43 research outputs found

    Enhanced Solid-State NMR Correlation Spectroscopy of Quadrupolar Nuclei Using Dynamic Nuclear Polarization

    No full text
    By means of a true sensitivity enhancement for a solid-state NMR spectroscopy (SSNMR) experiment performed under dynamic nuclear polarization (DNP) conditions, corresponding to 4ā€“5 orders of magnitude of time savings compared with a conventional SSNMR experiment, it is shown that it is possible to record interface-selective <sup>27</sup>Alā€“<sup>27</sup>Al two-dimensional dipolar correlation spectra on mesoporous alumina, an advanced material with potential industrial applications. The low efficiency of cross-polarization and dipolar recoupling for quadrupolar nuclei is completely negated using this technique. The important presence of pentacoordinated Al has not only been observed, but its role in bridging interfacial tetra- and hexacoordinated Al has been determined. Such structural information, collected at low temperature (āˆ¼103 K) and 9.4 T with the use of DNP, would have been impossible to obtain under standard conditions, even using a higher magnetic field. However, here it is demonstrated that this information can be obtained in only 4 h. This work clearly opens a new avenue for the application of SSNMR to quadrupolar nuclei and notably the atomic-scale structure determination of catalysis materials such as mesoporous alumina

    Disorder and Sorption Preferences in a Highly Stable Fluoride-Containing Rare-Earth <i>fcu</i>-Type Metalā€“Organic Framework

    No full text
    Rare-earth (RE) metalā€“organic frameworks (MOFs) synthesized in the presence of fluorine-donating modulators or linkers are an important new subset of functional MOFs. However, the exact nature of the REaXb core of the molecular building block (MBB) of the MOF, where X is a Ī¼2Ā orĀ 3-bridging group, remains unclear. Investigation of one of the archetypal members of this family with the stable fcu framework topology, Y-fum-fcu-MOF (1), using a combination of experimental techniques, including high-field (20 T) solid-state nuclear magnetic resonance spectroscopy, has determined two sources of framework disorder involving the Ī¼3-X face-capping group of the MBB and the fumarate (fum) linker. The core of the MBB of 1 is shown to contain a mixture of Ī¼3-Fā€“ and (OH)āˆ’ groups with preferential occupation at the crystallographically different face-capping sites that result in different internally lined framework tetrahedral cages. The fum linker is also found to display a disordered arrangement involving bridgingā€“ or chelatingā€“bridging bis-bidentate modes over the fum linker positions without influencing the MBB orientation. This linker disorder will, upon activation, result in the creation of Y3+ ions with potentially one or two additional uncoordinated sites possessing differing degrees of Lewis acidity. Crystallographically determined hostā€“guest relationships for simple sorbates demonstrate the favored sorption sites for N2, CO2, and CS2 molecules that reflect the chemical nature of both the framework and the sorbate species with the structural partitioning of the Ī¼3-groups apparent in determining the favored sorption site of CS2. The two types of disorder found within 1 demonstrate the complexity of fluoride-containing RE-MOFs and highlight the possibility to tune this and other frameworks to contain different proportions and segregations of Ī¼3-face-capping groups and degrees of linker disorder for specifically tailored applications

    2011 IEEE International Conference on RFID Photovoltaic Enhanced UHF RFID Tag Antennas for Dual Purpose Energy Harvesting

    Get PDF
    Abstractā€”The most significant barrier to improving passive RFID tag performance for both fixed function ID tags and enhanced RFID tags is the limitation on the amount of power that can be harvested for operation. This paper presents a novel approach for incorporating solar harvesting capability into existing passive RFID tags without increasing the parts count or changing the tag assembly process. Our approach employs the tagā€™s antenna as a dual function element in which the antenna simultaneously harvests RF energy, communicates with the RFID reader, and harvests solar energy for auxiliary power. This is accomplished by using low cost, printable photovoltaics deposited on flexible substrate to form part of the antennaā€™s radiating structure. Several prototype UHF RFID antennas are demonstrated using commercially available thin film, amorphous solar cells. To quantify the improvement in tag performance, Intelā€™s WISP was used as an initial test vehicle. The effective read range of the tag was increased by six times and exceeded the readerā€™s sensitivity limitations. Additionally, the new antenna allowed for sensing and computing operations to take place independent of the RFID reader under typical office lighting conditions

    Disorder and Sorption Preferences in a Highly Stable Fluoride-Containing Rare-Earth <i>fcu</i>-Type Metalā€“Organic Framework

    No full text
    Rare-earth (RE) metalā€“organic frameworks (MOFs) synthesized in the presence of fluorine-donating modulators or linkers are an important new subset of functional MOFs. However, the exact nature of the REaXb core of the molecular building block (MBB) of the MOF, where X is a Ī¼2Ā orĀ 3-bridging group, remains unclear. Investigation of one of the archetypal members of this family with the stable fcu framework topology, Y-fum-fcu-MOF (1), using a combination of experimental techniques, including high-field (20 T) solid-state nuclear magnetic resonance spectroscopy, has determined two sources of framework disorder involving the Ī¼3-X face-capping group of the MBB and the fumarate (fum) linker. The core of the MBB of 1 is shown to contain a mixture of Ī¼3-Fā€“ and (OH)āˆ’ groups with preferential occupation at the crystallographically different face-capping sites that result in different internally lined framework tetrahedral cages. The fum linker is also found to display a disordered arrangement involving bridgingā€“ or chelatingā€“bridging bis-bidentate modes over the fum linker positions without influencing the MBB orientation. This linker disorder will, upon activation, result in the creation of Y3+ ions with potentially one or two additional uncoordinated sites possessing differing degrees of Lewis acidity. Crystallographically determined hostā€“guest relationships for simple sorbates demonstrate the favored sorption sites for N2, CO2, and CS2 molecules that reflect the chemical nature of both the framework and the sorbate species with the structural partitioning of the Ī¼3-groups apparent in determining the favored sorption site of CS2. The two types of disorder found within 1 demonstrate the complexity of fluoride-containing RE-MOFs and highlight the possibility to tune this and other frameworks to contain different proportions and segregations of Ī¼3-face-capping groups and degrees of linker disorder for specifically tailored applications

    Untangling the Condensation Network of Organosiloxanes on Nanoparticles using 2D <sup>29</sup>Siā€“<sup>29</sup>Si Solid-State NMR Enhanced by Dynamic Nuclear Polarization

    No full text
    Silica (SiO<sub>2</sub>) nanoparticles (NPs) were functionalized by silanization to produce a surface covered with organosiloxanes. Information about the surface coverage and the nature, if any, of organosiloxane polymerization, whether parallel or perpendicular to the surface, is highly desired. To this extent, two-dimensional homonuclear <sup>29</sup>Si solid-state NMR could be employed. However, owing to the sensitivity limitations associated with the low natural abundance (4.7%) of <sup>29</sup>Si and the difficulty and expense of isotopic labeling here, this technique would usually be deemed impracticable. Nevertheless, we show that recent developments in the field of dynamic nuclear polarization under magic angle spinning (MAS-DNP) could be used to dramatically increase the sensitivity of the NMR experiments, resulting in a timesaving factor of āˆ¼625 compared to conventional solid-state NMR. This allowed the acquisition of previously infeasible data. Using both through-space and through-bond 2D <sup>29</sup>Siā€“<sup>29</sup>Si correlation experiments, it is shown that the required reaction conditions favor lateral polymerization and domain growth. Moreover, the natural abundance correlation experiments permitted the estimation of <sup>2</sup><i>J</i><sup>Siā€“Oā€“Si</sup>-couplings (13.8 Ā± 1.4 Hz for surface silica) and interatomic distances (3.04 Ā± 0.08 ƅ for surface silica) since complications associated with many-spin systems and also sensitivity were avoided. The work detailed herein not only demonstrates the possibility of using MAS-DNP to greatly facilitate the acquisition of 2D <sup>29</sup>Siā€“<sup>29</sup>Si correlation spectra but also shows that this technique can be used in a routine fashion to characterize surface grafting networks and gain structural constraints, which can be related to a systemā€™s chemical and physical properties

    Dynamic Nuclear Polarization NMR of Lowā€‘Ī³ Nuclei: Structural Insights into Hydrated Yttrium-Doped BaZrO<sub>3</sub>

    No full text
    We demonstrate that solid-state NMR spectra of challenging nuclei with a low gyromagnetic ratio such as yttrium-89 can be acquired quickly with indirect dynamic nuclear polarization (DNP) methods. Proton to <sup>89</sup>Y cross polarization (CP) magic angle spinning (MAS) spectra of Y<sup>3+</sup> in a frozen aqueous solution were acquired in minutes using the AMUPol biradical as a polarizing agent. Subsequently, the detection of the <sup>89</sup>Y and <sup>1</sup>H NMR signals from technologically important hydrated yttrium-doped zirconate ceramics, in combination with DFT calculations, allows the local yttrium and proton environments present in these protonic conductors to be detected and assigned to different hydrogen-bonded environments

    Additional file 1: of Durable regression of Medulloblastoma after regional and intravenous delivery of anti-HER2 chimeric antigen receptor T cells

    No full text
    Figure S1. Characterization of HER2 CAR T cell phenotype. Human T cells were either mock transduced or transduced with HER2 CAR as previously described in Methods. Cells were taken from culture on Day 7 and stained for CD4, CD8, and either a panel of markers of T cell activation (A) or a panel of markers of T cell exhaustion (B). CAR+ T cells were identified by Protein-L staining as previously shown in Fig. 1. Histograms for each population of T cells are shown above, as well as the relevant FMO controls. (PPTX 389 kb

    Additional file 3: of Durable regression of Medulloblastoma after regional and intravenous delivery of anti-HER2 chimeric antigen receptor T cells

    No full text
    Figure S3. Linear regression data used for calculating statistics from Figs. 2, 3, 4, and 5. Data is presented as spider plots, with each line representing data from an individual mouse, and linear regression lines and equations overlaid. Fig.ƂĀ 2b. Fig.ƂĀ 3b. Fig.ƂĀ 4b. Fig.ƂĀ 5b. (PPTX 274 kb

    Additional file 1: Figure S1. of Identifying biomarkers of dementia prevalent among amnestic mild cognitively impaired ethnic female patients

    No full text
    Plasma biomarkers that did not significantly change among ethnicities and disease status. Graphs represent six out of 12 biomarkers that were not significantly changed among ethnic groups with aMCI disease status compared with age-matched controls (NC). Statistical analyses were performed in a two by three factorial design with post-hoc analyses using IBM SPSS Statistics 22. An outlier test via IBM SPSS Statistics 22 was performed on each data set and outliers were removed. (TIFF 1521 kb
    corecore