Investigation of ordered shell nanoparticles as catalytic platforms for organic synthesis

Thesis (Ph. D.)--Massachusetts Institute of Technology, Dept. of Materials Science and Engineering, 2009.Includes bibliographical references.By observing the molecular structure of nature, the field of nanotechnology is exploring the significant versatility and complexity of the local, molecular environment. Through the careful positioning of the components of atoms and molecules into well-defined patterns or structures, unique properties and functions can be developed that are not obtainable by the basic components alone. This structure of the local environment is deeply important to catalysis, in which the catalyst affects a chemical transformation without being consumed itself. In pursuit of control over local molecular structure, previous work has discovered a general, spontaneous ordering of long, aliphatic molecules on the surfaces of nanoparticles. This ordering generates stripe-like domains, termed ripple domains, which have widths less than a nanometer and well-defined spatial separations. This structuring reminds us of the sub-nanometer ordering seen in biological enzymes, and we seek to investigate catalytic reactions occurring at the interface of the ripple domain interface as a possible new method in organic synthesis. Using nanoparticles as my chosen platform for the ripple domain, I have conducted research to test the hypothesis that the local ordering in the ripple domain shell can improve the catalytic rate of reaction. I am guided by recent evidence that the unique ripple domain morphology can cause ordering in the solvation shell that surrounds the nanoparticle, and thus alter the surface energy observed on the interface. Our investigation has found that when ripple domain gold-core nanoparticles synthesized with an imidazole terminated ligand are used in the general acid-base hydrolysis of an aromatic ester that the catalytic rate is modulated by the presence of the ripple domain, however the degree of modulation varies substantially between synthetic batches, preventing a conclusion of any statistical significance on the ability of the ripple domain to influence the catalytic reactivity.In mixed ethanol: water solvent I find that the ripple domain can modulate the catalyst rate in a non-monotonic manner, and when compared to a homo-ligand non-ripple catalyst particle, the modulated catalyst rate can be either enhanced or attenuated depending on the ligand ratio used. In pure water, non-ripple, homo-ligand catalyst particles have higher catalytic rates than ripple-domain particles; however the binding constant and attempt frequency of these types of particles is modulated by changes in the ripple domain, and provides evidence that the monolayer structure is affecting catalysis by producing a local environment capable of holding a reactive intermediate state. The results provide a beginning link between nanoparticle monolayer morphology and catalysis, and open the way to developing nanoparticles as selective catalysts based on changes in the structure of the monolayer.by Benjamin H. Wunsch.Ph.D

Deterministic Lateral Displacement:Challenges and Perspectives

The advent of microfluidics in the 1990s promised a revolution in multiple industries from healthcare to chemical processing. Deterministic lateral displacement (DLD) is a continuous-flow microfluidic particle separation method discovered in 2004 that has been applied successfully and widely to the separation of blood cells, yeast, spores, bacteria, viruses, DNA, droplets, and more. Deterministic lateral displacement is conceptually simple and can deliver consistent performance over a wide range of flow rates and particle concentrations. Despite wide use and in-depth study, DLD has not yet been fully elucidated or optimized, with different approaches to the same problem yielding varying results. We endeavor here to provide up-to-date expert opinion on the state-of-art and current fundamental, practical, and commercial challenges with DLD as well as describe experimental and modeling opportunities. Because these challenges and opportunities arise from constraints on hydrodynamics, fabrication, and operation at the micro- and nanoscale, we expect this Perspective to serve as a guide for the broader micro- and nanofluidic community to identify and to address open questions in the field

Reinterpretation of LHC Results for New Physics: Status and recommendations after Run 2

We report on the status of efforts to improve the reinterpretation of searches and measurements at the LHC in terms of models for new physics, in the context of the LHC Reinterpretation Forum. We detail current experimental offerings in direct searches for new particles, measurements, technical implementations and Open Data, and provide a set of recommendations for further improving the presentation of LHC results in order to better enable reinterpretation in the future. We also provide a brief description of existing software reinterpretation frameworks and recent global analyses of new physics that make use of the current data

National survey of outcomes and practices in acute respiratory distress syndrome in Singapore

The authors acknowledge the following as the total funding sources for this study: 1. SICM NICER grant: logistical, non-monetary, support from the Society of Intensive Care Medicine Singapore. This was in the form of Ngee Ann Polytechnic students (8) who collected the data for the study for one month. 2. NMRC (National medical research council) grant for Dr, Matthew Cove (partial support for this study): This was in the shape of salary support for all his research related activity. (NMRC/TA/0015/2013) (MEC)

Combined searches for the production of supersymmetric top quark partners in proton-proton collisions at root s=13 TeV

A combination of searches for top squark pair production using proton-proton collision data at a center-of-mass energy of 13 TeV at the CERN LHC, corresponding to an integrated luminosity of 137 fb(-1) collected by the CMS experiment, is presented. Signatures with at least 2 jets and large missing transverse momentum are categorized into events with 0, 1, or 2 leptons. New results for regions of parameter space where the kinematical properties of top squark pair production and top quark pair production are very similar are presented. Depending on themodel, the combined result excludes a top squarkmass up to 1325 GeV for amassless neutralino, and a neutralinomass up to 700 GeV for a top squarkmass of 1150 GeV. Top squarks with masses from 145 to 295 GeV, for neutralino masses from 0 to 100 GeV, with a mass difference between the top squark and the neutralino in a window of 30 GeV around the mass of the top quark, are excluded for the first time with CMS data. The results of theses searches are also interpreted in an alternative signal model of dark matter production via a spin-0 mediator in association with a top quark pair. Upper limits are set on the cross section for mediator particle masses of up to 420 GeV

Search for new particles in events with energetic jets and large missing transverse momentum in proton-proton collisions at root s=13 TeV

A search is presented for new particles produced at the LHC in proton-proton collisions at root s = 13 TeV, using events with energetic jets and large missing transverse momentum. The analysis is based on a data sample corresponding to an integrated luminosity of 101 fb(-1), collected in 2017-2018 with the CMS detector. Machine learning techniques are used to define separate categories for events with narrow jets from initial-state radiation and events with large-radius jets consistent with a hadronic decay of a W or Z boson. A statistical combination is made with an earlier search based on a data sample of 36 fb(-1), collected in 2016. No significant excess of events is observed with respect to the standard model background expectation determined from control samples in data. The results are interpreted in terms of limits on the branching fraction of an invisible decay of the Higgs boson, as well as constraints on simplified models of dark matter, on first-generation scalar leptoquarks decaying to quarks and neutrinos, and on models with large extra dimensions. Several of the new limits, specifically for spin-1 dark matter mediators, pseudoscalar mediators, colored mediators, and leptoquarks, are the most restrictive to date.Peer reviewe

Probing effective field theory operators in the associated production of top quarks with a Z boson in multilepton final states at root s=13 TeV

Peer reviewe

Search for lepton-flavor violating decays of the Higgs boson in the mu tau and e tau final states in proton-proton collisions at root s=13 TeV

A search is presented for lepton-flavor violating decays of the Higgs boson to mu t and et. The dataset corresponds to an integrated luminosity of 137 fb(-1) collected at the LHC in proton-proton collisions at a center-of-mass energy of 13 TeV. No significant excess has been found, and the results are interpreted in terms of upper limits on lepton-flavor violating branching fractions of the Higgs boson. The observed (expected) upper limits on the branching fractions are, respectively, B(H -> mu t) e tau) < 0.22(0.16)% at 95% confidence level.Peer reviewe

Search for long-lived particles decaying to jets with displaced vertices in proton-proton collisions at root s=13 Te V

A search is presented for long-lived particles produced in pairs in proton-proton collisions at the LHC operating at a center-of-mass energy of 13 TeV. The data were collected with the CMS detector during the period from 2015 through 2018, and correspond to a total integrated luminosity of 140 fb(-1). This search targets pairs of long-lived particles with mean proper decay lengths between 0.1 and 100 mm, each of which decays into at least two quarks that hadronize to jets, resulting in a final state with two displaced vertices. No significant excess of events with two displaced vertices is observed. In the context of R-parity violating supersymmetry models, the pair production of long-lived neutralinos, gluinos, and top squarks is excluded at 95% confidence level for cross sections larger than 0.08 fb, masses between 800 and 3000 GeV, and mean proper decay lengths between 1 and 25 mm.Peer reviewe

Search for top squark production in fully hadronic final states in proton-proton collisions at root s=13 TeV

A search for production of the supersymmetric partners of the top quark, top squarks, is presented. The search is based on proton-proton collision events containing multiple jets, no leptons, and large transverse momentum imbalance. The data were collected with the CMS detector at the CERN LHC at a center-of-mass energy of 13 TeV, and correspond to an integrated luminosity of 137 fb(-1). The targeted signal production scenarios are direct and gluino-mediated top squark production, including scenarios in which the top squark and neutralino masses are nearly degenerate. The search utilizes novel algorithms based on deep neural networks that identify hadronically decaying top quarks and W bosons, which are expected in many of the targeted signal models. No statistically significant excess of events is observed relative to the expectation from the standard model, and limits on the top squark production cross section are obtained in the context of simplified supersymmetric models for various production and decay modes. Exclusion limits as high as 1310 GeVare established at the 95% confidence level on the mass of the top squark for direct top squark production models, and as high as 2260 GeV on the mass of the gluino for gluino-mediated top squark production models. These results represent a significant improvement over the results of previous searches for supersymmetry by CMS in the same final state.Peer reviewe