Using NaCl particles as porogen to prepare a highly adsorbent chitosan membranes

Macroporous chitosan membranes were prepared by using NaCl particles porogen and genipin as cross-linking agent. For characterization and sorption behavior comparison, other genipin cross-linked chitosan membranes were prepared by either freeze drying or by using silica particles as porogen. The mean pore diameter, the porosity, the crystallinity index (CrI) as well as the effect of the drying procedures of these chitosan membranes were examined. NaCl reduced the CrI of the chitosan membrane. The oven drying (OD) procedure decreased the mean pore diameter, the porosity, and increased the CrI of the chitosan membranes when compared with the vacuum drying (VD) procedure. The heat treatment of chitosan membrane in aqueous NaOH to attract silica porogen increased the CrI of the membrane. Under the same conditions, the membranes prepared with NaCl had better sorption performance on RR 189 and Cu²⁺ than other membranes. The maximum sorption capacity (q_e) reached 1836.17 mg RR 189/g chitosan and 151.98 mg Cu²⁺/g chitosan. The pore diameter (d_pore) of the membranes was much larger than the diameter of the adsorbate molecules (d_adsorbate), such that the ratio of d_pore/d_adsorbate had little influence on q_e. The porosity and the amorphous extent of the membranes were almost the same on q_e. When using tyrosinase catalyzing, the hydrocaffeic acid (HCA) grafted on the NaCl treated chitosan membrane was almost 10 times more than on chitosan beads. The chitosan membrane prepared with NaCl can be used as a good adsorbent with high loading capacity for implanting molecules (such as ligands, enzymes, etc.) on.     

Stereodivergent Synthesis of 17‐α and 17‐β‐Aryl Steroids: Application and Biological Evaluation of D‐Ring Cortistatin Analogues

One stereocenter makes all the difference : The synthesis and biological evaluation of 17‐epi‐cortistatin A is reported from a common intermediate used to procure natural cortistatin A. The synthesis features a unique stereocontrolled Raney‐Ni reduction process that can be employed to reliably produce both α‐ and β‐configured D‐ring aryl steroids. Biological evaluations of these “cortalogs” are reported for the first time.

     

In situ spectral imaging of marker proteins in gastric cancer with near-infrared and visible quantum dots probes

This study presents the investigation of bioconjugating ability of near-infrared (NIR) CdSeTe/ZnS quantum dots (QDs) (710 nm) and visible CdSe QDs (595 nm) in immunofluorescent staining for cancer biomarkers in gastric cancer tissues probed with the homemade Hadamard transform (HT) spectral imaging microscope and a commercial multispectral imaging system. The results show that imunostaining ability of NIR QDs probes is stronger than that of visible QDs when the two kinds of QDs are simultaneously used to probe the cancer biomarkers such as cytokeratin 20 (CK20) and proliferating cell nuclear antigen (PCNA) in gastric cancer tissues. Moreover, when the two QDs probes are used for immunostaining successively for the same target molecules, staining order has great influences on the final results due to their different conjugating ability to the marker proteins. The results imply that NIR QDs hold more promise for real-time imaging of tumor tissues due to its higher sensitivity and contrast. In addition, the results also demonstrate the potential of Hadamard transform spectral imaging as a useful tool in biomedical analysis and quantitative evaluation for tumor tissues.     

无机纳米粒子的生物合成

无机纳米粒子的生物合成是指利用自然界中细菌、放线菌和真菌等微生物或一些高等植物在常温、常压下合成无机纳米粒子,不需使用有毒化学原料或不产生有毒副产品。该方法不仅是一种绿色的、环境友好的新型纳米材料合成策略,而且对深入了解生物矿化机理以及从理论上指导先进功能材料的设计和合成具有重要意义,因此近年来受到了化学、材料、生物科学等领域研究者的广泛关注。本文根据纳米粒子组成,分别综述了国内外利用生物体合成金属、硫化物和氧化物等无机纳米粒子的研究进展,重点讨论了生物合成的机理。结果表明:生物合成的无机纳米粒子具有尺寸分布窄、稳定性高、生物相容性好、产率高和成本低等优点; 为了适应高金属离子浓度的外界环境,生物体往往通过吸附、还原或沉淀、累积或排出等一系列生化过程改变金属离子的溶解性和毒性,从而导致无机纳米粒子的形成; 合成无机纳米粒子后,微生物通常仍具有繁殖能力,表明这些微生物可以被用于生产无机纳米粒子的生物工厂。然而,生物合成无机纳米粒子涉及到的生理过程非常复杂,微生物种类繁多,不同种类之间的差异也非常大。因此,在阐释生物合成机理、拓展纳米材料的种类和形貌、纳米粒子的后处理和应用等问题上仍需进一步深入研究。     

Optical and structural characteristics of yttrium doped ZnO films using sol–gel technology

Yttrium-doped ZnO gel was spin-coated on the SiO₂/Si substrate. The as-prepared ZnO:Y (YZO) thin films then underwent a rapid thermal annealing (RTA) process conducted at various temperatures. The structural and photoluminescence characteristics of the YZO films were discussed thereafter. Our results indicated that the grain size of YZO thin films being treated with various annealing temperatures became smaller as compared to the ones without being doped with yttrium. Furthermore, unlike other ZnO films, the grains of YZO thin films appeared to separate from one another rather than aggregating together as both types of the films were annealed under the same environment. The photoluminescence characteristic measured showed that the UV emission was the only radiation obtained. However, the UV emission intensity of YZO thin film was much stronger than that of the ZnO thin film after annealing them with the same condition. It was also found that the intensity increased with an increase in the annealing temperature, which was caused by the exciton generated and the texture surface of the YZO thin film.     

Visible and infrared luminescence properties of Er-doped Y2Ti2O7 nanocrystals

Er³⁺-doped Y₂Ti₂O₇ nanocrystals were fabricated by the sol-gel method. While the annealing temperature exceeds 757 °C, amorphous pyrochlore phase Er_xY_2−xTi₂O₇ transfers to well-crystallized nanocrystals, and the average crystal size increases from ∼70 to ∼180 nm under 800-1000 °C/1 h annealing. Er_xY_2−xTi₂O₇ nanocrystals absorbing 980 nm photons can produce the upconversion (526, 547, and 660 nm; ²H_11/2→⁴I_15/2, ⁴S_3/2→⁴I_15/2, and ⁴F_9/2→⁴I_15/2, respectively) and Stokes (1528 nm; ⁴I_13/2→⁴I_15/2) photoluminescence (PL). The infrared PL decay curve is single-exponential for Er³⁺ (5 mol%)-doped Y₂Ti₂O₇ nanocrystals but slightly nonexponential for Er³⁺ (10 mol%)-doped Y₂Ti₂O₇ nanocrystals. For 5 and 10 mol% doping concentrations, the mechanism of up-converted green light is the two-photon excited-state absorption. Much stronger intensity of red light relative to green light was observed for the sample with 10 mol% dopant. This phenomenon can be attributed to the reduced distance between Er³⁺-Er³⁺ ions, resulting in the enhancement of the energy-transfer upconversion and cross-relaxation mechanisms.     

Synthesis of 1,5-diphenylpent-3-en-1-yne derivatives utilizing an aqueous B-alkyl Suzuki cross coupling reaction

1,5-Diphenylpent-3-en-1-yne derivatives were isolated in minor quantities from terrestrial plants and exhibited strong anti-inflammatory activity. A cross coupling reaction between B-benzyl-9-BBN and chloroenynes under mild condition was developed resulting in the formation of different 1,5-diphenylpent-3-en-1-yne derivatives with a full control on the E/Z selectivity. Several substrates bearing electron-donating and electron-withdrawing substituents were tolerable under the reaction conditions affording the corresponding products in good yields. This is the first study to report the synthesis of a vast array of novel 1,5-diphenylpent-3-en-1-yne derivatives paving the way for the preparation of tailored derivatives on mass scale necessary for biological studies and drug development.     

Development and application of immunoaffinity column chromatography for atrazine in complex sample media

A rabbit antibody immunoaffinity (IA) column procedure was evaluated as a cleanup method for the determination of atrazine in soil, sediment, and food. Four IA columns were prepared by immobilizing a polyclonal rabbit anti-atrazine antibody solution to HiTrap Sepharose columns. Atrazine was bound to the IA columns when the loading solvents were either 100% water, 2% acetonitrile in water, or 10% methanol in phosphate buffered saline (PBS). Quantitative removal of atrazine from the IA columns was achieved with elution solvents of either 70% ethanol in water, 70% methanol in water, or 100% methanol. One control column was prepared using nonspecific rabbit IgG antibody. This control column did not retain any applied atrazine indicating atrazine did not bind indiscriminately to protein or the Sepharose support. The four IA columns showed reproducible coupling efficiency for the immobilization of the atrazine antibody and consistent binding and releasing of atrazine. The coupling efficiency (4.25 mg of antibody in 1 mL of resin bed) for the four IA columns ranged from 93 to 97% with an average of 96 ± 2% (2.1%). Recoveries of the 500, 50, and 5 ng mL⁻¹ atrazine standard solutions from the four IA columns were 107 ± 7% (6.5%), 122 ± 14% (12%), and 114 ± 9% (8.0%) respectively, based on enzyme-linked immunosorbent assay (ELISA) data. The maximum loading was approximately 700 ng of atrazine for each IA column (∼0.16 μg of atrazine per mg of antibody). The IA columns could withstand 100% methanol as the elution solvent and could be reused more than 50 times with no change in performance. The IA columns were challenged with soil, sediment, and duplicate-diet food samples and effectively removed interferences from these various matrices for subsequent gas chromatography/mass spectrometry (GC/MS) or ELISA analysis. The log-transformed ELISA and GC/MS data were significantly correlated for soil, sediment and food samples although the ELISA values were slightly higher than those obtained by GC/MS. The IA column cleanup procedure coupled with ELISA analysis could be used as an alternative effective analytical method for the determination of atrazine in complex sample media such as soil, sediment, and food samples.     

Approaches to open fullerenes: synthesis and thermal stability of cis-1 bis(isobenzofuran) Diels-Alder adducts of C60

In a quest to form wider openings within the cage of the fullerene C60 through controlled bond-breaking reactions, we have examined the double saturation of adjacent C=C bonds within a six-membered ring of C60. We have investigated the double Diels-Alder cycloaddition of two tethered isobenzofurans to the fullerene C60. We obtained cis-1 adducts in good yields after reacting the methylene- or quinoxaline-tethered bis(isobenzofuran) precursors 2a-k with parent 3,6-dihydro-1,2,4,5-tetrazine (3b). The X-ray structure of the methylene-tethered bis(isobenzofuran)-C60 adduct 4b has been obtained; four-eclipsed substituents are held rigidly by the bicyclic addends. The cis-1 bis(isobenzofuran) bisadducts 4b and 4e-j are kinetically far more stable toward thermal retro-Diels-Alder fragmentation than are mono(isobenzofuran) adducts of C60, in solution and in the solid state as determined by 1H NMR spectroscopy or thermogravimetric analysis. A methodology for the reversible solubilization of other fullerene derivatives based on this work is also presented.