Bimetallic Two-Dimensional Metal–Organic Frameworks for the Chemiresistive Detection of Carbon Monoxide

This paper describes the demonstration of a series of heterobimetallic, isoreticular 2D conductive metal–organic frameworks (MOFs) with metallophthalocyanine (MPc, M=Co and Ni) units interconnected by Cu nodes towards low-power chemiresistive sensing of ppm levels of carbon monoxide (CO). Devices achieve a sub-part-per-million (ppm) limit of detection (LOD) of 0.53 ppm toward CO at a low driving voltage of 0.1 V. MPc-based Cu-linked MOFs can continuously detect CO at 50 ppm, the permissible exposure limit required by the Occupational Safety and Health Administration (OSHA), for multiple exposures, and realize CO detection in air and in humid environment. Diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), density functional theory (DFT) calculations, and comparison experiments suggest the contribution of Cu nodes to CO binding and the essential role of MPc units in tuning and amplifying the sensing response

Conductive Stimuli-Responsive Coordination Network Linked with Bismuth for Chemiresistive Gas Sensing

This paper describes the design, synthesis, characterization, and performance of a novel semiconductive crystalline coordination network, synthesized using 2,3,6,7,10,11-hexahydroxytriphenylene (HHTP) ligands interconnected with bismuth ions, toward chemiresistive gas sensing. Bi(HHTP) exhibits two distinct structures upon hydration and dehydration of the pores within the network, Bi(HHTP)-α and Bi(HHTP)-β, respectively, both with unprecedented network topology (2,3-c and 3,4,4,5-c nodal net stoichiometry, respectively) and unique corrugated coordination geometries of HHTP molecules held together by bismuth ions, as revealed by a crystal structure resolved via microelectron diffraction (MicroED) (1.00 Å resolution). Good electrical conductivity (5.3 × 10–3 S·cm–1) promotes the utility of this material in the chemical sensing of gases (NH3 and NO) and volatile organic compounds (VOCs: acetone, ethanol, methanol, and isopropanol). The chemiresistive sensing of NO and NH3 using Bi(HHTP) exhibits limits of detection 0.15 and 0.29 parts per million (ppm), respectively, at low driving voltages (0.1–1.0 V) and operation at room temperature. This material is also capable of exhibiting unique and distinct responses to VOCs at ppm concentrations. Spectroscopic assessment via X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared spectroscopic methods (i.e., attenuated total reflectance-infrared spectroscopy (ATR-IR) and diffuse reflectance infrared Fourier transformed spectroscopy (DRIFTS)), suggests that the sensing mechanisms of Bi(HHTP) to VOCs, NO, and NH3 comprise a complex combination of steric, electronic, and protic properties of the targeted analytes

Quantum harmonic oscillator systems with disorder

We study many-body properties of quantum harmonic oscillator lattices with disorder. A sufficient condition for dynamical localization, expressed as a zero-velocity Lieb-Robinson bound, is formulated in terms of the decay of the eigenfunction correlators for an effective one-particle Hamiltonian. We show how state-of-the-art techniques for proving Anderson localization can be used to prove that these properties hold in a number of standard models. We also derive bounds on the static and dynamic correlation functions at both zero and positive temperature in terms of one-particle eigenfunction correlators. In particular, we show that static correlations decay exponentially fast if the corresponding effective one-particle Hamiltonian exhibits localization at low energies, regardless of whether there is a gap in the spectrum above the ground state or not. Our results apply to finite as well as to infinite oscillator systems. The eigenfunction correlators that appear are more general than those previously studied in the literature. In particular, we must allow for functions of the Hamiltonian that have a singularity at the bottom of the spectrum. We prove exponential bounds for such correlators for some of the standard models

Epitaxial Self-Assembly of Interfaces of 2D Metal–Organic Frameworks for Electroanalytical Detection of Neurotransmitters

This paper identifies the electrochemical properties of individual facets of anisotropic layered conductive metal–organic frameworks (MOFs) based on M3(2,3,6,7,10,11-hexahydroxytriphenylene)2 (M3(HHTP)2) (M = Co, Ni). The electroanalytical advantages of each facet are then applied toward the electrochemical detection of neurochemicals. By employing epitaxially controlled deposition of M3(HHTP)2 MOFs on electrodes, the contribution of the basal plane ({001} facets) and edge sites ({100} facets) of these MOFs can be individually determined using electrochemical characterization techniques. Despite having a lower observed heterogeneous electron transfer rate constant, the {001} facets of the M3(HHTP)2 systems prove more selective and sensitive for the detection of dopamine than the {100} facets of the same MOF, with the limit of detection (LOD) of 9.9 ± 2 nM in phosphate-buffered saline and 214 ± 48 nM in a simulated cerebrospinal fluid. Langmuir isotherm studies accompanied by all-atom MD simulations suggested that the observed improvement in performance and selectivity is related to the adsorption characteristics of analytes on the basal plane versus edge sites of the MOF interfaces. This work establishes that the distinct crystallographic facets of 2D MOFs can be used to control the fundamental interactions between analyte and electrode, leading to tunable electrochemical properties by controlling their preferential orientation through self-assembly

Alkalilimnicola ehrlichii sp. nov., a novel, arsenite-oxidizing haloalkaliphilic gammaproteobacterium capable of chemoautotrophic or heterotrophic growth with nitrate or oxygen as the electron acceptor

A facultative chemoautotrophic bacterium, strain MLHE-1T, was isolated from Mono Lake, an alkaline hypersaline soda lake in California, USA. Cells of strain MLHE-1T were Gram-negative, short motile rods that grew with inorganic electron donors (arsenite, hydrogen, sulfide or thiosulfate) coupled with the reduction of nitrate to nitrite. No aerobic growth was attained with arsenite or sulfide, but hydrogen sustained both aerobic and anaerobic growth. No growth occurred when nitrite or nitrous oxide was substituted for nitrate. Heterotrophic growth was observed under aerobic and anaerobic (nitrate) conditions. Cells of strain MLHE-1T could oxidize but not grow on CO, while CH4 neither supported growth nor was it oxidized. When grown chemoautotrophically, strain MLHE-1T assimilated inorganic carbon via the Calvin-Benson-Bassham reductive pentose phosphate pathway, with the activity of ribulose 1,5-bisphosphate carboxylase (RuBisCO) functioning optimally at 0.1 M NaCl and at pH 7.3. Strain MLHE-1T grew over broad ranges of pH (7.3-10.0; optimum, 9.3), salinity (115-190 g l-1; optimum 30 g l-1) and temperature (113-40 °C; optimum, 30 °C). Phylogenetic analysis of 16S rRNA gene sequences placed strain MLHE-1T in the class Gammaproteobacteria (family Ectothiorhodospiraceae) and most closely related to Alkalispirillum mobile (98.5%) and Alkalilimnicola halodurans (98.6%), although none of these three haloalkaliphilic micro-organisms were capable of photoautotrophic growth and only strain MLHE-1T was able to oxidize As(III). On the basis of physiological characteristics and DNA-DNA hybridization data, it is suggested that strain MLHE-1T represents a novel species within the genus Alkalilimnicola for which the name Alkalilimnicola ehrlichii is proposed. The type strain is MLHE-1T (=DSM 17681T =ATCC BAA-1101T). Aspects of the annotated full genome of Alkalilimnicola ehrlichii are discussed in the light of its physiology. © 2007 IUMS

Global Bounds for the Lyapunov Exponent and the Integrated Density of States of Random Schr\"odinger Operators in One Dimension

In this article we prove an upper bound for the Lyapunov exponent $\gamma(E)$ and a two-sided bound for the integrated density of states $N(E)$ at an arbitrary energy $E>0$ of random Schr\"odinger operators in one dimension. These Schr\"odinger operators are given by potentials of identical shape centered at every lattice site but with non-overlapping supports and with randomly varying coupling constants. Both types of bounds only involve scattering data for the single-site potential. They show in particular that both $\gamma(E)$ and $N(E)-\sqrt{E}/\pi$ decay at infinity at least like $1/\sqrt{E}$. As an example we consider the random Kronig-Penney model.Comment: 9 page

Fabrication of Multifunctional Electronic Textiles Using Oxidative Restructuring of Copper into a Cu-Based Metal–Organic Framework

This paper describes a novel synthetic approach for the conversion of zero-valent copper metal into a conductive two-dimensional layered metal–organic framework (MOF) based on 2,3,6,7,10,11-hexahydroxytriphenylene (HHTP) to form Cu3(HHTP)2. This process enables patterning of Cu3(HHTP)2 onto a variety of flexible and porous woven (cotton, silk, nylon, nylon/cotton blend, and polyester) and non-woven (weighing paper and filter paper) substrates with microscale spatial resolution. The method produces conductive textiles with sheet resistances of 0.1–10.1 MΩ/cm2, depending on the substrate, and uniform conformal coatings of MOFs on textile swatches with strong interfacial contact capable of withstanding chemical and physical stresses, such as detergent washes and abrasion. These conductive textiles enable simultaneous detection and detoxification of nitric oxide and hydrogen sulfide, achieving part per million limits of detection in dry and humid conditions. The Cu3(HHTP)2 MOF also demonstrated filtration capabilities of H2S, with uptake capacity up to 4.6 mol/kgMOF. X-ray photoelectron spectroscopy and diffuse reflectance infrared spectroscopy show that the detection of NO and H2S with Cu3(HHTP)2 is accompanied by the transformation of these species to less toxic forms, such as nitrite and/or nitrate and copper sulfide and Sx species, respectively. These results pave the way for using conductive MOFs to construct extremely robust electronic textiles with multifunctional performance characteristics

Under-reporting and Poor Adherence to Monitoring Guidelines for Severe Cases of Isoniazid Hepatotoxicity

IMPORTANCE: Mutations in known causal Alzheimer disease (AD) genes account for only 1% to 3% of patients and almost all are dominantly inherited. Recessive inheritance of complex phenotypes can be linked to long (>1-megabase [Mb]) runs of homozygosity (ROHs) detectable by single-nucleotide polymorphism (SNP) arrays. OBJECTIVE: To evaluate the association between ROHs and AD in an African American population known to have a risk for AD up to 3 times higher than white individuals. DESIGN, SETTING, AND PARTICIPANTS: Case-control study of a large African American data set previously genotyped on different genome-wide SNP arrays conducted from December 2013 to January 2015. Global and locus-based ROH measurements were analyzed using raw or imputed genotype data. We studied the raw genotypes from 2 case-control subsets grouped based on SNP array: Alzheimer's Disease Genetics Consortium data set (871 cases and 1620 control individuals) and Chicago Health and Aging Project-Indianapolis Ibadan Dementia Study data set (279 cases and 1367 control individuals). We then examined the entire data set using imputed genotypes from 1917 cases and 3858 control individuals. MAIN OUTCOMES AND MEASURES: The ROHs larger than 1 Mb, 2 Mb, or 3 Mb were investigated separately for global burden evaluation, consensus regions, and gene-based analyses. RESULTS: The African American cohort had a low degree of inbreeding (F ~ 0.006). In the Alzheimer's Disease Genetics Consortium data set, we detected a significantly higher proportion of cases with ROHs greater than 2 Mb (P = .004) or greater than 3 Mb (P = .02), as well as a significant 114-kilobase consensus region on chr4q31.3 (empirical P value 2 = .04; ROHs >2 Mb). In the Chicago Health and Aging Project-Indianapolis Ibadan Dementia Study data set, we identified a significant 202-kilobase consensus region on Chr15q24.1 (empirical P value 2 = .02; ROHs >1 Mb) and a cluster of 13 significant genes on Chr3p21.31 (empirical P value 2 = .03; ROHs >3 Mb). A total of 43 of 49 nominally significant genes common for both data sets also mapped to Chr3p21.31. Analyses of imputed SNP data from the entire data set confirmed the association of AD with global ROH measurements (12.38 ROHs >1 Mb in cases vs 12.11 in controls; 2.986 Mb average size of ROHs >2 Mb in cases vs 2.889 Mb in controls; and 22% of cases with ROHs >3 Mb vs 19% of controls) and a gene-cluster on Chr3p21.31 (empirical P value 2 = .006-.04; ROHs >3 Mb). Also, we detected a significant association between AD and CLDN17 (empirical P value 2 = .01; ROHs >1 Mb), encoding a protein from the Claudin family, members of which were previously suggested as AD biomarkers. CONCLUSIONS AND RELEVANCE: To our knowledge, we discovered the first evidence of increased burden of ROHs among patients with AD from an outbred African American population, which could reflect either the cumulative effect of multiple ROHs to AD or the contribution of specific loci harboring recessive mutations and risk haplotypes in a subset of patients. Sequencing is required to uncover AD variants in these individuals

Discovery of chlorophyll d: isolation and characterization of a far-red cyanobacterium from the original site of manning and strain (1943) at Moss Beach, California

© The Author(s), 2022. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Kiang, N. Y., Swingley, W. D., Gautam, D., Broddrick, J. T., Repeta, D. J., Stolz, J. F., Blankenship, R. E., Wolf, B. M., Detweiler, A. M., Miller, K. A., Schladweiler, J. J., Lindeman, R., & Parenteau, M. N. Discovery of chlorophyll d: isolation and characterization of a far-red cyanobacterium from the original site of manning and strain (1943) at Moss Beach, California. Microorganisms, 10(4), (2022): 819, https://doi.org/10.3390/microorganisms10040819.We have isolated a chlorophyll-d-containing cyanobacterium from the intertidal field site at Moss Beach, on the coast of Central California, USA, where Manning and Strain (1943) originally discovered this far-red chlorophyll. Here, we present the cyanobacterium’s environmental description, culturing procedure, pigment composition, ultrastructure, and full genome sequence. Among cultures of far-red cyanobacteria obtained from red algae from the same site, this strain was an epiphyte on a brown macroalgae. Its Qyin vivo absorbance peak is centered at 704–705 nm, the shortest wavelength observed thus far among the various known Acaryochloris strains. Its Chl a/Chl d ratio was 0.01, with Chl d accounting for 99% of the total Chl d and Chl a mass. TEM imagery indicates the absence of phycobilisomes, corroborated by both pigment spectra and genome analysis. The Moss Beach strain codes for only a single set of genes for producing allophycocyanin. Genomic sequencing yielded a 7.25 Mbp circular chromosome and 10 circular plasmids ranging from 16 kbp to 394 kbp. We have determined that this strain shares high similarity with strain S15, an epiphyte of red algae, while its distinct gene complement and ecological niche suggest that this strain could be the closest known relative to the original Chl d source of Manning and Strain (1943). The Moss Beach strain is designated Acaryochloris sp. (marina) strain Moss Beach.N.Y.K., M.N.P. and R.E.B. were supported by the NASA Virtual Planetary Laboratory team (VPL), which was funded under NASA Astrobiology Institute Cooperative Agreement Number NNA13AA93A, and Grant Number 80NSSC18K0829. This work also benefited from participation in the NASA Nexus for Exoplanet Systems Science (NExSS) research coordination network (RCN). W.D.S, N.Y.K. and M.N.P. were also supported by a NASA Exobiology grant No. 80NSSC19K0478. J.TB. was supported by the NASA Postdoctoral Program (NPP) award number NPP168014S. N.Y.K. received training support from the NASA Goddard Space Flight Center Training Office to take the Microbial Diversity course at the Marine Biological Laboratory, Woods Hole, MA, USA

The Complete Genome Sequence and Analysis of the Epsilonproteobacterium Arcobacter butzleri

BACKGROUND: Arcobacter butzleri is a member of the epsilon subdivision of the Proteobacteria and a close taxonomic relative of established pathogens, such as Campylobacter jejuni and Helicobacter pylori. Here we present the complete genome sequence of the human clinical isolate, A. butzleri strain RM4018. METHODOLOGY/PRINCIPAL FINDINGS: Arcobacter butzleri is a member of the Campylobacteraceae, but the majority of its proteome is most similar to those of Sulfuromonas denitrificans and Wolinella succinogenes, both members of the Helicobacteraceae, and those of the deep-sea vent Epsilonproteobacteria Sulfurovum and Nitratiruptor. In addition, many of the genes and pathways described here, e.g. those involved in signal transduction and sulfur metabolism, have been identified previously within the epsilon subdivision only in S. denitrificans, W. succinogenes, Sulfurovum, and/or Nitratiruptor, or are unique to the subdivision. In addition, the analyses indicated also that a substantial proportion of the A. butzleri genome is devoted to growth and survival under diverse environmental conditions, with a large number of respiration-associated proteins, signal transduction and chemotaxis proteins and proteins involved in DNA repair and adaptation. To investigate the genomic diversity of A. butzleri strains, we constructed an A. butzleri DNA microarray comprising 2238 genes from strain RM4018. Comparative genomic indexing analysis of 12 additional A. butzleri strains identified both the core genes of A. butzleri and intraspecies hypervariable regions, where <70% of the genes were present in at least two strains. CONCLUSION/SIGNIFICANCE: The presence of pathways and loci associated often with non-host-associated organisms, as well as genes associated with virulence, suggests that A. butzleri is a free-living, water-borne organism that might be classified rightfully as an emerging pathogen. The genome sequence and analyses presented in this study are an important first step in understanding the physiology and genetics of this organism, which constitutes a bridge between the environment and mammalian hosts