frame. None of the four predicted products shows significant homologies to known proteins in the available databases.Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/30054/1/0000422.pd