Adapting decarbonylation chemistry for the development of prodrugs capable of in vivo delivery of carbon monoxide utilizing sweeteners as carrier molecules

Carbon monoxide as an endogenous signaling molecule exhibits pharmacological efficacy in various animal models of organ injury. To address the difficulty in using CO gas as a therapeutic agent for widespread applications, we are interested in developing CO prodrugs through bioreversible caging of CO in an organic compound. Specifically, we have explored the decarboxylation–decarbonylation chemistry of 1,2-dicarbonyl compounds. Examination and optimization of factors favorable for maximal CO release under physiological conditions led to organic CO prodrugs using non-calorific sweeteners as leaving groups attached to the 1,2-dicarbonyl core. Attaching a leaving group with appropriate properties promotes the desired hydrolysis–decarboxylation–decarbonylation sequence of reactions that leads to CO generation. One such CO prodrug was selected to recapitulate the anti-inflammatory effects of CO against LPS-induced TNF-α production in cell culture studies. Oral administration in mice elevated COHb levels to the safe and efficacious levels established in various preclinical and clinical studies. Furthermore, its pharmacological efficacy was demonstrated in mouse models of acute kidney injury. These studies demonstrate the potential of these prodrugs with benign carriers as orally active CO-based therapeutics. This represents the very first example of orally active organic CO prodrugs with a benign carrier that is an FDA-approved sweetener with demonstrated safety profiles in vivo.

1,2-Dicarbonyl compounds with FDA-approved sweeteners as leaving groups deliver CO for protection against acute kidney injury in mice.     

Application of SPE Using Multi-Walled Carbon Nanotubes as Adsorbent and Rapid Resolution LC-MS-MS for the Simultaneous Determination of 11 Triazine Herbicides Residues in River Water

A method for the simultaneous determination of 11 triazine herbicides residues in river water has been developed. It involves solid-phase extraction (SPE) pretreatment step and rapid resolution liquid chromatography-tandem mass spectrometry (RRLC-MS-MS). In the SPE pretreatment step, the adsorptive performance of MWCNTs material as SPE adsorbent and the elution capability of five kinds of solvents were investigated; in the LC separation step, a rapid resolution high throughput LC column, was used and the gradient elution mode adopted. The linear correlation coefficients (r ²) of the method for 11 target analytes varied between 0.9930 and 0.9980, the mean recoveries were in the range of 73.0 and 98.0% with relative standard deviations (RSD) 2.6 ~ 4.2%, the method detection limits (MDL) were all below 0.1 ng L^?1. An expanded uncertainty of not more than 20% was estimated for each analyte at the spiked concentration of 4.0 μg L^?1. The proposed method was applied to the determination of the residue concentrations of 11 pollutants in Songhuajiang River water.     

Polymethacrylate monolithic and hybrid particle-monolithic columns for reversed-phase and hydrophilic interaction capillary liquid chromatography

We prepared hybrid particle-monolithic polymethacrylate columns for micro-HPLC by in situ polymerization in fused silica capillaries pre-packed with 3–5 μm C₁₈ and aminopropyl silica bonded particles, using polymerization mixtures based on laurylmethacrylate–ethylene dimethacrylate (co)polymers for the reversed-phase (RP) mode and [2-(methacryloyloxy)ethyl]-dimethyl-(3-sulfopropyl) zwitterionic (co)polymers for the hydrophilic interaction (HILIC) mode. The hybrid particle-monolithic columns showed reduced porosity and hold-up volumes, approximately 2–2.5 times lower in comparison to the pure monolithic columns prepared in the whole volume of empty capillaries. The elution volumes of sample compounds are also generally lower in comparison to packed or pure monolithic columns. The efficiency and permeability of the hybrid columns are intermediate in between the properties of the reference pure monolithic and particle-packed columns. The chemistries of the embedded solid particles and of the interparticle monolithic moiety in the hybrid capillary columns contribute to the retention to various degrees, affecting the selectivity of separation. Some hybrid columns provided improved separations of proteins in comparison to the reference particle-packed columns in the reversed-phase mode. Zwitterionic hybrid particle-monolithic columns show dual mode retention HILIC/RP behaviour depending on the composition of the mobile phase and allow separations of polar compounds such as phenolic acids in the HILIC mode at lower concentrations of acetonitrile and, often in shorter analysis time in comparison to particle-packed and full-volume monolithic columns.     

Determination and quantification of active phenolic compounds in pigeon pea leaves and its medicinal product using liquid chromatography–tandem mass spectrometry

A novel method using liquid chromatography coupled to electrospray ionization mass spectrometry (LC-ESI-MS) has been optimized and established for the qualitative and quantitative analysis of ten active phenolic compounds originating from the pigeon pea leaves and a medicinal product thereof (Tongluo Shenggu capsules). In the present study, the chromatographic separation was achieved by means of a HiQ Sil C18V reversed-phase column with a mobile phase consisting of methanol and 0.1% formic acid aqueous solution. Low-energy collision-induced dissociation tandem mass spectrometry (CID-MS/MS) using the selected reaction monitoring (SRM) analysis was employed for the detection of ten analytes which included six flavonoids, two isoflavonoids and two stilbenes. All calibration curves showed excellent coefficients of determination (r(2) ≥ 0.9937) within the range of tested concentrations. The intra- and inter-day variations were below 5.36% in terms of relative standard deviation (RSD). The recoveries were 95.08-104.98% with RSDs of 2.06-4.26% for spiked samples of pigeon pea leaves. The method developed was a rapid, efficient and accurate LC-MS/MS method for the detection of phenolic compounds, which can be applied for quality control of pigeon pea leaves and related medicinal products.     

刚性衬底上铜铟硒纳米棒阵列的合成与表征

在覆盖有钨电极的硅衬底上利用多孔阳极氧化铝模板为生长掩膜电沉积合成垂直排列的铜铟硒纳米棒阵列. 多孔阳极氧化铝模板由阳极氧化磁控溅射制备的铝膜制成. 扫描电子显微镜结果表明,该纳米棒阵列结构致密,直径约100 nm长度约1μm,纵横比为10. X射线衍射、微区拉曼光谱和高分辨透射电子显微镜结果表明,真空条件下450 oC退火处理的铜铟硒纳米棒是多晶纯相的黄铜矿结构的铜铟硒,在纳米棒轴向方向上有比较大的晶粒尺寸. 能量色散X射线光谱表明,铜铟硒纳米棒的化学组成接近InSe₂的化学计量比,由吸收光谱分析推算铜铟硒纳米棒带隙为0.96 eV.     

基于GUI的阿贝-波特滤波实验的计算机仿真

介绍了阿贝-波特空间滤波的实验原理,在Matlab环境下建立了带有图形用户界面（GUI）的计算机仿真平台.不仅可以准确地完成针对不同输入图像、不同滤波要求的滤波过程,还可以通过调整滤波器参数观察滤波效果的差异,形象地展现光学空间滤波过程的物理本质,提高教学效果.     

Synthesis of Ethynylated Phenothiazine Based Fluorescent Boronic Acid Probes

Ethynylated phenothiazine based fluorescent boronic acid probes were prepared. Sonogashira coupling reaction was used to introduce substituted phenylethynylene fragments to the phenothiazine fluorophore to extend the π-conjugation and to enhance the emission property. The photophysical properties and the binding properties of these probes with hydroxyl acids were investigated. We found that the probes with significant ICT effect show emissions which are sensitive to solvent polarity. The phenothiazine moiety is proved to be electron-donating. We found the substitution profile imparts significant effect on the photophysical properties of the probes. For example, one of the probes shows d-PeT effect, whereas the regioisomer probe with similar π-conjugation fragment but different substitution profile shows the a-PeT effect. The easy derivatization of phenothiazine fluorophore, the structure-photophysical property relation and the novel d-PeT fluorescence transduction profile of the phenothiazine based probes described herein may inspire more investigation into this fascinating research area.     

Geometric Phase and Sidebands

Geometric phase of mixed state is expanded for a two-level atom interacting with a quantized field mode, where master equation is a modified Bloch equation with constant terms that are used to explain emergence of sidebands in the spectrum of the fluorescent light. The results show that geometric phase transition is observed for medium initial angle when the Rabi frequency associated with the driving field becomes comparable to the spectral width of the atom. We find that the geometric phase transition depends on population inversion and Bloch radius, which is helpful to understand mechanism of sideband.     

Applications of vertically oriented TiO2 micro-pillars array on the electrode of dye-sensitized solar cell

In this research, dye-sensitized solar cells based on TiO₂ micro-pillars fabricated by inductive couple plasma etcher were investigated by analyses of X-ray diffraction (XRD), scanning electron microscopy (SEM), contact angle, ultraviolet-visible absorption spectra (UV-vis), and current-voltage characteristics. X-ray diffraction patterns show that the TiO₂ anatase phase forms while sintering at 450 °C for 30 min. The SEM images reveal that the diameter and height of TiO₂ micro-pillars are about 3 and 0.8 μm, respectively. The measurements of contact angle between TiO₂ micro-pillars and deionized water (DI water) reveal that the TiO₂ micro-pillars is super-hydrophilic while annealed at 450 °C for 30 min.The absorption spectrum of TiO₂ micro-pillars is better than TiO₂ thin film and can be widely improved in visible region with N3 dye adsorbed. The results of current-voltage (I-V) characteristics analysis reveal that dye-sensitized solar cell with TiO₂ micro-pillars electrode has better I-V characteristics and efficiency than TiO₂ film electrodes. This result may be due to the annealed TiO₂ micro-pillars applied on the electrode of dye-sensitized solar cell can increase the contact area between TiO₂ and dye, resulting in the enhancement of I-V characteristics and efficiency for dye-sensitized solar cell.     

Effect of heat treatment on ZrO2-embedded electrospun carbon fibers used for efficient electromagnetic interference shielding

ZrO₂-embedded carbon fibers were prepared for use as an electromagnetic interference (EMI) shielding material by electrospinning and heat treatment methods. Structural changes were observed in the ZrO₂ and in the carbon structures by XRD and Raman spectroscopy, respectively. During heat treatment, XRD analysis results revealed a transition from a monoclinic structure to a tetragonal structure in ZrO₂ and a graphitization in the structural formation of carbon fibers was observed by Raman spectroscopy. It was observed that these structural changes in the ZrO₂ and the carbon fibers improved the real and imaginary permittivities by a factor of more than 3.5. The EMI shielding efficiency (SE) improved along with the permittivity with higher treatment temperatures and greater amounts of embedded ZrO₂; the highest average EMI SE achieved was 31.79 dB in 800-8500 MHz. The heat treatment played an important role in the improvements in the permittivity and in the EMI SE because of the heat-induced structural changes of the ZrO₂-embedded electrospun carbon fibers. We suggest that the EMI shielding of the fibers is primarily due to the absorption of electromagnetic waves, which prevents secondary EMI by reflection of electromagnetic waves.