Multipolar Porphyrin-Triazatruxene Arrays for Two-Photon Fluorescence Cell Imaging

Two-photon excited fluorescent (TPEF) materials are highly desirable for bioimaging applications owing to their unique characteristics of deep-tissue penetration and high spatiotemporal resolution. Herein, by connecting one, two, or three electron-deficient zinc porphyrin units to an electron-rich triazatruxene core via ethynyl π-bridges, conjugated multipolar molecules TAT-(ZnP) _n (n=1–3) were developed as TPEF materials for cell imaging. The three new dyes present high fluorescence quantum yields (0.40–0.47) and rationally improved two-photon absorption (TPA) properties. In particular, the peak TPA cross section of TAT-ZnP (436 GM) is significantly larger than that of the ZnP reference (59 GM). The δ_TPA values of TAT-(ZnP)₂ and TAT-(ZnP)₃ further increase to 1031 and up to 1496 GM, respectively, indicating the effect of incorporated ZnP units on the TPA properties. The substantial improvement of the TPEF properties is attributed to the formation of π-conjugated quadrapole/octupole molecules and the extension of D -π-A-D systems, which has been rationalized by density function theory (DFT) calculations. Moreover, all of the three new dyes display good biocompatibility and preferential targeting ability toward cytomembrane, thus can be superior candidates for TPEF imaging of living cells. Overall, this work demonstrated a promising strategy for the development of porphyrin-based TPEF materials by the construction and extension of D -π-A-D multipolar array.     

Biodegradable Black-Phosphorus-Nanosheet-Based Nanoagent for Enhanced Chemo-Photothermal Therapy

Black phosphorus nanosheet (BPNS) is a promising multifunctional material in the biomedical field with biodegradability and low side effects, however its features are always weakened severely owing to its poor stability. Here, a novel method is developed for improving the defect of BPNS based on the effective protection of poly(lactic-co-glycolic acid) (PLGA), which preserves the stable photothermal therapy (PTT) effect of BPNS and biodegradability of the material. Meanwhile, doxorubicin (DOX) is loaded on BPNS/PLGA to get BPNS/PLGA/DOX for further chemotherapy and preventing the recurrence of tumor after PTT. The presented combined therapeutic strategy exploits the strengths and improves the defects of BPNS, thus developing an efficient and safe nanoagent for cancer therapy, which affords and reveals the great potential of BPNS in nanomedicine.     

Improved Interfacial Bonding Strength and Reliability of Functionalized Graphene Oxide for Cement Reinforcement Applications

Poor bonding strength between nanomaterials and cement composites inevitably lead to the failure of reinforcement. Herein, a novel functionalization method for the fabrication of functionalized graphene oxide (FGO), which is capable of forming highly reliable covalent bonds with cement hydration products, and therefore, suitable for use as an efficient reinforcing agent for cement composites, is discussed. The bonding strength between cement and aggregates was improved more than 21 times with the reinforcement of FGO. The fabricated FGO also demonstrated many important features, including high reliability in cement pastes, good dispersibility, and efficient structural refinement of cement hydration products. With the incorporation of FGO, cement mortar samples demonstrated up to 40 % increased early and ultimate strength. Such results make the fast demolding and manufacture of light constructions become highly possible, and show strong advantages on improving productivity, saving cost, and reducing CO₂ emissions in practical applications.     

In Vivo Metabolism Study of Timosaponin BIII in Rat Using HPLC-QTOF-MS/MS

Timosaponin BIII, as one of the steroid saponins isolated from Anemarrhena asphodeloides Bge., was proved to have many pharmacological activities in recent years and became a natural active compound with good development prospect. In the present study, a simple and rapid method using high-performance liquid chromatography/quadrupole-time-of-flight mass spectrometry was developed for the determination of the structures of timosaponin BIII and its metabolites in rats after administrating intragastrically at 300 mg kg⁻¹. By comparing their changes in molecular masses (ΔM), retention times and spectral patterns with those of the parent compound, nine metabolites were detected and identified in urine, and eight in plasma as well as four in brain. It is also indicated that the deglycosylation and oxidation reactions were the main metabolic pathways in the biotransformation of timosaponin BIII in vivo and the structures of the nine metabolites were identified and proposed to be timosaponin BII(M1), the hydroxylated metabolite of TBII(M2), the hydroxylated metabolites of TBIII(M3 and M4), deglycosylation and monooxygenation product of TBIII(M5), the deglycosylation product of TBII(M6), timosaponin AIII(M8), the isomers of timosaponin AIII(M7 and M9).

     

Sulfur and Nitrogen Codoped Carbon Tubes as Bifunctional Metal‐Free Electrocatalysts for Oxygen Reduction and Hydrogen Evolution in Acidic Media

Invited for the cover of this issue is the group of Qiang Wu and Zheng Hu at Nanjing University. The image depicts sulfur and nitrogen codoped carbon tubes as bifunctional metal‐free electrocatalysts for oxygen reduction and hydrogen evolution in acidic media. Read the full text of the article at 10.1002/chem.201601535 .     

A nonconvex formulation for low rank subspace clustering: algorithms and convergence analysis

We consider the problem of subspace clustering with data that is potentially corrupted by both dense noise and sparse gross errors. In particular, we study a recently proposed low rank subspace clustering approach based on a nonconvex modeling formulation. This formulation includes a nonconvex spectral function in the objective function that makes the optimization task challenging, e.g., it is unknown whether the alternating direction method of multipliers (ADMM) framework proposed to solve the nonconvex model formulation is provably convergent. In this paper, we establish that the spectral function is differentiable and give a formula for computing the derivative. Moreover, we show that the derivative of the spectral function is Lipschitz continuous and provide an explicit value for the Lipschitz constant. These facts are then used to provide a lower bound for how the penalty parameter in the ADMM method should be chosen. As long as the penalty parameter is chosen according to this bound, we show that the ADMM algorithm computes iterates that have a limit point satisfying first-order optimality conditions. We also present a second strategy for solving the nonconvex problem that is based on proximal gradient calculations. The convergence and performance of the algorithms is verified through experiments on real data from face and digit clustering and motion segmentation.     

Coupled Sliding Discharges: A Scalable Nonthermal Plasma System Utilizing Positive and Negative Streamers on Opposite Sides of a Dielectric Layer

A nonthermal plasma system based on simultaneously formed positive and negative streamers on either side of a dielectric layer is described. The coupled sliding discharge (CSD) reactor based on this concept was found to be scalable by stacking and operating multiple electrode assemblies in parallel, similarly to the shielded sliding discharge (SSD) reactor reported earlier. A comparison of the two systems showed that although the energy density in the CSD reactor was lower, the efficiency for NO conversion and ozone synthesis from dry air were significantly higher. The energy cost for 50 % NO removal was ~30 eV/molecule compared to ~60 eV/molecule in the case of the SSD under the same conditions of 330 ppm initial NO concentration in air. The energy cost decreased to ~12 eV/molecule in both cases when NO was mixed with plasma-activated air at the outlet of the reactor to utilize ozone for NO conversion i.e., indirect plasma treatment. The energy yield for ozone generation from dry air was at ~70 g/kWh, comparable in both systems. The results show that the concept of a CSD, as that of SSDs, allows the construction of compact, efficient plasma reactors.     

Solvent‐free inkjet printing process for the fabrication of conductive,transparent, and flexible ionic liquid‐polymer gel structures

A new and solvent‐free process for the fabrication of inkjet printed ionic liquid‐polymer gel microstructures with high‐resolution (line widths of ～40 μm), good electrical conductivity (5–30 mS cm^?1), optical transparency, and mechanical flexibility is presented. Carrying out the printing and polymerization process in nitrogen atmosphere eliminates the inhibiting influence of oxygen and guarantees homogeneously gelled structures. Careful selection and combination of ionic liquids (ILs) and unsaturated monomers makes it possible to achieve low viscosities which are printable with commercially available inkjet printers and printheads without adding extra solvents. By using different types and amounts of ILs and monomers the resulting properties of the printed IL‐polymer gels can be controlled in terms of ionic conductivity, optical transmission, and mechanical flexibility. Higher conductivities are possible by using a bifunctional instead of a monofunctional monomer, which allows one to lower the amount of monomer without loss in mechanical strength. Cast samples make it possible to obtain data of transmission (～90% for 170‐μm thick films) and mechanical flexibility (E = 0.02–0.23 MPa) of bulk material. Comparing electrical conductivity of printed and cast samples, the higher values of printed samples indicate the conductivity enhancing influence of moisture absorbed from the surrounding atmosphere after the fabrication process. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2011