Monochromophore-Based Phosphorescence and Fluorescence from Pure Organic Assemblies for Ratiometric Hypoxia Detection

Hypoxia is a parameter related to many diseases. Ratiometric hypoxia probes often rely on a combination of an O₂-insensitive fluorophore and an O₂-sensitive phosphor in a polymer matrix, which require high cost and multi-step synthesis of transition metal complexes. The two-chromophore hypoxia probes encounter unfavorable energy transfer processes and different stabilities of the chromophores. Reported herein is a pure organic ratiometric hypoxia nanoprobe, assembled by a monochromophore, naphthalimide ureidopyrimidinone (BrNpA-UPy), bridged by a bis-UPy-functionalized benzyl skeleton. The joint factors of quadruple hydrogen bonding, the rigid backbone of UPy, and bromine substitution of the naphthalimide derivative facilitate bright phosphorescence (Φ_P=7.7 %, τ_P=3.2 ms) and fluorescence of the resultant nanoparticles (SNPs) at room temperature, which enable accurate, ratiometric, sensitive oxygen detection (K_sv=189.6 kPa⁻¹) in aqueous solution as well as in living HeLa cells.     

Oversampling Free Energy Perturbation Simulation in Determination of the Ligand-Binding Free Energy

Determination of the ligand-binding affinity is an extremely interesting problem. Normally, the free energy perturbation (FEP) method provides an appropriate result. However, it is of great interest to improve the accuracy and precision of this method. In this context, temperature replica exchange molecular dynamics implementation of the FEP computational approach, which we call replica exchange free energy perturbation (REP) was proposed. In particular, during REP simulations, the system can easily escape from being trapped in local minima by exchanging configurations with high temperatures, resulting in significant improvement in the accuracy and precision of protein–ligand binding affinity calculations. The distribution of the decoupling free energy was enlarged, and its mean values were decreased. This results in changes in the magnitude of the calculated binding free energies as well as in alteration in the binding mechanism. Moreover, the REP correlation coefficient with respect to experiment ( R^REP = 0.85 ± 0.15 ) is significantly boosted in comparison with the FEP one ( R^FEP = 0.64 ± 0.30 ). Furthermore, the root-mean-square error (RMSE) of REP is also smaller than FEP, RMSE^REP = 4.28 ± 0.69 versus RMSE^FEP = 5.80 ± 1.11 kcal/mol, respectively. © 2019 Wiley Periodicals, Inc.     

Mechanistic Insights into the Interface‐Directed Transformation of Thiols into Disulfides and Molecular Hydrogen by Visible‐Light Irradiation of Quantum Dots

Quantum dots (QDs) offer new and versatile ways to harvest light energy. However, there are few examples involving the utilization of QDs in organic synthesis. Visible‐light irradiation of CdSe QDs was found to result in virtually quantitative coupling of a variety of thiols to give disulfides and H₂ without the need for sacrificial reagents or external oxidants. The addition of small amounts of nickel(II) salts dramatically improved the efficiency and conversion through facilitating the formation of hydrogen atoms, thereby leading to faster regeneration of the ground‐state QDs. Mechanistic studies reveal that the coupling reaction occurs on the QD surfaces rather than in solution and offer a blueprint for how these QDs may be used in other photocatalytic applications. Because no sacrificial agent or oxidant is necessary and the catalyst is reusable, this method may be useful for the formation of disulfide bonds in proteins as well as in other systems sensitive to the presence of oxidants.     

Asymmetric Synthesis of a Fused Tricyclic Hydronaphthofuran Scaffold by Desymmetric [2+2+2] Cycloaddition

A rhodium(I)‐BINAP‐catalyzed highly enantioselective [2+2+2] cycloaddition of enynes with alkynes has been developed. Diverse fused tricyclic hydronaphthofuran scaffolds with three consecutive stereogenic centers were constructed in one step from easily available materials with excellent chemo‐, regio‐, diastereo‐, and enantioselectivity. Notable features of these reactions include 100 % atom economy, very broad scope, and mild reaction conditions.     

Development of a laser-based measurement system for evaluation of the scraping workpiece quality

A laser-based measurement system for evaluation of the scraping workpiece quality that can eliminate contact-induced measurement errors and increase measurement accuracy is proposed. The laser-based measurement system comprises a light-scattering-type triangulation laser, a computer numerical control (CNC) machine tool, and an analog-to-digital (A/D) card. The triangulation laser measures the depth of the scraping spots and the CNC machine tool locates their position. The 3D data of the scraping workpiece is then drawn using the least squares method. Cast iron and Turcite workpieces can be measured. Five parameters of the scraping workpiece, namely peak points per square inch, percentage of points, distribution of heights of points or depth of surroundings, edge shape of the grooves, and flatness, can be evaluated. The scanning rate and sampling rate of the laser-based measurement system are 100 mm/s and 10 KHz, respectively. In the future, an appliance machine based on the proposed system will be designed for the on-line detection of scraping workpieces.     

Atomic force microscopy-based repeated machining theory for nanochannels on silicon oxide surfaces

The atomic force microscopy (AFM)-based repeated nanomachining of nanochannels on silicon oxide surfaces is investigated both theoretically and experimentally. The relationships of the initial nanochannel depth vs. final nanochannel depth at a normal force are systematically studied. Using the derived theory and simulation results, the final nanochannel depth can be predicted easily. Meanwhile, if a nanochannel with an expected depth needs to be machined, a right normal force can be selected simply and easily in order to decrease the wear of the AFM tip. The theoretical analysis and simulation results can be effectively used for AFM-based fabrication of nanochannels.     

Triple negative permeability band in plasmon-hybridized cut-wire-pair metamaterials

We expand the picture of plasmon hybridization in metamagnetic structure via numerically studying the electromagnetic coupling in the metallic cut-wire-pair super cells. It is shown that a triple negative permeability band can be achieved by systematically controlling the plasmon hybridization in such the structure. The corresponding transmission properties as well as the electromagnetic responses of the plasmon-hybridized structures were presented by using the finite integration technique simulations. Our results would reveal a promising design to obtain the multiple negative refractions based on the combination of hybridized cut-wire-pairs and continuous wires.     

Nonisothermal crystallization kinetics of poly(ε‐caprolactone) blocks in double crystalline triblock copolymers containing poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) and poly(ε‐caprolactone) units

The poly(3‐hydroxbutyrate‐co‐3‐hydroxyvalerate)/poly(ε‐caprolactone) block copolymers (PHCLs) with three different weight ratios of PCL blocks (38%, named PHCL‐38; 53%, named PHCL‐53; and 60%, named PHCL‐60) were synthesized by using PHBV with two hydroxyl end groups to initiate ring‐opening polymerization of ε‐caprolactone. During DSC cooling process, melt crystallization of PHCL‐53 at relatively high cooling rates (9, 12, and 15 °C min^?1) and PHCL‐60 at all the selected cooling rates corresponded to PCL blocks so that PHCL‐53 and PHCL‐60 were used to study the nonisothermal crystallization behaviors of PCL blocks. The kinetics of PCL blocks in PHCL‐53 and PHCL‐60 under nonisothermal crystallization conditions were analyzed by Mo equation. Mo equation was successful in describing the nonisothermal crystallization kinetics of PCL blocks in PHCLs. Crystallization activation energy were estimated using Kissinger's method. The results of kinetic parameters showed that both blocks crystallized more difficultly than corresponding homopolymers. With the increase of PCL content, the crystallization rate of PCL block increased gradually. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2010