First diamino Daphniphyllum alkaloid, daphnipaxinin, with an unprecedented heterohexacyclic skeleton from Daphniphyllum paxianum

[structure: see text] The first diamino Daphniphyllum alkaloid, daphnipaxinin (1), with an unprecedented hexacyclic fused skeleton, along with a known alkaloid, daphnicyclidin A (2), was isolated from the stem of Daphniphyllum paxianum Rosenth. The structure and absolute stereochemistry of 1 were established by spectral methods, especially two-dimensional NMR techniques and CD analysis.     

Hemin-histamine-montmorillonite clay conjugate as a model biocatalyst to mimic natural peroxidase

We successfully synthesized the first hemin-montmorillonite bio-conjugate with an amino acid residue to mimic natural peroxidase enzyme. Histamine was intercalated in montmorillonite by cation exchange, then a hemin molecule was loaded onto the histamine-montmorillonite with an adsorption capacity of 7.0 mg g-1. The hemin-histamine-montmorillonite conjugate shows high peroxidase activity as indicated by the oxidation of guaiacol, which is attributed to the activation of hemin by Fe–N complex formation between the imidazole group in histamine and the iron ion in the hemin molecule. Temperature- dependent peroxidase activity for this synthesized biomimetic material indicates that raising the reaction temperature could significantly enhance the activity of the conjugate. The biomimetic catalyst has good reusability; nearly 100% activity can be retained after three cycles. Because montmorillonite clay is widely distributed in the environment, this material offers great potential for in situ and ex situ remediation of many organic contaminants in surface/subsurface soils.     

Synthesis and characterization of temperature-sensitive cellulose-graft-poly(N-isopropylacrylamide) copolymers

A new series of cellulose-graft-poly(N-isopropylacrylamide)(cellulose-g-PNIPAM) copolymers were prepared by atom transfer radical polymerization(ATRP) of N-isopropylacrylamide monomers from a cellulose-based macro-initiator, which was homogeneously synthesized in an ionic liquid 1-allyl-3-methylimidazolium chloride(Amim Cl). The composition of cellulose-g-PNIPAM copolymers could be adjusted by altering the feeding ratio and reaction time. The resultant copolymers with relatively high content of PNIPAM segments(molar substitution of PNIPAM ? 18.3) were soluble in water at room temperature. Aqueous solutions of cellulose-g-PNIPAM copolymers exhibited clear temperature-sensitive behavior, and their sol-to-gel phase transition properties were investigated by dynamic light scattering(DLS) and UV measurements. Compared with pure PNIPAM, the cellulose-g-PNIPAM copolymers possessed higher lower critical solution temperatures(LCST) in a range from 36.9 ?C to 40.8 ?C, which are close to normal human body temperature, and could be tuned by adjusting the content of PNIPAM segments in copolymers. Spherical structure of cellulose-g-PNIPAM copolymers formed at temperatures above LCST and its morphology was observed by TEM and SEM. These novel cellulose-g-PNIPAM copolymers may be attractive substrates for some biomedical applications, such as drug release and tissue engineering.     

一种合成4-羟基苯并香豆素的简便有效方法（英文）

1-萘酚(1a)或2-萘酚(1b)与米氏酸(2)在无溶剂条件下进行研磨反应,分别得到丙二酸单萘基酯3a和3b。然后在Eaton试剂(五氧化二磷+甲基磺酸)的作用下,反应温度为85℃的条件下,3a和3b发生分子内的环化反应,得到目标化合物4-羟基苯并[h]香豆素(4a)和4-羟基苯并[f]香豆素(4b),其收率分别为78%和75%,其结构均已通过波谱数据和元素分析得以表征确认。     

Reduction of nitroaromatics to arylnitrenium ions by vinyl halide cations

The title reduction of nitroaromatics ArNO(2) by vinyl halide radical cations CH(2)[double bond]CH-X(+*)(X = Cl or Br) to form arylnitrenium ions ArNH(+) involves a change in oxidation number of nitrogen from +3 to -1. This novel reaction provides a new route for the generation of arylnitrenium ions, a highly selective method for the detection of explosives in mixtures, and offers clues to the carcinogenic activity of nitroaromatics in vivo.     

Direct and quantitative analysis of underivatized acylcarnitines in serum and whole blood using paper spray mass spectrometry

A simple protocol for rapid quantitation of acylcarnitines in serum and whole blood has been developed using paper spray mass spectrometry. Dried serum and whole blood containing a mixture of ten acylcarnitines at various concentrations were analyzed as spots from paper directly without any sample pretreatment, separation, or derivatization. The composition of the spray solvent was found to be a critical factor: for serum samples, spray solvent of methanol/water/formic acid (80:20:0.1) gave the best signal intensity while for blood samples which contain more matrix components, acetonitrile/water (90:10) was a much more suitable spray solvent. For the paper type and size used, 0.5 μL of sample provided an optimal signal for both serum and whole blood samples. For quantitative profiling, the limits of quantitation obtained from both serum and blood were much lower than the clinically validated cutoff values for diagnosis of fatty acid oxidation disorders in newborn screening. Linearity (R(2) > 0.95) and reproducibility (RSD ~10 %) were achieved in the concentration ranges from 100 nM to 5 μM for the C2 acylcarnitine, and for other acylcarnitines, these values were from 10 to 500 nM. Acylcarnitine profiles offer an effective demonstration of the fact that paper spray mass spectrometry is an appropriate, simple, rapid method with high sensitivity and high reproducibility applicable to newborn screening tests.     

Tailoring the structure of metal oxide nanostructures towards enhanced sensing properties for environmental applications

The present article reviews recent works in our laboratory about the sensing properties to toxic gases using nanostructured WO(3), TiO(2), FTiO(2), and CuO functionalized quartz crystal microbalance (QCM) sensors. WO(3) and TiO(2) functionalized QCM sensors have much shorter response time than those functionalized by conventional hydrogen-bond acidic branched copolymers for detection of dimethyl methylphosphonate (DMMP). FTiO(2) functionalized QCM sensors can improve the gas sensing characteristics by shortening the response time but at the price of partial irreversibility. The sensing mechanism was examined by diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). Varied CuO nanostructures were synthesized by simple modulation of reaction conditions. All the as-prepared CuO was applied on QCM resonators and explored for HCN sensing. Surprisingly, responses of all the sensors to HCN were found to be in an opposite direction as compared with other common volatile substances, offering excellent selectivity for HCN detection. The sensitivity was very high, and the response and recovery were very fast. Comparison of the specific surface areas of CuO nanostructures showed that CuO of higher surface area is more sensitive than that of lower surface area, indicating that the specific surface area of these CuO nanostructures plays an important role in the sensitivity of related sensors. Based on experimental results, a sensing mechanism was proposed in which a surface redox reaction occurs between CuO and Cu(2)O on the CuO nanostructures reversibly upon contact with HCN and air, respectively. The CuO functionalized QCM sensors are considered to be a promising candidate for trace HCN gas detection in practical applications.     

Synthesis and Characterization of Cationic Glycidyl-Based Poly(aminoester)-Folic Acid Targeting Conjugates and Study on Gene Delivery

A new poly(aminoester) (EPAE-FA) containing folic acid and amino groups in the backbone and side chain was synthesized. EPAE-FA self-assembled readily with the plasmid DNA (pCMV-βgal) in HEPES buffer and was characterized by dynamic light scattering, zeta potential, fluorescence images, and XTT cell viability assays. To evaluate the transfection effect of graft ratio of FA on the EPAE system, EPAE-FA polymers with two different graft ratios (EPAE-FA12k and EPAE-FA14k) were also prepared. This study found that all EPAE-FA polymers were able to bind plasmid DNA and yielded positively charged complexes with nano-sized particles ( < 200 nm). To assess the transfection efficiency mediated by EPAE and EPAE-FA polymers, we performed in vitro transfection activity assays using FR-negative (COS-7) and FR-positive (HeLa) cells. The EPAE-FA12k/DNA and EPAE-FA14k/DNA complexes were able to transfect HeLa cell in vitro with higher transfection efficiency than PEI25k/DNA at the similar weight ratio. These results demonstrated that the introduction of FA into EPAE system had a significant effect on transferring ability for FR-positive cells (HeLa). Examination of the cytotoxicity of PEI25k and EPAE-FA system revealed that EPAE-FA system had lower cytotoxicity. In this paper, EPAE-FA seemed to be a novel cationic poly(aminoester) for gene delivery and an interesting candidate for further study.     

Rapid finding and quantification of the major antioxidant in water extracts of three marine drug organisms from China by online HPLC-DAD/MS-DPPH

A method based on high-performance liquid chromatography (HPLC) with diode array detector coupled with electrospray ionisation-mass spectrometry and an online detection system for radical scavenging was established and used to rapidly find and quantify antioxidant compounds in the water extracts of Hippocampus japonicus Kaup, Hippocampus kuda Bleeker and Syngnathus acus Linnaeus. The online screening results revealed the presence of one major radical scavenging compound identified as hypoxanthine by comparison of mass data and retention time with the standard. Subsequently, the developed HPLC method was applied to quantify hypoxanthine in different H. japonicus, H. kuda and S. acus samples. The results indicated that the developed HPLC method is simple and reliable for the quantification of hypoxanthine with a detection limit at 0.002 μg mL(-1), and a high recovery from 96.3% to 102.1%. This method provides a powerful tool for rapid identification and quantification of free radical scavenging compounds in complex marine natural products.     

Monodisperse rutile microspheres with ultrasmall nanorods on surfaces: Synthesis, characterization, luminescence, and photocatalysis

This work demonstrates the process of building optoelectrically cooperative surface wetting in smart and precise way. The superhydrophobic photosensitive film is constructed with TiO(2) nanotube arrays. Compared with conventional organic dyes, CdS quantum dots (QDs) as sensitizer layer are modified on TiO(2) nanotubes surface to improve photosensitivity of the composited surface in visible light region, which offer the benefit for designing and fabricating solid state hetero-junction devices. ITO glass is introduced as top electrode to apply electrical and optical stimuli and the patterned wetting is instantly obtained with masking light through ITO. The optoelectrically cooperative wettability conversion occurred on superhydrophobic TiO(2) nanotube surface at critical voltage of 12 V, which was decreased by 18 V comparing with only using electric stimulus. This study provides potential applications for TiO(2) nanotube arrays to the associated research of liquid reprography, location-controlled microfluidic device and lab-on-chip.