Self‐Propelled Janus Mesoporous Silica Nanomotors with Sub‐100 nm Diameters for Drug Encapsulation and Delivery

The synthesis of an innovative self‐propelled Janus nanomotor with a diameter of about 75 nm that can be used as a drug carrier is described. The Janus nanomotor is based on mesoporous silica nanoparticles (MSNs) with chromium/platinum metallic caps and propelled by decomposing hydrogen peroxide to generate oxygen as a driving force with speeds up to 20.2 μm s^?1 (about 267 body lengths per second). The diffusion coefficient (D) of nanomotors with different H₂O₂ concentrations is calculated by tracking the movement of individual particles recorded by means of a self‐assembled fluorescence microscope and is significantly larger than free Brownian motion. The traction of a single Janus MSN nanomotor is estimated to be about 13.47×10^?15 N. Finally, intracellular localization and drug release in vitro shows that the amount of Janus MSN nanomotors entering the cells is more than MSNs with same culture time and particle concentrations, meanwhile anticancer drug doxorubicin hydrochloride loaded in Janus MSNs can be slowly released by biodegradation of lipid bilayers in cells.     

De Novo Design of an Endohedral Heteronuclear Dimetallofullerene (UGd)@C60 with Exceptional Structural and Electronic Properties

Ever since the first synthesis of La@C₈₂ and U@C₂₈, there has been a growing interest in the study of endohedral metallofullerenes (EMFs) because of their great potential in various applications. Here we design a novel heteronuclear EMF (U‐Gd)@C₆₀, by using density functional theory (DFT), which shows an encapsulation energy of about ?5.53 eV, comparable to that of U₂@C_60, La₂@C₈₀, and Lu₂@C₇₆. (U‐Gd)@C₆₀ is found to have a surprising twofold, single‐electron U?Gd bond that results from the strong nanoconfinement of the fullerene, dominated by uranium′s 5f and 6d and gadolinium′s 5d atomic orbitals. The ground state shows an 11‐et high spin state, and the net spins distributed on the U‐pole carbons are relatively scattered, while they are highly concentrated on the Gd‐pole carbons. The exceptional electronic characteristics of this novel EMF, containing both uranium and gadolinium atoms encapsulated, might prove useful for future applications in nuclear energy and biomedicine.     

Highly Efficient Electrocatalysts for Oxygen Reduction Based on 2D Covalent Organic Polymers Complexed with Non‐precious Metals

A class of 2D covalent organic polymers (COPs) incorporating a metal (such as Fe, Co, Mn) with precisely controlled locations of nitrogen heteroatoms and holes were synthesized from various N‐containing metal–organic complexes (for example, metal–porphyrin complexes) by a nickel‐catalyzed Yamamoto reaction. Subsequent carbonization of the metal‐incorporated COPs led to the formation of COP‐derived graphene analogues, which acted as efficient electrocatalysts for oxygen reduction in both alkaline and acid media with a good stability and free from any methanol‐crossover/CO‐poisoning effects.     

Palladium‐catalyzed direct arylation of polyfluoroarene and facile synthesis of liquid crystal compounds

A convenient approach has been developed to prepare polyfluorobiphenyl by Pd(OAc)₂/PCy₃‐catalyzed direct arylation of polyfluoroarenes with aromatic halides in the presence of Cs₂CO₃ as base and toluene as solvent. In most cases, the desired arylated products of aromatic bromides were obtained in good to excellent yield at 80°C, and aryl chlorides also gave modest to good yields of arylated products at 110°C. According to this efficient C―C bondforming method, polyfluorobiphenyl liquid crystal compounds were prepared by Pd‐catalyzed direct arylation reactions of polyfluoroarenes with long alkyl chain substituted aryl bromides in 62–96% yield. Copyright © 2014 John Wiley & Sons, Ltd.     

Comparative pharmacokinetic study of two boswellic acids in normal and arthritic rat plasma after oral administration of Boswellia serrata extract or Huo Luo Xiao Ling Dan by LC‐MS

Huo Luo Xiao Ling Dan (HLXLD), a Chinese herbal formula composed of 11 different herbs, has been used traditionally for the treatment of arthritis and other chronic inflammatory diseases. However, the pharmacokinetic profile of its anti‐inflammatory bioactive compounds has not been elucidated. Boswellic acids are the bioactive compounds with potent anti‐inflammatory activity isolated from Boswellia serrate which is one of the 11 herbs of HLXLD. The objective of the study was to compare the pharmacokinetics of the two bioactive bowsellic acids: 11‐keto‐β‐boswellic acid and 3‐O‐acetyl‐11‐keto‐β‐boswellic following oral administration of HLXLD or Boswellia serrata extract alone in normal and arthritic rats. An LC‐MS method was developed and validated for the determination of 11‐keto‐β‐boswellic acid and 3‐O‐acetyl‐11‐keto‐β‐boswellic in the comparative pharmacokinetic study. The results showed that there were significant differences in pharmacokinetic parameters between normal and arthritic groups. Interestingly, the absorptions of two boswellic acids were significantly higher in HLXLD than Boswellia serrata extract alone, indicating the synergistic effect of other herbal ingredients in HLXLD. This comparative pharmacokinetic study provided direct evidence supporting the notion that the efficacy of a complex mixture such as HLXLD is better than that of single components in treating human diseases. Copyright © 2014 John Wiley & Sons, Ltd.     

High‐performance segmented polyurea by transesterification of diphenyl carbonates with aliphatic diamines

In an effort to develop a green process for the production of elastomeric polyurethane–urea (PUaE) through a nonisocyanate route, a highly practical method was found using diphenyl carbonate (DPC) instead of diisocyanate as the carbonylation agent. The transesterification of aliphatic diamines in a solvent such as tetramethylene sulfone (TMS) with DPC results in a new process obtaining new segmented PUaE with high molecular weights and excellent mechanical performance. The key to the present success lies in the timing and sequence of the diamine addition forming initial carbamate intermediates in situ and then in shifting the equilibrium toward polyurea product formation by phenol removal from the TMS solution so that high‐molecular‐weight polyurea could be formed favorably. The most optimized polyurea films made in this study has a η_inh of 0.64, with high‐performance characteristics showing tensile strength of greater than 30 MPa and elongation exceeding 400% with decomposition temperature (5%) of >280 °C. Well‐defined soft‐ and hard‐segment domains were observed for the products as determined by atomic force microscope. This new improved process to produce segmented polyurea thereby complies fully with the principles of green chemistry using readily available chemicals. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 2781–2790     

Chiral sensing of Eu(III)‐containing achiral polymer complex from chiral amino acids coordination induction

The β‐diketonate‐based achiral polymer P‐1 could be synthesized by the polymerization of 3,7‐dibromo‐2,8‐dimethoxy‐5,5‐dioctyl‐5H‐dibenzo[b,d]silole ( M1 ) with (Z)?1,3‐bis(4‐ethynylphenyl)?3‐hydroxyprop‐en‐1‐one ( M2 ) via typical Sonogashira coupling reaction. The β‐diketonate unit in the main chain backbone of P‐1 can further coordinate with Eu(TTA)_x [TTA^? = 4,4,4‐trifluoro‐1‐(thiophen‐2‐yl)butane‐1,3‐dionate anion, X = 1, 2, 3] to afford corresponding Eu(III)‐containing polymer complexes. The resulting achiral polymer complex P‐2 (X = 2) can exhibit strong circular dichroism (CD) response toward both N‐Boc‐l and d‐ proline enantiomers. The CD signal was preliminarily attributed to coordination induction between chiral N‐Boc‐proline and the Eu(III) complex moiety. The linear regression analysis of CD sensing shows a good agreement between the magnitude of molar ellipticity and concentration of chiral N‐Boc‐l or d‐ proline, which indicates this kind Eu(III)‐containing achiral polymer complex can be used as a chiral probe for enantioselective recognition of N‐Boc‐l or d‐ proline enantiomers based on Cotton effect of CD spectra. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 3080–3086     

The Injury and Cumulative Effects on Human Skin by UV Exposure from Artificial Fluorescence Emission

The injury and cumulative effects of UV emission from fluorescence lamp were studied. UV intensity from fluorescence lamp was measured, and human skin samples (hips, 10 volunteers) were exposed to low‐dose UV irradiation (three times per week for 13 consecutive weeks). Three groups were examined: control group without UV radiation; low‐dose group with a cumulative dose of 50 J cm^?2 which was equivalent to irradiation of the face during indoor work for 1.5 years; and high‐dose group with 1000 J cm^?2 cumulative dose equivalent to irradiation of the face during outdoor activities for 1 year. Specific indicators were measured before and after UVA irradiation. The findings showed that extending the low‐dose UVA exposure decreased the skin moisture content and increased the transepidermal water loss as well as induced skin color changes (decreased L* value, increased M index). Furthermore, irradiated skin showed an increased thickness of cuticle and epidermis, skin edema, light color and unclear staining collagen fibers in the dermis, and elastic fiber fragmentation. In addition, MMP‐1, p53 and SIRT1 expression was also increased. Long‐term exposure of low‐dose UVA radiation enhanced skin photoaging. The safety of the fluorescent lamp needs our attention.     

An effective colorimetric and ratiometric fluorescent probe for bisulfite in aqueous solution

We have developed the first two-photon colorimetric and ratiometric fluorescent probe, BICO, for the detection of bisulfite (HSO₃⁻) in aqueous solution. The probe contains coumarin and benzimidazole moieties and can detect HSO₃⁻ based on the Michael addition reaction with a limit of detection 5.3 × 10⁻⁸ M in phosphate-buffered saline solution. The probe was used to detect bisulfite in tap water, sugar and dry white wine. Moreover, test strips were made and used easily. We successfully applied the probe to image living cells, using one-photon fluorescence imaging. BICO overcomes the limitations in sensitivity of previously reported probes and the solvation effect of bisulfite, which demonstrates its excellent value in practical application.