Linear and nonlinear optical properties of ZnO nanorod arrays

Polarization-dependent linear absorption, second-harmonic generation （SHG） and 3rd-order nonlinearities of wellaligned ZnO nanorod arrays have been investigated with ps pulses. The depressed spectral width and the enhanced intensity of reflective SHG along the long axis of ZnO nanorods were observed by using p-polarized pulses, which is explained by the optical confinements. The nonlinear absorption coefficient measured with s-polarization reached the maximum 4.0×10^4cm/GW at the wavelength -750nm, which revealed a large two-photon resonance absorption attributed to the quantum confined exciton when the polarization is vertical to the long axis of ZnO nanorod.     

Discovery of a new nontoxic cuprate superconducting system Ga-Ba-Ca-Cu-O

Superconductivity is observed in a new nontoxic cuprate system Ga-Ba-Ca-Cu-O,with T_c=82 K for Ga Ba_2Ca_5Cu_6O_(14+δ)(Ga-1256)and T_c=116 K probably for Ga Ba_2Ca_3Cu_4O_(10+δ)(Ga-1234)or Ga Ba_2Ca_2Cu_3O_(8+δ)(Ga-1223),respectively.All compounds are fabricated by solid state reaction method under high pressure and high temperature.Samples are characterized by resistivity,magnetization and X-ray diffraction(XRD)measurements.The temperature dependence of magnetization measured in both zero-field-cooled and field-cooled processes on one sample(S1)shows two superconducting transitions at about 82 K and113 K.The estimated shielding fraction for the phase with T_cof 82 K is about 67%,while the fraction for another phase with T_(c )of 113 K is quite small.The XRD Rietveld refinement for S1 indicates two main phases existing in the sample,Ga-1256 with fraction of about 58%and non-superconducting Ca_(0.85)Cu O_2with fraction of about 42%respectively.Thus,we can conclude the superconducting phase with transition temperature of 82 K is due to Ga-1256.The resistivity measurement also confirms the superconductivity for S1,and the resistivity reaches zero at about 82 K.The temperature dependence of magnetization for another sample(S2)shows much higher superconducting shielding fraction for the phase with T_cof 116 K,which may be a promising prospective for the synthesis of Ga-1234 or Ga-1223 phase.     

The Special “Morse Code” between Solvent Polarity and Morphology Flexibility in a POSS–Dendrimer Supramolecular System

An amazing phenomenon of the relative magnitude of modulus of two liquid-crystal (LC) gels is found inverted under/above their phase transition temperature T_LC-iso, which is further proved to be caused by their diverse morphology flexibility. By testing the polarity of two LCs, gelator POSS-G1-Boc (POSS=polyhedral oligomeric silsesquioxane) was discovered to self-assemble into more flexible structures in a relatively low polar LC, whereas more rigid ones are formed in higher polar LC. Hence, a fitting function to connect morphology flexibility with solvent polarity was established, which can even be generalized to a number of common solvents. Experimental observations and coarse-grained molecular dynamics simulations revealed that solvent polarity mirrors a “Morse code”, with each “code” corresponding to a specific morphology flexibility.     

Development of Lysosome-Targeted Fluorescent Probes for Cys by Regulating the Boron-dipyrromethene (BODIPY) Molecular Structure

Our previous discovery suggested that substituents on the 1,7 positions delicately modulate the sensing ability of the meso-arylmercapto boron-dipyrromethene (BODIPY) to biothiols. In this work, the impact of delicate modulations on the sensing ability is investigated. Therefore, 1,7-dimethyl, 3,5-diaryl substituted BODIPY is designed and developed and its conformationally restricted species with a meso-arylmercapto moiety ( DM-BDP-SAr and DM-BDP-R-SAr ) as selective fluorescent probes for Cys. Moreover, the lysosome-target probes ( Lyso-S and Lyso-D ) based on DM-BDP-SAr carrying one or two morpholinoethoxy moieties were developed. They were able to detect Cys selectively in vitro with low detection limits. Both Lyso-S and Lyso-D localized nicely in lysosomes in living HeLa cells and exhibited red fluorescence for Cys. Moreover, a novel fluorescence quenching mechanism was proposed from the calculations by density functional theory (DFT). The probes may go through intersystem crossing (from singlet excited state to triplet excited state) to result in fluorescence quenching.     

Synthesis and characterization of degradable hyperbranched poly(2‐ethyl‐2‐oxazoline)

Hyperbranched poly(2‐ethyl‐2‐oxazoline) was synthesized by a combination of cationic ring‐opening polymerization and the oxidation of thiol to disulfide groups. A three‐arm star poly(2‐ethyl‐2‐oxazoline) (PEtOx) was first synthesized using 1,3,5‐tris(bromomethyl) benzene as an initiator. The star PEtOx was end‐capped with potassium ethyl xanthate. Similarly, a linear PEtOx was synthesized and end‐capped with potassium ethyl xanthate using benzyl bromide as an initiator. Hyperbranched PEtOx was then obtained by in situ cleaving and subsequent oxidation of the star PEtOx and linear PEtOx mixture with n‐butylamine as both a cleaving agent and a base in tetrahydrofuran. The linear PEtOx was used to prevent the formation of gel. The hyperbranched PEtOx can be cleaved with dithiothreitol to trithiol and monothiol polymer. The hyperbranched PEtOx shows no remaining thiols using Ellman's assay. The resulting hyperbranched PEtOx was hydrolyzed to a novel hyperbranched polyethyleneimine with degradable disulfide linkages. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 2030–2037     

A Biosilification Fusion Protein for a ‘Self‐immobilising’ Sarcosine Oxidase Amperometric Enzyme Biosensor

Monomeric sarcosine oxidase (mSOx) fusion with the silaffin peptide, R5, designed previously for easy protein production in low resource areas, was used in a biosilification process to form an enzyme layer electrode biosensor. mSOx is a low activity enzyme (10–20 U/mg) requiring high amounts of enzyme to obtain an amperometric biosensor signal, in the clinically useful range <1 mM sarcosine, especially since the K_m is >10 mM. An amperometric biosensor model was fitted to experimental data to investigate dynamic range. mSOx constructs were designed with 6H (6×histidine) and R5 (silaffin) peptide tags and compared with native mSOx. Glutaraldehyde (GA) cross‐linked proteins retained ～5 % activity for mSOx and mSOx‐6H and only 0.5 % for mSOx‐R5. In contrast R5 catalysed biosilification on (3‐mercaptopropyl) trimethoxysilane (MPTMS) and tetramethyl orthosilicate (TMOS) particles created a ‘self‐immobilisation’ matrix retaining 40 % and 76 % activity respectively. The TMOS matrix produced a thick layer (>500 μm) on a glassy carbon electrode with a mediated current due to sarcosine in the clinical range for sarcosinemia (0–1 mM). The mSOx‐R5 fusion protein was also used to catalyse biosilification in the presence of creatinase and creatininase, entrapping all three enzymes. A mediated GC enzyme linked current was obtained with dynamic range available for creatinine determination of 0.1–2 mM for an enzyme layer ～800 nm.     

Electron Configuration Modulation of Nickel Single Atoms for Elevated Photocatalytic Hydrogen Evolution

The emerging metal single‐atom catalyst has aroused extensive attention in multiple fields, such as clean energy, environmental protection, and biomedicine. Unfortunately, though it has been shown to be highly active, the origins of the activity of the single‐atom sites remain unrevealed to date owing to the lack of deep insight on electronic level. Now, partially oxidized Ni single‐atom sites were constructed in polymeric carbon nitride (CN), which elevates the photocatalytic performance by over 30‐fold. The 3d orbital of the partially oxidized Ni single‐atom sites is filled with unpaired d‐electrons, which are ready to be excited under irradiation. Such an electron configuration results in elevated light response, conductivity, charge separation, and mobility of the photocatalyst concurrently, thus largely augmenting the photocatalytic performance.     

One-pot ligation strategy for atypical ubiquitin chains synthesis by using the trifluoroacetamidomethyl-protected isopeptide-linked Ub (Tfacm-isoUb) unit

Protein chemical synthesis can provide the homogeneous atypical ubiquitin chains that are usually difficult to obtain by other methods. Herein, we report a new one-pot ligation approach for the synthesis of atypical Ub chains based on the Tfacm-protected isoUb building block with operational simplicity and high efficiency. The key intermediate, the Tfacm-protected isoUb building block can be readily prepared by Fmoc SPPS. The practicality and efficiency of the new method is demonstrated by the successful preparation of K11-linked di-Ub.