传感器用镓掺杂氧化锌纳米盘/纳米花状结构催化剂的制备及表面表征

采用简便的旋涂过程和一步水热法在压电基片上制备了Ga掺杂的ZnO纳米薄膜(GZO)。在水热处理过程中,通过添加不同的聚合物可形成纳米盘和纳米花状形貌的薄膜。采用场发射扫描电镜(Fe-SEM)、X射线衍射(XRD)和Raman光谱表征了样品的形貌、微结构和组成。 XRD和FE-SEM结果证明,在AlN/Si压电基片上形成的纳米盘、纳米棒和纳米花状GZO均为纤维锌矿相。采用浸渍法进一步在所制GZO样品上固定了绿色的荧光蛋白质(GFP)。运用原子力显微镜和荧光光谱分析了GFP与GZO表面结合的性质,考察了其用于传感器和生物成像技术的可行性。痕量GFP的固定使该材料产生荧光响应,表明其用于紫外光传感器时具有较好活性。     

Atomic Force Microscopy,Transmission Electron Microscopy,and Photon Correlation Spectroscopy: Three Techniques for Rapid Characterization of Optimized Self-Nanoemulsiying Drug Delivery System of Glibenclamide,Carvedilol, and Lovastatin

This article looks at atomic force microscopy as an important aid to characterize the self-nanoemulsifying formulation of glibenclamide, lovastatin, and carvedilol in conjunction with other sophisticated technique, viz., transmission electron microscopy and photon correlation spectroscopy. Sizes obtained by processing the atomic force microscopy (AFM) image are comparable with those obtained from transmission electron microscope. Although in the present study, the mean particle size obtained from photon correlation spectroscopy does not correlate to the findings of atomic force microscopy and transmission electron microscopy, but the poly-disperse index values correlate well with the findings of AFM and transmission electron microscopy where uniform particle size was observed in aqueous dispersion of self-nanoemulsifying formulation of glibenclamide, lovastatin, and carvedilol.     

原子力显微镜研究高分子超薄膜结晶机理及功能化调控

近十年来,随着功能高分子单晶(含单层或寡层片晶)工程及应用研究的不断深入,除了纳米尺度结晶形貌的表征以外,多功能原子力显微镜还被用于研究分子结构、结晶条件和后处理条件对功能高分子晶体性能(电、热、光、磁等)的影响,进一步还可采用扫描探针加工技术(机械刻蚀、电致刻蚀和热致刻蚀等)对其性能进行调控以构筑功能化聚集态结构和微图案.另一方面,超薄膜中单层或寡层片晶可为研究高分子结晶提供合适的模型体系,与原子力显微镜相结合,不但可以原位、实空间、高分辨地研究高分子的成核与生长过程(生长形态演变和生长动力学),还可以用于研究亚稳态折叠链片晶厚度和形态随热处理温度与时间的演化,从而加深对片晶内有序差异、片晶增厚与熔融行为和自诱导成核的认识.     

Green Algae as a Drug Delivery System for the Controlled Release of Antibiotics

New strategies to efficiently treat bacterial infections are crucial to circumvent the increase of resistant strains and to mitigate side effects during treatment. Skin and soft tissue infections represent one of the areas suffering the most from these resistant strains. We developed a new drug delivery system composed of the green algae, Chlamydomonas reinhardtii, which is generally recognized as safe, to target specifically skin diseases. A two-step functionalization strategy was used to chemically modify the algae with the antibiotic vancomycin. Chlamydomonas reinhardtii was found to mask vancomycin and the insertion of a photocleavable linker was used for the release of the antibiotic. This living drug carrier was evaluated in presence of Bacillus subtilis and, only upon UVA1-mediated release, growth inhibition of bacteria was observed. These results represent one of the first examples of a living organism used as a drug delivery system for the release of an antibiotic by UVA1-irradiation.     

Orienting the Demixion of a Diblock‐copolymer Using 193 nm Interferometric Lithography for the Controlled Deposition of Nanoparticles

DUV interferometric lithography and diblock copolymer self‐organization have successfully been combined to provide a simple and highly collective nanopatterning technique enabling the organization of nanoparticles over several orders of magnitude, from nanometre to millimetre. The nanostructural changes at the surface of the polymer film after thermal annealing have been monitored by AFM and the process parameters optimized for obtaining a long‐range organization of the lamellar domains. In particular, the impact of the annealing conditions and geometric parameters of the substrate patterns have been investigated. The nanopatterns resulting from the lamellar demixion of (PS‐b‐MMA) were used for a controlled deposition of nanoparticles. The affinity of the hydrophobic particles for the PS block was demonstrated, opening new doors towards the preparation of high‐density arrays of nanoparticles with potential applications in data storage.

     

Model experiments for a molecular understanding of polymer crystallization

Time‐resolved real‐space observations of morphology and pattern formation resulting from crystallization of ultrathin films of low‐molecular‐weight poly(ethylene oxide) (PEO) or diblock copolymers containing PEO shed light on the mechanisms of how polymer crystals are formed. We used simple but restricted geometries like thin films of controlled thickness or confinement resulting from block copolymer mesotructures. Under such conditions, we were able to relate the observed morphology and its temporal evolution directly to molecular processes and the kinetics of crystal growth. We demonstrate that changes in the morphology with time are due to different thermal histories and are the consequence of the mestable nature of polymer crystals. Information about the nucleation process was obtained by examining crystal formation in 12‐nm small spherical cells of a block copolymer mesostructure. We discuss the advantages of thin‐film studies for a better understanding of polymer crystallization. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 1869–1877, 2003     

Development of a Tubular Sensor Based on a Polypyrrole‐Doped Membrane for the Potentiometric Determination of the Dodecylsulfate Anion in a FIA System

Potentiostatic polymerization of polypyrrole doped with dodecylsulfate anion (DS^?) was carried out in situ over a tubular composite (graphite‐epoxy resin) support in order to develop a potentiometric DS^? sensor (TISE) suitable for flow injection analysis (FIA). The sensibility of the TISE was maximized using the SIMPLEX algorithm in terms of the concentration of the pyrrole monomer, the concentration of DS^?, the potential imposed and polymerization time. Response times between 2 and 4 minutes were observed. The analytical parameters obtained with the flow system were compared with those obtained in batch studies. In both, flow and batch analysis, potential vs. DS^? concentration curves displayed two linear regions with different slopes. Flow analysis for DS^? ion brings a total linear range of 1.58×10^?5 M to 3.88×10^?3 M with a maximum sensibility of 36.4 mV/concentration decade, meanwhile in batch studies the total linear range found was of 6.31×10^?6 M to 1.0×10^?3 M with a maximum sensibility of 54.49 mV. The flow system response pH range was from 5 to 8. The reproducibility in terms of the relative error of the mean of different experiments was 1.58%. Two salient features of the system designed and built are worthy of mention: the sensor presented high selectivity to the dodecyl sulfate ion as compared to other inorganic anions including other anionic surfactants. The sensor lifetime in the FIA system by means of the sensibility changes was found to be of approximately four months.     

Influence of molecular order on the local work function of nanographene architectures: a Kelvin-probe force microscopy study.

We report a Kelvin-probe force microscopy (KPFM) investigation on the structural and electronic properties of different submicron-scale supramolecular architectures of a synthetic nanographene, including extended layers, percolated networks and broken patterns grown from solutions at surfaces. This study made it possible to determine the local work function (WF) of the different pi-conjugated nanostructures adsorbed on mica with a resolution below 10 nm and 0.05 eV. It revealed that the WF strongly depends on the local molecular order at the surface, in particular on the delocalization of electrons in the pi-states, on the molecular orientation at surfaces, on the molecular packing density, on the presence of defects in the film and on the different conformations of the aliphatic peripheral chains that might cover the conjugated core. These results were confirmed by comparing the KPFM-estimated local WF of layers supported on mica, where the molecules are preferentially packed edge-on on the substrate, with the ultraviolet photoelectron spectroscopy microscopically measured WF of layers adsorbed on graphite, where the molecules should tend to assemble face-on at the surface. It appears that local WF studies are of paramount importance for understanding the electronic properties of active organic nanostructures, being therefore fundamental for the building of high-performance organic electronic devices, including field-effect transistors, light-emitting diodes and solar cells.     

The International Conference on Harmonisation Guidance in Practice: Stress Degradation Studies on Lamivudine and Development of a Validated Specific Stability-Indicating HPTLC Assay Method

A sensitive, selective, precise and stability-indicating high-performance thin-layer chromatographic method of analysis of lamivudine both as a bulk drug and in formulations was developed and validated. The solvent system consisted of carbon tetrachloride – methanol – chloroform - acetonitrile (7.0: 3.0: 2.0: 1.5, v/v/v/v). Densitometric analysis of lamivudine was carried out in the absorbance mode at 275 nm. This system was found to give compact spots for lamivudine (R_F value of 0.36 ± 0.02) following double development of chromatoplates with the same mobile phase. Lamivudine was subjected to acid and alkali hydrolysis, oxidation, dry heat and wet heat treatment and photo degradation. The drug undergoes degradation under acidic, basic conditions, oxidation, wet heat and photo degradation. Also the degraded products were well resolved from the pure drug with significantly different R_F values. Linearity was found to be in the range of 50 – 1000 ng spot^–1 with significantly high value of correlation coefficient. The linear regression analysis data for the calibration plots showed good linear relationship with r² = 0.9994 ± 0.05 in the working concentration range of 300 ng spot^–1 to 1000 ng spot^–1. The mean value of slope and intercept were 0.11 ± 0.08 and 10.47 ± 1.21, respectively. The method was validated for precision, robustness and recovery. The limit of detection and quantitation were 15 ng spot^–1 and 40 ng spot^–1 respectively. As the method could effectively separate the drug from its degradation products, it can be employed as a stability indicating one. Moreover, the proposed HPTLC method was utilized to investigate the kinetics of acid degradation process. Arrhenius plot was constructed and activation energy was calculated.     

Determination of Aluminum by Adsorptive Cathodic Stripping Voltammetry with 1,2‐Dihydroxyanthraquinone‐3‐Sulfonic Acid (DASA): Effect of Thin Mercury Film Electrode

An analytical technique for aluminum (Al) based upon the complexation reaction between Al and the ligand – DASA (1,2‐dihydroxy‐anthraquinone‐3‐sulfonic acid) has previously been implemented successfully at the hanging mercury drop electrode (HMDE). There are several advantages of using mercury film electrodes (TMFE) over the HMDE, particularly if disposal of mercury is of concern. The novelty of using TMFE for adsorptive cathodic stripping voltammetry (ACSV) of Al – DASA is demonstrated in this paper. The peak potential used for the detection of Al in this system was at ?1.15 V (vs. Ag/AgCl). The method produced a limit of detection (LOD) of 1 μM (n=5) and a linear working range of 1–20 μM Al. Atomic force microscopy methods were used to investigate the nature of the TMFE and its interaction with DASA. The mercury droplets on the TMFE have a limited volume and this may lead to overloading of the electrode at relatively low concentrations of DASA. Interferences from Fe, Ca, Zn and Mg were investigated with only Fe appearing to interfere with the Al‐DASA system. Two masking agents (o‐phenanthroline and 2,2′‐bipyridyl) were shown to be effective at preventing the Fe interference.     

Controlled melting of individual,nano‐meter‐sized,polymer crystals confined in a block copolymer mesostructure

We demonstrate a possibility to create custom‐made surface patterns on multiple length scales by melting selected nano‐meter‐sized polymer crystals confined in a highly ordered, spherical mesostructure of a hydrogenated poly(butadiene‐block‐ethylene oxide) (PB_h‐b‐PEO) block copolymer. With heatable probes of an atomic force microscope as a heat source, we succeeded to provide highly locally the thermal energy necessary to individually melt such crystals. Besides this possibility for modification of surface properties, we performed detailed in situ studies of thermally induced reorganization processes and subsequent melting of polymer crystals in confined volumes of a block copolymer mesostructure. Close to the melting point, the stability of the confined crystals could be improved by annealing. In addition, the crystal size increased at the expense of already‐molten crystals, indicating diffusion of PEO blocks across the highly incompatible PB_h matrix. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1312–1320, 2004     

Development and validation of a robust LC‐MS‐MS with atmospheric pressure chemical ionization for quantitation of carbazochrome sodium sulfonate in human plasma: application to a pharmacokinetic study

A highly selective and sensitive liquid chromatography coupled with atmospheric pressure chemical ionization tandem mass spectrometry (LC‐APCI‐MS‐MS) was developed and validated for the quantitation and pharmacokinetic study of carbazochrome sodium sulfonate in human plasma. Protein precipitation with 14% perchloric acid solution was selected for sample preparation, and amiloride hydrochloride was employed as an internal standard. The analytes were separated on a Hypersil ODS‐2 column by a multiple‐step linear gradient elution with a mobile phase consisting of 0.2% formic acid solution and methanol pumped at a flow rate of 1.0 mL/min. The determination was optimized and carried out with positive atmospheric pressure chemical ionization by selective reaction monitoring of the ion of m/z 148, the protonated thermodegraded fragment of the free acidic form of carbazochrome sodium sulfonate selected as the parent, and the ion of m/z 107 as the optimum collision induced dissociation (CID) product. The method was fully validated over a concentration range of 0.5–50 ng/mL, with the lower limit of quantitation of 0.5 ng/mL. The application of the LC‐MS‐MS method was demonstrated for the specific and quantitative analysis of carbazochrome sodium sulfonate in human plasma from a pharmacokinetic study in 24 healthy male Chinese volunteers after a single oral administration of 90 mg carbazochrome sodium sulfonate capsules. Copyright © 2010 John Wiley & Sons, Ltd.     

Development of Imidazoline‐2‐Thiones Based Two‐Photon Fluorescence Probes for Imaging Hypochlorite Generation in a Co‐Culture System

We designed and prepared the imidazoline‐2‐thione containing OCl^? probes, PIS and NIS , which operate through specific reactions with OCl^? that yield corresponding fluorescent imidazolium ions. Importantly, we demonstrated that PIS can be employed to image OCl^? generation in macrophages in a co‐culture system. We have also employed two‐photon microscopy and PIS to image OCl^? in live cells and tissues, indicating that this probe could have wide biological applications.     

Development of a Continuous‐Flow System for Asymmetric Hydrogenation Using Self‐Supported Chiral Catalysts

Well‐designed, self‐assembled, metal–organic frameworks were constructed by simple mixing of multitopic MonoPhos‐based ligands ( 3 ; MonoPhos=chiral, monodentate phosphoramidites based on the 1,1′‐bi‐2‐naphthol platform) and [Rh(cod)₂]BF₄ (cod=cycloocta‐1,5‐diene). This self‐supporting strategy allowed for simple and efficient catalyst immobilization without the use of extra added support, giving well‐characterized, insoluble (in toluene) polymeric materials ( 4 ). The resulting self‐supported catalysts ( 4 ) showed outstanding catalytic performance for the asymmetric hydrogenation of a number of α‐dehydroamino acids ( 5 ) and 2‐aryl enamides ( 7 ) with enantiomeric excess (ee) ranges of 94–98 % and 90–98 %, respectively. The linker moiety in 4 influenced the reactivity significantly, albeit with slight impact on the enantioselectivity. Acquisition of reaction profiles under steady‐state conditions showed 4 h and 4 i to have the highest reactivity (turnover frequency (TOF)=95 and 97 h^?1 at 2 atm, respectively), whereas appropriate substrate/catalyst matching was needed for optimum chiral induction. The former was recycled 10 times without loss in ee (95–96 %), although a drop in TOF of approximately 20 % per cycle was observed. The estimation of effective catalytic sites in self‐supported catalyst 4 e was also carried out by isolation and hydrogenation of catalyst–substrate complex, showing about 37 % of the Rh^I centers in the self‐supported catalyst 4 e are accessible to substrate 5 c in the catalysis. A continuous flow reaction system using an activated C/ 4 h mixture as stationary‐phase catalyst for the asymmetric hydrogenation of 5 b was developed and run continuously for a total of 144 h with >99 % conversion and 96–97 % enantioselectivity. The total Rh leaching in the product solution is 1.7 % of that in original catalyst 4 h .     

Recent Progress on the Development of Biofuel Cells for Self‐Powered Electrochemical Biosensing and Logic Biosensing: A Review

Biofuel cells (BFCs) based on enzymes and microorganisms have been recently received considerable attention because they are recognized as an attractive type of energy conversion technology. In addition to the research activities related to the application of BFCs as power source, we have witnessed recently a growing interest in using BFCs for self‐powered electrochemical biosensing and electrochemical logic biosensing applications. Compared with traditional biosensors, one of the most significant advantages of the BFCs‐based self‐powered electrochemical biosensors and logic biosensors is their ability to detect targets integrated with chemical‐to‐electrochemical energy transformation, thus obviating the requirement of external power sources. Following my previous review (Electroanalysis­ 2012 , 24, 197–209), the present review summarizes, discusses and updates the most recent progress and latest advances on the design and construction of BFCs‐based self‐powered electrochemical biosensors and logic biosensors. In addition to the traditional approaches based on substrate effect, inhibition effect, blocking effect and gene regulation effect for BFCs‐based self‐powered electrochemical biosensors and logic biosensors design, some new principles including enzyme effect, co‐stabilization effect, competition effect and hybrid effect are summarized and discussed by me in details. The outlook and recommendation of future directions of BFCs‐based self‐powered electrochemical biosensors and logic biosensors are discussed in the end.     

Characterisation of morphology of self-assembled PEG monolayers: a comparison of mixed and pure coatings optimised for biosensor applications

For detection of low concentrations of analytes in complex biological matrices using optical biosensors, a high surface loading with capture molecules and a low nonspecific binding of nonrelevant matrix molecules are essential. To tailor biosensor surfaces in such a manner, poly(ethylene glycols) (PEG) in varying lengths were immobilised covalently onto glass-type surfaces in different mixing ratios and concentrations, and were subsequently modified with three different kinds of receptors. The nonspecific binding of a model protein (ovalbumin, OVA) and the maximum loading of the respective analytes to these prepared surfaces were monitored using label-free and time-resolved reflectometric interference spectroscopy (RIfS). The three different analytes used varied in size: 150 kDa for the anti-atrazine antibody, 60 kDa for streptavidin and 5 kDa for the 15-bp oligonucleotide. We investigated if the mixing of PEG in different lengths could increase the surface loadings of analyte mimicking a three-dimensional matrix as was found using dextrans as sensor coatings. In addition, the effect on the surface loading was investigated with regard to the size of the analyte molecule using such mixed PEGs on the sensor surface. For further characterisation of the surface coatings, polarisation modulation infrared reflection absorption spectroscopy, atomic force microscopy, and ellipsometry were applied. All authors contributed equally to this work.