Dye Sensitization Offers a Brighter Afterglow Nanoparticle Future for in vivo Recharged Luminescent Imaging

While concerns about improving recharged afterglow intensity in vivo still motivate further exploration, afterglow nanoparticles (AGNP) offer unique optical merit for autofluorescence-free biological imaging. Apart from efforts enhancing the afterglow emission properties of AGNP, improving afterglow excitation response to visible or near infrared light is important but has lacked success. Dye sensitization has been used to improve the optical response of photovoltaic nanomaterials and to enhance upconversion luminescence efficiency. This concept has recently been expanded and applied to AGNPs. As a new multifunctional nanoprobe, such dye-sensitized AGNP takes advantage of both high spatial resolution fluorescence imaging and sensitive afterglow imaging. This Concept introduces the background, the concept, mechanism, and related imaging application, as well as reviewing existing challenges and proposing future developmental directions for the dye-sensitized AGNPs.     

Cyclotetrabenzoin: Facile Synthesis of a Shape‐Persistent Molecular Square and Its Assembly into Hydrogen‐Bonded Nanotubes

Cyanide‐catalyzed benzoin condensation of terephthaldehyde produces a cyclic tetramer, which we propose to name cyclotetrabenzoin. Cyclotetrabenzoin is a square‐shaped macrocycle ornamented with four α‐hydroxyketone functionalities pointing away from the central cavity, the dimensions of which are 6.9×6.9 Å. In the solid state, these functional groups extensively hydrogen bond, resulting in a microporous three‐dimensional organic framework with one‐dimensional nanotube channels. This material exhibits permanent—albeit low‐porosity, with a Langmuir surface area of 52 m² g^?1. Cyclotetrabenzoin’s easy and inexpensive synthesis and purification may inspire the creation of other shape‐persistent macrocycles and porous molecular crystals by benzoin condensation.     

Wedge Operations and Doubling Operations of Real Toric Manifolds

This paper deals with two things.First,the cohomology of canonical extensions of real topological toric manifolds is computed when coefficient ring G is a commutative ring in which 2 is unit in G.Second,the author focuses on a specific canonical extensions called doublings and presents their various properties.They include existence of infinitely many real topological toric manifolds admitting complex structures,and a way to construct infinitely many real toric manifolds which have an odd torsion in their cohomology groups.Moreover,some questions about real topological toric manifolds related to Halperin's toral rank conjecture are presented.     

On the vanishing of homology in random Čech complexes

We compute the homology of random ?ech complexes over a homogeneous Poisson process on the d‐dimensional torus, and show that there are, coarsely, two phase transitions. The first transition is analogous to the Erd?s ‐Rényi phase transition, where the ?ech complex becomes connected. The second transition is where all the other homology groups are computed correctly (almost simultaneously). Our calculations also suggest a finer measurement of scales, where there is a further refinement to this picture and separation between different homology groups. © 2016 Wiley Periodicals, Inc. Random Struct. Alg., 51, 14–51, 2017     

Alternating link and its generalization

The alternating links give a classical class of links. They play an important role in Knot Theory. Ozsváth and Szabó introduced a quasi-alternating link which is a generalization of an alternating link. In this paper we review some results of alternating links and quasi-alternating links on the Jones polynomial and the Khovanov homology. Moreover, we introduce a long pass link. Several problems worthy of further study are provided.     

Radical Reactivity of the Biradical [⋅P(μ-NTer)2P⋅] and Isolation of a Persistent Phosphorus-Cantered Monoradical [⋅P(μ-NTer)2P-Et]

The activation of C−Br bonds in various bromoalkanes by the biradical [⋅P(μ-NTer)₂P⋅] ( 1 ) (Ter=2,6-bis-(2,4,6-trimethylphenyl)-phenyl) is reported, yielding trans-addition products of the type [Br−P(μ-NTer)₂P−R] ( 2 ), so-called 1,3-substituted cyclo-1,3-diphospha-2,4-diazanes. This addition reaction, which represents a new easy approach to asymmetrically substituted cyclo-1,3-diphospha-2,4-diazanes, was investigated mechanistically by different spectroscopic methods (NMR, EPR, IR, Raman); the results suggested a stepwise radical reaction mechanism, as evidenced by the in-situ detection of the phosphorus-centered monoradical [⋅P(μ-NTer)₂P-R].< To provide further evidence for the radical mechanism, [⋅P(μ-NTer)₂P-Et] ( 3Et ⋅) was synthesized directly by reduction of the bromoethane addition product [Br-P(μ-NTer)₂P-Et] ( 2 a ) with magnesium, resulting in the formation of the persistent phosphorus-centered monoradical [⋅P(μ-NTer)₂P-Et], which could be isolated and fully characterized, including single-crystal X-ray diffraction. Comparison of the EPR spectrum of the radical intermediate in the addition reaction with that of the synthesized new [⋅P(μ-NTer)₂P-Et] radical clearly proves the existence of radicals over the course of the reaction of biradical [⋅P(μ-NTer)₂P⋅] ( 1 ) with bromoethane. Extensive DFT and coupled cluster calculations corroborate the experimental data for a radical mechanism in the reaction of biradical [⋅P(μ-NTer)₂P⋅] with EtBr. In the field of hetero-cyclobutane-1,3-diyls, the demonstration of a stepwise radical reaction represents a new aspect and closes the gap between P-centered biradicals and P-centered monoradicals in terms of radical reactivity.     

U.S. EPA Regulatory Perspectives on the Use of QSAR for New and Existing Chemical Evaluations

Abstract

As testing is not required, ecotoxicity or fate data are available for ≈ 5% of the approximately 2,300 new chemicals/year (26,000 + total) submitted to the US-EPA. The EPA's Office of Pollution Prevention and Toxics (OPPT) regulatory program was forced to develop and rely upon QSARs to estimate the ecotoxicity and fate of most of the new chemicals evaluated for hazard and risk assessment. QSAR methods routinely result in ecotoxicity estimations of acute and chronic toxicity to fish, aquatic invertebrates, and algae, and in fate estimations of physical/chemical properties, degradation, and bioconcentration. The EPA's Toxic Substances Control Act (TSCA) Inventory of existing chemicals currently lists over 72,000 chemicals. Most existing chemicals also appear to have little or no ecotoxicity or fate data available and the OPPT new chemical QSAR methods now provide predictions and cross-checks of test data for the regulation of existing chemicals. Examples include the Toxics Release Inventory (TRI), the Design for the Environment (DfE), and the OECD/SIDS/HPV Programs. QSAR screening of the TSCA Inventory has prioritized thousands of existing chemicals for possible regulatory testing of: 1) persistent bioaccumulative chemicals, and 2) the high ecotoxicity of specific discrete organic chemicals.     

Computational chemistry in drug lead discovery and design

The main contributions of our group during the last 15 years developing and using biomolecular simulation tools in drug lead discovery and design, in close collaboration with experimental researchers, are presented. Special emphasis has been given to methodological improvements in the following areas: (1) target homology modeling incorporating knowledge about known ligands to accurately characterize the binding site; (2) designing alternative strategies to account for protein flexibility in high-throughput docking; (3) development of stochastic- and normal-mode-based methods to de novo design structurally diverse protein conformers; (4) development and validation of quantum mechanical semi-empirical linear-scaling calculations to correctly estimate ligand binding free energy. Several successful cases of computer-aided drug discovery are also presented, especially our recent work on viral targets.