We report broad bandwidth, 0.1-10 THz time-domain spectroscopy of linear and electro-optic polymers. The common THz optical component materials high-density polyethylene, polytetrafluoroethylene, polyimide (Kapton), and polyethylene cyclic olefin copolymer (Topas) were evaluated for broadband THz applications. Host polymers polymethyl methacrylate, polystyrene, and two types of amorphous polycarbonate were also examined for suitability as host for several important chromophores in guest-host electro-optic polymer composites for use as broadband THz emitters and sensors.
In response to the emergence of SARS-CoV-2 variants of concern, the global scientific community, through unprecedented effort, has sequenced and shared over 11 million genomes through GISAID, as of May 2022. This extraordinarily high sampling rate provides a unique opportunity to track the evolution of the virus in near real-time. Here, we present outbreak.info, a platform that currently tracks over 40 million combinations of Pango lineages and individual mutations, across over 7,000 locations, to provide insights for researchers, public health officials and the general public. We describe the interpretable visualizations available in our web application, the pipelines that enable the scalable ingestion of heterogeneous sources of SARS-CoV-2 variant data and the server infrastructure that enables widespread data dissemination via a high-performance API that can be accessed using an R package. We show how outbreak.info can be used for genomic surveillance and as a hypothesis-generation tool to understand the ongoing pandemic at varying geographic and temporal scales.In December 2019, a series of cases of pneumonia of unknown origin appeared in Wuhan, China and on 7 January 2020, the virus responsible for the diseases was identified as a novel coronavirus, SARS-CoV-2 (ref. 1 ). The first SARS-CoV-2 genome was made publicly available on 10 January 2020 (refs. 2,3 ). Since then, the global scientific community, through an unprecedented effort, has sequenced and shared over 11 million genomes through GISAID (https://gisaid.org/), as of May 2022 (ref. 4 ). To keep track of the evolving genetic diversity of SARS-CoV-2, Rambaut
This
article describes the design and development of squaraine-based
semiconducting polymer dots (Pdots) that show large Stokes shifts
and narrow-band emissions in the near-infrared (NIR) region. Fluorescent
copolymers containing fluorene and squaraine units were synthesized
and used as precursors for preparing the Pdots, where exciton diffusion
and likely through-bond energy transfer led to highly bright and narrow-band
NIR emissions. The resulting Pdots exhibit the emission full width
at half-maximum of ∼36 nm, which is ∼2 times narrower
than those of inorganic quantum dots in the same wavelength region
(∼66 nm for Qdot705). The squaraine-based Pdots show a high
fluorescence quantum yield (QY) of 0.30 and a large Stokes shift of
∼340 nm. Single-particle analysis indicates that the average
per-particle brightness of the Pdots is ∼6 times higher than
that of Qdot705. We demonstrate bioconjugation of the squaraine Pdots
and employ the Pdot bioconjugates in flow cytometry and cellular imaging
applications. Our results suggest that the narrow bandwidth, high
QY, and large Stokes shift are promising for multiplexed biological
detections.
A facile approach to soluble star-shaped oligothiophene-functionalized polycyclic aromatics based on truxene is developed in this Communication. The Suzuki coupling reactions afford the thiophene-containing polycyclic aromatics with long branches (about 2.1 nm length from the heart to the periphery) from truxene precursor with excellent yields. The unsubstituted alpha-positions of thiophene rings allow for efficient halogenation and for further functionalization. The investigation of proton NMR spectra indicates that the hexahexyl groups efficiently prevent the self-association through the arene-arene pi-stacking. Chemical shifts belonging to methylene groups move more upfield than do those of methyl groups. These chemical shift values (about 0.5-0.6 ppm) are quite lower than those of normal methyl and methylene groups. We also prepare a dendritic hyperbranched polymer P1 through FeCl3 mediated oxidative polymerizations. The photophysical properties of all compounds possessing good symmetry are investigated by UV-vis and emission measurement.
We have successfully utilized epoxyisophorone ring-opening chemistry to efficiently incorporate the butylthio group to the phenyltetraene bridge of highly efficient nonlinear optical chromophores in high overall yield. By following the guidance of Dewar’s rules, the sulfur atom functions as a moderate π-accepting group at a starred position of the conjugated bridge. Several of very critical material parameters of the phenyltetraenic chromophores for device applications have been intrinsically and simultaneously improved through such a simple and straightforward engineering of molecular structures. Compared with the nonsubstituted analogue 2, thiolated chromophore 1 achieves higher molecular hyperpolarizability (34%), enhanced E-O coefficient (38%), significantly improved photochemical stability against 1O2 (by an order of magnitude), and better optical transparency (17 nm blue-shifted λmax absorption spectrum).
Two series of novel fully conjugated oligomers, oligothiophene-functionalized 9,9'-spirobifluorene derivatives, have been developed in this contribution. First, four 9,9'-spirobifluorene bromide derivatives (compounds 1a-d) are prepared through various synthetic routes. Oligothiophene derivatives with or without substituents are synthesized through the Grignard and Suzuki coupling reactions. The Negishi coupling reactions between oligothienylzinc chloride and various 9,9'-spirobifluorene bromides with Pd(PPh(3))(4) as catalyst successfully produce the desired compounds, unsubstituted oligothiophene-functionalized 9,9'-spirobifluorene derivatives, compounds 2 to 4a-d. Since the Negishi coupling reactions afford regioregularly head-to-tail (H-T) oligo(4-n-hexylthiophene)-functionalized 9,9'-spirobifluorene derivatives in poor yields, the Suzuki coupling reactions between sodium 4-n-hexylthienyl-2-boronate 8, and various 9,9'-spirobifluorene-based bromides 1a-d and 9-16 are employed to produce highly regioregular head-to-tail oligothiophene-functionalized 9,9'-spirobifluorene derivatives (compounds 5 to 7a-d) in very high yields. We also investigate the effect of solvents on the Suzuki coupling reactions. The structure and purity of all compounds are verified by FT-IR, (1)H and (13)C NMR, MS, and elemental analysis.
Recent developments of molecular architectural control and solid-state engineering have led to exceptionally large electro-optic (EO) activities in organic and polymeric nonlinear optical (NLO) materials. A new generation of NLO dendrimers has been developed to generate well-defined nano-objects, minimize strong intermolecular electrostatic interactions, and improve poling efficiency and stability. A facile and reliable Diels-Alder "click" reaction was applied for lattice hardening to improve physical properties of cross-linkable EO polymers. The "click" chemistry also provides means to study the relationship between EO activity, chromophore shape, and number density of the chromophore, systematically. The NLO dendrimers or polymers were used as hosts for guest chromophores to increase chromophore concentration and improve poling efficiency. A variety of nanostructured organic and polymeric materials with ultrahigh r 33 values (>350 pm/V at the wavelength of 1310 nm, more than 10 times that of LiNbO 3 ) and excellent temporal alignment stability at 85 °C were achieved by the approaches.
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