203 research outputs found

    Pressure-gradient sorption calorimetry of flexible porous materials : implications for intrinsic thermal management

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    CITATION: Feldmann, W. K.; Esterhuysen, C. & Barbour, L. J. 2020. Pressure-Gradient Sorption Calorimetry of Flexible Porous Materials: Implications for Intrinsic Thermal Management. ChemSusChem, 13 (19): 5220-5223. doi:10.1002/cssc.202001469The original publication is available at https://chemistry-europe.onlinelibrary.wiley.com/journal/1864564xThermal management is an important consideration for applications that involve gas sorption by flexible porous materials. A pressure-gradient differential scanning calorimetric method was developed to measure the energetics of adsorption and desorption both directly and continuously. The method was applied to the uptake and release of CO2 by the well-known flexible metal–organic frameworks MIL-53(Al) and MOF-508b. High-resolution differential enthalpy plots and total integral enthalpy values for sorption allow comprehensive assessment of the thermal behavior of the materials throughout the entire sorption process. During adsorption, the investigated materials display the ability to offset exothermic adsorption enthalpy against endothermic structural transition enthalpy, and vice versa during desorption. The results show that flexible materials offer reduced total integral heat over a working range when compared to rigid materials.https://chemistry-europe.onlinelibrary.wiley.com/doi/10.1002/cssc.202001469Publishers versio

    Inclusion of a dithiadiazolyl radical in a seemingly non-porous solid

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    Inclusion of the dithiadiazolyl radical PhCNSSNβ€’ into the dynamically porous metallocycle [Cu2(L1)2Cl4], where L1 is the bidentate ligand 1,3-bis(imidazol-1-ylmethyl)-2,4,6- trimethylbenzene, has been achieved by gas phase diffusion. Single crystal X-ray diffraction, powder X-ray diffraction, UV-visible spectroscopy, EPR and SQUID magnetometry studies confirm inclusion of the radical into this seemingly non-porous material, and illustrate the presence of antiferromagnetic coupling between the paramagnetic host and guest species. The radical guest is readily released by heating or by the addition of solvent (CH2Cl2)

    Ring size effect on the solid state assembly of propargyl substituted hexa- and octacyclic peptoids

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    The investigation of the solid state assembly of propargyl substituted hexa- and octacyclic peptoids highlights the effect of ring size in determining the packing arrangement of the macrocycles. A layered arrangement is obtained in the case of the hexacyclic peptoid 1 and a tubular arrangement in the case of the octacyclic peptoid 2. Guest molecules either intercalate between the layers as in 1 or are located within the peptoid nanotube as in 2

    Microporosity of a guanidinium organodisulfonate hydrogen-bonded framework

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    CITATION: Brekalo, I. et al. 2020. Microporosity of a Guanidinium Organodisulfonate Hydrogen-Bonded Framework. Angewandte Chemie, 59(5):1997-2002. doi:10.1002/anie.201911861The original publication is available at https://onlinelibrary.wiley.com/journal/15213757Guanidinium organosulfonates (GSs) are a large and well-explored archetypal family of hydrogen-bonded organic host frameworks that have, over the past 25β€…years, been regarded as nonporous. Reported here is the only example to date of a conventionally microporous GS host phase, namely guanidinium 1,4-benzenedisulfonate (p-G2BDS). p-G2BDS is obtained from its acetone solvate, AcMe@G2BDS, by single-crystal-to-single-crystal (SC-SC) desolvation, and exhibits a Type I low-temperature/pressure N2 sorption isotherm (SABET=408.7(2)β€…m2 gβˆ’1, 77β€…K). SC-SC sorption of N2, CO2, Xe, and AcMe by p-G2BDS is explored under various conditions and X-ray diffraction provides a measurement of the high-pressure, room temperature Xe and CO2 sorption isotherms. Though p-G2BDS is formally metastable relative to the β€œcollapsed”, nonporous polymorph, np-G2BDS, a sample of p-G2BDS survived for almost two decades under ambient conditions. np-G2BDS reverts to zCO2@p-G2BDS or yXe@p-G2BDS (y,z=variable) when pressure of CO2 or Xe, respectively, is applied.https://onlinelibrary.wiley.com/doi/pdf/10.1002/anie.201911861Publishers versio

    Direct determination of enthalpies of sorption using pressure-gradient differential scanning calorimetry: CO2 sorption by Cu-HKUST

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    CITATION: Feldmann, W. K. et al. 2020. Direct Determination of Enthalpies of Sorption Using Pressure-Gradient Differential Scanning Calorimetry: CO2 Sorption by Cu-HKUST. ChemSusChem, 13(1): 102-105. doi:10.1002/cssc.201902990The original publication is available at https://chemistry-europe.onlinelibrary.wiley.com/journal/1864564xEnthalpy of sorption (Ξ”H) is an important parameter for the design of separation processes using adsorptive materials. A pressure-ramped calorimetric method is described and tested for the direct determination of Ξ”H values. Combining a heatflow thermogram with a single sorption isotherm enables the determination of Ξ”H as a function of loading. The method is validated by studying CO2 sorption by the well-studied metal–organic framework Cu-HKUST over a temperature range of 288–318β€…K. The measured Ξ”H values compare well with previously reported data determined by using isosteric and calorimetric methods. The pressure-gradient differential scanning calorimetry (PGDSC) method produces reliable high-resolution results by direct measurement of the enthalpy changes during the sorption processes. Additionally, PGDSC is less labor-intensive and time-consuming than the isosteric method and offers detailed insight into how Ξ”H changes over a given loading range.https://chemistry-europe.onlinelibrary.wiley.com/doi/full/10.1002/cssc.201902990Publishers versio

    Benchmark Acetylene Binding Affinity and Separation through Induced Fit in a Flexible Hybrid Ultramicroporous Material

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    Structural changes at the active site of an enzyme induced by binding to a substrate molecule can result in enhanced activity in biological systems. Herein, we report that the new hybrid ultramicroporous material sql-SIFSIX-bpe-Zn exhibits an induced fit binding mechanism when exposed to acetylene, Cβ‚‚Hβ‚‚. The resulting phase change affords exceptionally strong Cβ‚‚Hβ‚‚ binding that in turn enables highly selective Cβ‚‚Hβ‚‚/Cβ‚‚Hβ‚„ and Cβ‚‚Hβ‚‚/COβ‚‚ separation demonstrated by dynamic breakthrough experiments. sql-SIFSIX-bpe-Zn was observed to exhibit at least four phases: as-synthesised (Ξ±); activated (Ξ²); and Cβ‚‚Hβ‚‚ induced phases (Ξ²' and Ξ³). sql-SIFSIX-bpe-Zn-Ξ² exhibited strong affinity for Cβ‚‚Hβ‚‚ at ambient conditions as demonstrated by benchmark isosteric heat of adsorption (Qst ) of 67.5β€…kJ mol⁻¹ validated through in situ pressure gradient differential scanning calorimetry (PG-DSC). Further, in situ characterisation and DFT calculations provide insight into the mechanism of the Cβ‚‚Hβ‚‚ induced fit transformation, binding positions and the nature of host-guest and guest-guest interactions

    Visible‐Light‐Triggered Photoswitching of Diphosphene Complexes

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    Although diphosphene transition metal complexes are known to undergo E to Z isomerization upon irradiation with UV light, their potential for photoswitching has remained poorly explored. In this study, we present diphosphene complexes capable of reversible photoisomerizations through haptotropic rearrangements. The compounds [(2-ΞΊ2P,ΞΊ6C)Mo(CO)2][OTf] (3 a[OTf]), [(2-ΞΊ2P,ΞΊ6C)Fe(CO)][OTf] (3 b[OTf]), and [(2-ΞΊ2P)Fe(CO)4][OTf] (4[OTf]) were prepared using the triflate salt [(LC)P=P(Dipp)][OTf] (2[OTf) as a precursor (LC=4,5-dichloro-1,3-bis(2,6-diisiopropylphenyl)-imidazolin-2-yl; Dipp=2,6-diisiopropylphenyl, OTf=triflate). Upon exposure to blue or UV light (Ξ»=400β€…nm, 470β€…nm), the initially red-colored Ξ·2-diphosphene complexes 3 a,b[OTf] readily undergo isomerization to form blue-colored Ξ·1-complexes [(2-ΞΊ1P,ΞΊ6C)M(CO)n][OTf] (5 a,b[OTf]; a: M=Mo, n=2; b: M=Fe, n=1). This haptotropic rearrangement is reversible, and the (ΞΊ2P,ΞΊ6C)-coordination mode gradually reverts back upon dissolution in coordinating solvents or more rapidly upon exposure to yellow or red irradiation (Ξ»=590β€…nm, 630β€…nm). The electronic reasons for the reversible visible-light-induced photoswitching observed for 3 a,b[OTf] are elucidated by DFT calculations. These calculations indicate that the photochromic isomerization originates from the S1 excited state and proceeds through a conical intersection

    Genomic catastrophes frequently arise in esophageal adenocarcinoma and drive tumorigenesis

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    Oesophageal adenocarcinoma (EAC) incidence is rapidly increasing in Western countries. A better understanding of EAC underpins efforts to improve early detection and treatment outcomes. While large EAC exome sequencing efforts to date have found recurrent loss-offunction mutations, oncogenic driving events have been underrepresented. Here we use a combination of whole-genome sequencing (WGS) and single-nucleotide polymorphism-array profiling to show that genomic catastrophes are frequent in EAC, with almost a third (32%, nΒΌ40/123) undergoing chromothriptic events. WGS of 22 EAC cases show that catastrophes may lead to oncogene amplification through chromothripsis-derived double-minute chromosome formation (MYC and MDM2) or breakage-fusion-bridge (KRAS, MDM2 and RFC3). Telomere shortening is more prominent in EACs bearing localized complex rearrangements. Mutational signature analysis also confirms that extreme genomic instability in EAC can be driven by somatic BRCA2 mutations. These findings suggest that genomic catastrophes have a significant role in the malignant transformation of EAC

    Genome Stability of Lyme Disease Spirochetes: Comparative Genomics of Borrelia burgdorferi Plasmids

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    Lyme disease is the most common tick-borne human illness in North America. In order to understand the molecular pathogenesis, natural diversity, population structure and epizootic spread of the North American Lyme agent, Borrelia burgdorferi sensu stricto, a much better understanding of the natural diversity of its genome will be required. Towards this end we present a comparative analysis of the nucleotide sequences of the numerous plasmids of B. burgdorferi isolates B31, N40, JD1 and 297. These strains were chosen because they include the three most commonly studied laboratory strains, and because they represent different major genetic lineages and so are informative regarding the genetic diversity and evolution of this organism. A unique feature of Borrelia genomes is that they carry a large number of linear and circular plasmids, and this work shows that strains N40, JD1, 297 and B31 carry related but non-identical sets of 16, 20, 19 and 21 plasmids, respectively, that comprise 33–40% of their genomes. We deduce that there are at least 28 plasmid compatibility types among the four strains. The B. burgdorferi ∼900 Kbp linear chromosomes are evolutionarily exceptionally stable, except for a short ≀20 Kbp plasmid-like section at the right end. A few of the plasmids, including the linear lp54 and circular cp26, are also very stable. We show here that the other plasmids, especially the linear ones, are considerably more variable. Nearly all of the linear plasmids have undergone one or more substantial inter-plasmid rearrangements since their last common ancestor. In spite of these rearrangements and differences in plasmid contents, the overall gene complement of the different isolates has remained relatively constant

    Lost in translation: Returning germline genetic results in genome-scale cancer research

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    Background: The return of research results (RoR) remains a complex and well-debated issue. Despite the debate, actual data related to the experience of giving individual results back, and the impact these results may have on clinical care and health outcomes, is sorely lacking. Through the work of the Australian Pancreatic Cancer Genome Initiative (APGI) we: (1) delineate the pathway back to the patient where actionable research data were identified; and (2) report the clinical utilisation of individual results returned. Using this experience, we discuss barriers and opportunities associated with a comprehensive process of RoR in large-scale genomic research that may be useful for others developing their own policies. Methods: We performed whole-genome (n = 184) and exome (n = 208) sequencing of matched tumour-normal DNA pairs from 392 patients with sporadic pancreatic cancer (PC) as part of the APGI. We identified pathogenic germline mutations in candidate genes (n = 130) with established predisposition to PC or medium-high penetrance genes with well-defined cancer associated syndromes or phenotypes. Variants from candidate genes were annotated and classified according to international guidelines. Variants were considered actionable if clinical utility was established, with regard to prevention, diagnosis, prognostication and/or therapy. Results: A total of 48,904 germline variants were identified, with 2356 unique variants undergoing annotation and in silico classification. Twenty cases were deemed actionable and were returned via previously described RoR framework, representing an actionable finding rate of 5.1%. Overall, 1.78% of our cohort experienced clinical benefit from RoR. Conclusion: Returning research results within the context of large-scale genomics research is a labour-intensive, highly variable, complex operation. Results that warrant action are not infrequent, but the prevalence of those who experience a clinical difference as a result of returning individual results is currently low
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