Showing papers by "Seth M. Cohen published in 2014"
TL;DR: The resulting materials are among the first examples of Zr(IV)-based UiO MOFs with coordinatively unsaturated active metal centers and are active and efficient catalysts for the oxidation of alcohols to ketones using a wide range of substrates.
Abstract: An isolated metal-monocatecholato moiety has been achieved in a highly robust metal-organic framework (MOF) by two fundamentally different postsynthetic strategies: postsynthetic deprotection (PSD) and postsynthetic exchange (PSE). Compared with PSD, PSE proved to be a more facile and efficient functionalization approach to access MOFs that could not be directly synthesized under solvothermal conditions. Metalation of the catechol functionality residing in the MOFs resulted in unprecedented Fe-monocatecholato and Cr-monocatecholato species, which were characterized by X-ray absorption spectroscopy, X-band electron paramagnetic resonance spectroscopy, and (57)Fe Mossbauer spectroscopy. The resulting materials are among the first examples of Zr(IV)-based UiO MOFs (UiO = University of Oslo) with coordinatively unsaturated active metal centers. Importantly, the Cr-metalated MOFs are active and efficient catalysts for the oxidation of alcohols to ketones using a wide range of substrates. Catalysis could be achieved with very low metal loadings (0.5-1 mol %). Unlike zeolite-supported, Cr-exchange oxidation catalysts, the MOF-based catalysts reported here are completely recyclable and reusable, which may make them attractive catalysts for 'green' chemistry processes.
250 citations
TL;DR: Two synthetic approaches are reported to prepare a highly crystalline Zr(IV)-based metal-organic framework (MOF) containing open 2,2'-bipyridine (bpy) chelating sites that exhibits efficient and recyclable catalytic activity for the Suzuki-Miyaura cross-coupling reaction.
183 citations
Posted Content•
09 Jan 2014
TL;DR: The Precision IceCube Next Generation Upgrade (PINGU) is a proposed low-energy in-fill array of the IceCube Neutrino Observatory as mentioned in this paper, which will feature the world's largest effective volume for neutrinos at an energy threshold of a few GeV.
Abstract: The Precision IceCube Next Generation Upgrade (PINGU) is a proposed low-energy in-fill array of the IceCube Neutrino Observatory. Leveraging technology proven with IceCube, PINGU will feature the world's largest effective volume for neutrinos at an energy threshold of a few GeV, improving the sensitivity to several aspects of neutrino oscillation physics at modest cost. With its unprecedented statistical sample of low-energy atmospheric neutrinos, PINGU will have highly competitive sensitivity to $
u_{\mu}$ disappearance, the $\theta_{23}$ octant, and maximal mixing, will make the world's best $
u_{\tau}$ appearance measurement, allowing a unique probe of the unitarity of the PMNS mixing matrix, and will be able to distinguish the neutrino mass ordering at $3\sigma$ significance with less than 4 years of data. PINGU can also extend the indirect search for solar WIMP dark matter complimentary to the on-going and planned direct dark matter experiments. At the lower end of the energy range, PINGU may use neutrino tomography to directly probe the composition of the Earth's core. With its increased module density, PINGU will improve IceCube's sensitivity to galactic supernova neutrino bursts and enable it to extract the neutrino energy spectral shape.
178 citations
TL;DR: In this paper, neutrinos and supernovae were investigated in the context of neutrino detectors with the aim of detecting supernova supernovas, and the results were published on 2014-05-19, modified on 2017-05/12.
Abstract: Keywords: neutrinos ; supernovae: general ; instrumentation: detectors ; errata ; addenda Reference EPFL-ARTICLE-198916doi:10.1051/0004-6361/201117810eView record in Web of Science Record created on 2014-05-19, modified on 2017-05-12
120 citations
TL;DR: Spectral and cepstral acoustic measures and the VHI should be viewed as providing relatively unique, meaningful, and complementary information in a large and diverse group of voice-disordered and control subjects.
84 citations
TL;DR: 2D IR spectroscopy with pulse-shaping techniques can probe the ultrafast structural fluctuations of MOFs and use 2D IR and other ultrafast IR methods to elucidate the timescales for ultra fast structural fluctuations and how they are influenced by a solvent filling the pores.
Abstract: The structural elasticity of metal–organic frameworks (MOFs) is a key property for their functionality. Here, we show that 2D IR spectroscopy with pulse-shaping techniques can probe the ultrafast structural fluctuations of MOFs. 2D IR data, obtained from a vibrational probe attached to the linkers of UiO-66 MOF in low concentration, revealed that the structural fluctuations have time constants of 7 and 670 ps with no solvent. Filling the MOF pores with dimethylformamide (DMF) slows the structural fluctuations by reducing the ability of the MOF to undergo deformations, and the dynamics of the DMF molecules are also greatly restricted. Methodology advances were required to remove the severe light scattering caused by the macroscopic-sized MOF particles, eliminate interfering oscillatory components from the 2D IR data, and address Forster vibrational excitation transfer.
76 citations
TL;DR: 1,3,5-Tris(4-phosphonophenyl)benzene was synthesized via a microwave heating assisted route and was subsequently used for the preparation of a new zirconium phosphonate with honeycomb-like structure displaying remarkable thermal stability and hydrolysis resistance.
53 citations
TL;DR: To evaluate the frequency, timing, and factors that influence referral of patients with laryngeal/voice disorders to otolaryngology following initial evaluation by a primary care physician (PCP).
Abstract: Objectives/Hypothesis
To evaluate the frequency, timing, and factors that influence referral of patients with laryngeal/voice disorders to otolaryngology following initial evaluation by a primary care physician (PCP).
Study Design
Retrospective analysis of a large, national administrative US claims database.
Methods
Patients with a laryngeal disorder based on International Classification of Diseases, Ninth Revision, Clinical Modification codes from January 1, 2004 to December 31, 2008, seen by a PCP as an outpatient (with or without otolaryngology involvement), and continuously enrolled for 12 months were included. Patient age, gender, geographic region, last PCP laryngeal diagnosis, comorbid conditions, time from first PCP visit to first otolaryngology visit, number of PCP outpatient visits, and number of PCP laryngeal diagnoses were collected. Cox and generalized linear regressions were performed.
Results
A total of 149,653 unique patients saw a PCP as an outpatient for a laryngeal/voice disorder, with 136,152 (90.9%) only seeing a PCP, 6,013 (4.0%) referred by a PCP to an otolaryngologist, and 3,820 (2.6%) self-referred to an otolaryngologist. Acute laryngitis had a lower hazard ratio (HR) for otolaryngology referral than chronic laryngitis, nonspecific dysphonia, and laryngeal cancer. Having multiple comorbid conditions was associated with a greater HR for otolaryngology referral than having no comorbidities. Patient age, gender, and geographic region also affected otolaryngology referral. The time to otolaryngology evaluation ranged from 3 months. PCP-referred patients had less time to the otolaryngology evaluation than self-referred patients.
Conclusions
Multiple factors affected otolaryngology referral for patients with laryngeal/voice disorders. Further education of PCPs regarding appropriate otolaryngology referral for laryngeal/voice disorders is needed.
Level of Evidence
2b. Laryngoscope, 124:214–220, 2014
35 citations
TL;DR: A series of geometrically constrained, cross-linked benzene dicarboxylic acid (bdc) derivatives have been synthesized and incorporated into the canonical isoreticular metal- organic framework (IRMOF) lattice, providing a new dimension to rational ligand design for metal-organic frameworks.
Abstract: A series of geometrically constrained, cross-linked benzene dicarboxylic acid (bdc) derivatives have been synthesized and incorporated into the canonical isoreticular metal-organic framework (IRMOF) lattice. Only certain cross-links, which allow for the proper relative orientation of the bdc subunits, form the desired IRMOF. Design criteria from these cross-linked ligands allowed for the rational design of two oligomeric ligands composed of three bdc monomers tethered together. These oligomeric ligands were also readily incorporated into an IRMOF lattice with a high degree of crystallinity and porosity, providing a new dimension to rational ligand design for metal-organic frameworks.
34 citations
TL;DR: The binding of a series of metal-binding pharmacophores related to the ligand 1-hydroxypyridine-2-(1H)-thione in the active site of human carbonic anhydrase II (hCAII) has been investigated and suggests metal coordination by metalloenzyme inhibitors is a malleable interaction.
Abstract: The binding of a series of metal-binding pharmacophores (MBPs) related to the ligand 1-hydroxypyridine-2-(1H)-thione (1,2-HOPTO) in the active site of human carbonic anhydrase II (hCAII) has been investigated. The presence and/or position of a single methyl substituent drastically alters inhibitor potency and can result in coordination modes not observed in small-molecule model complexes. It is shown that this unexpected binding mode is the result of a steric clash between the methyl group and a highly ordered water network in the active site that is further stabilized by the formation of a hydrogen bond and favorable hydrophobic contacts. The affinity of MBPs is dependent on a large number of factors including donor atom identity, orientation, electrostatics, and van der Waals interactions. These results suggest that metal coordination by metalloenzyme inhibitors is a malleable interaction and that it is thus more appropriate to consider the metal-binding motif of these inhibitors as a pharmacophore rath...
33 citations
TL;DR: Great than expected laryngeal pathology was seen in these professional singers, who identified themselves as healthy, which possibly indicates a minimal impact on their singing voice and/or perception of vocal health.
TL;DR: UiO-66 metal-organic framework, modified with catechol-substructures and metalated with Cr provides an efficient, completely recyclable and reusable catalyst for oxidation of alcohols to ketones.
Abstract: UiO-66 metal-organic framework, modified with catechol-substructures and metalated with Cr provides an efficient, completely recyclable and reusable catalyst for oxidation of alcohols to ketones.
TL;DR: Data demonstrate that the mode of binding by small metal-binding groups can be significantly influenced by the protein active site, and results in unconventional modes of metal coordination not found in typical coordination compounds or even carefully engineered active site models.
Abstract: The binding of three closely related chelators: 5-hydroxy-2-methyl-4H-pyran-4-thione (allothiomaltol, ATM), 3-hydroxy-2-methyl-4H-pyran-4-thione (thiomaltol, TM), and 3-hydroxy-4H-pyran-4-thione (thiopyromeconic acid, TPMA) to the active site of human carbonic anhydrase II (hCAII) has been investigated. Two of these ligands display a monodentate mode of coordination to the active site Zn(2+) ion in hCAII that is not recapitulated in model complexes of the enzyme active site. This unprecedented binding mode in the hCAII-thiomaltol complex has been characterized by both X-ray crystallography and X-ray spectroscopy. In addition, the steric restrictions of the active site force the ligands into a 'flattened' mode of coordination compared with inorganic model complexes. This change in geometry has been shown by density functional computations to significantly decrease the strength of the metal-ligand binding. Collectively, these data demonstrate that the mode of binding by small metal-binding groups can be significantly influenced by the protein active site. Diminishing the strength of the metal-ligand bond results in unconventional modes of metal coordination not found in typical coordination compounds or even carefully engineered active site models, and understanding these effects is critical to the rational design of inhibitors that target clinically relevant metalloproteins.
TL;DR: Differences in laryngeal diagnosis over time in outpatients evaluated by primary care physicians and/or otolaryngologists in a large, national administrative US claims database are examined.
Abstract: ObjectiveAccurate diagnosis of a voice disorder is an essential first step toward its appropriate treatment. We examined differences in laryngeal diagnosis over time in outpatients evaluated by primary care physicians (PCPs) and/or otolaryngologists.Study Design and SettingRetrospective analysis of data from a large, national administrative US claims database.Subjects and MethodsPatients with laryngeal disorders based on International Classification of Diseases, Ninth Revision, Clinical Modification codes from January 1, 2004, to December 31, 2008, with at least 2 outpatient visits by a PCP and/or otolaryngologist and continuously enrolled for 12 months were included. The initial and final laryngeal diagnoses were tabulated.ResultsOf approximately 55 million individuals, 29,501 met inclusion criteria. More than half the patients in the PCP to otolaryngology group and one-third of the otolaryngology to otolaryngology group had different laryngeal diagnoses over time. Three-fourths of patients with an initi...
TL;DR: The frequency of, diagnoses associated with, and factors related to VLS use in the evaluation of outpatients with laryngeal/voice disorders are evaluated.
Abstract: Objective
Videolaryngostroboscopy (VLS) is considered an important diagnostic tool in the evaluation of patients with laryngeal/voice disorders. We evaluated the frequency of, diagnoses associated with, and factors related to VLS use in the evaluation of outpatients with laryngeal/voice disorders.
TL;DR: Pediatricians encounter barriers in the assessment of voice problems in their patients and must continue to provide outreach to pediatricians to enhance the screening and management of patients with voice disorders.
TL;DR: To evaluate differences in evaluation and workup of laryngopharyngeal neuropathy in a population of general otolaryngologists and fellowship‐trained laryNGologists, a large number of patients with confirmed or suspected neuropathy are surveyed.
Abstract: Objectives/Hypothesis
To evaluate differences in evaluation and workup of laryngopharyngeal neuropathy in a population of general otolaryngologists and fellowship-trained laryngologists.
Study Design
Survey.
Methods
Members of the American Laryngological Association (ALA) and a general otolaryngologist database from the American Academy of Otolaryngology–Head and Neck Surgery (AAO-HNS) were surveyed. A questionnaire was e-mailed or mailed to 179 members of the ALA and 900 members from the AAO-HNS database.
Results
Responses were received from 43 subjects in the ALA group (24.5%) and 96 in the AAO-HNS database group (10.6%). Compared to the general otolaryngologists surveyed, ALA members were found to be more likely to practice in academics (79.6% vs. 6.6%) and to have been fellowship trained (79.5% vs. 16.5%). Among the general otolaryngologists, 44.6% reported being unfamiliar with laryngopharyngeal neuropathy compared to 0% from the ALA group (P < .0001). After accounting for the respondents unfamiliar with the condition, the general otolaryngologists reported being less comfortable in diagnosing laryngopharyngeal neuropathy (P < .0001) and were more concerned about the over-diagnosis of laryngopharyngeal reflux when compared to the ALA (P = .0030).
Conclusion
General otolaryngologists and fellowship-trained laryngologist have several differences in the knowledge, workup, and treatment of chronic laryngopharyngeal neuropathy. This may translate to unnecessary treatments and tests for effected patients and should be addressed with further education targeting general otolaryngologists.
Level of Evidence
4. Laryngoscope, 124:955–960, 2014
TL;DR: It has been found that the structural ordering of aryl groups within the IRMOF pores results in hysteretic H2 sorption, while the same aryal groups introduced in a disordered manner displays reversible H1 sorption that is more typical of the IR MOF family.
Patent•
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TL;DR: In this paper, the authors provided compounds and methods for treating infectious diseases, inter alia, useful inhibitors of metalloproteins, e.g. UDP-3-O-(R 3-hydroxymyristoyl)-N-acetylglucosamine deacetylase (LpxC).
Abstract: Provided herein, inter alia, are compounds and methods for treating infectious diseases. The compounds provided herein are, inter alia, useful for the treatment of bacterial infections. The compounds provided herein are, inter alia, useful inhibitors of metalloproteins, e.g. UDP-3-O-(R-3-hydroxymyristoyl)-N-acetylglucosamine deacetylase (LpxC).
TL;DR: A 96-member chelator fragment library (CFL-1.1) was screened to identify inhibitors of the lymphoid tyrosine phosphatase in the absence and presence of zinc acetate, indicating that the oxidized quinone species is likely the active inhibitor.
TL;DR: The compound cisplatin (cis-diaaminedichloroplatinum(II), Platinol ), a simple inorganic coordination compound containing no carbon atoms, is one of the world’s most widely prescribed anticancer agents and has long been touted as a great triumph of medicinal inorganic chemistry.
Abstract: The subdiscipline of bioinorganic chemistry known as ‘metals in medicine’ or ‘medicinal inorganic chemistry’ has matured into a rich and diverse area of research. The modern era of medicinal inorganic chemistry started as a relatively boutique community investigating a handful of subjects, largely focused on the use of metal ion complexes as therapeutics (‘metallopharmaceuticals’) or diagnostics (‘metallodiagnostics’). The compound cisplatin (cis-diaaminedichloroplatinum(II), Platinol ), a simple inorganic coordination compound containing no carbon atoms, is one of the world’s most widely prescribed anticancer agents and has long been touted as a great triumph of medicinal inorganic chemistry. Similarly, the widespread use of imaging agents based on gadolinium(III) for magnetic resonance imaging (MRI) and technetium-99m for nuclear medicine imaging are considered some of the more visible successes of ‘metals in medicine’.
Patent•
26 Jun 2014TL;DR: In this article, the ROS-sensitive prodrug compositions and methods of treating ROS-associated diseases by administering the ROSsensitive pro-drug compositions are presented, and the methods for treating ROSassociated diseases are described.
Abstract: Provided herein are ROS-sensitive prodrug compositions and methods of treating ROS-associated diseases by administering the ROS-sensitive prodrug compositions.
Patent•
07 Feb 2014TL;DR: In this article, compositions including boronic esters, which in the presence of H 2 O 2, provide for the detection of ROS compounds such as endogenous H 2O 2 and methods of using the compositions to detect ROS compounds.
Abstract: Herein are provided, inter alia, compositions including boronic esters, which in the presence of H 2 O 2 , provide for the detection of ROS compounds such as endogenous H 2 O 2 and methods of using the compositions to detect ROS compounds.
TL;DR: In this paper, the authors proposed a method to solve a set of computational problems in the field of industrial and manufacturing engineering, using a combination of computational simulation and industrial simulation techniques.
Abstract: 1 Department of Chemistry & Biochemistry, University of California, San Diego, La Jolla, California 92093, United States 2 Fundamental Computational Sciences Directorate and Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, Richland, Washington 99354, United States 3 Department of Industrial and Manufacturing Engineering, Florida State University, Tallahassee, Florida 32306, United States
TL;DR: Administrative and national survey databases have an important role in the field of health services research and the concept of health Services research will be presented.
Abstract: Administrative and national survey databases have an important role in the field of health services research. In this article, the concept of health services research will be presented. The types o...