Caro's Acid Supported on Silica Gel. Part V: A Mild and Selective Reagent for Conversion of Trimethyl Silyl ethers to the Corresponding Hydroxy Compounds

Mild and efficient method for deprotection of silyl ethers to alcohols is described using Caro's acid supported on silica gel. Reactions are carried out in dichloromethane at room temperature and their parent hydroxy compounds obtained in good to excellent yields. Using this procedure, tetrahydropyranyl ethers (THP) remain intact during desilylation reaction.

     

Photodynamic Therapy and the Biophysics of the Tumor Microenvironment

Targeting the tumor microenvironment (TME) provides opportunities to modulate tumor physiology, enhance the delivery of therapeutic agents, impact immune response and overcome resistance. Photodynamic therapy (PDT) is a photochemistry-based, nonthermal modality that produces reactive molecular species at the site of light activation and is in the clinic for nononcologic and oncologic applications. The unique mechanisms and exquisite spatiotemporal control inherent to PDT enable selective modulation or destruction of the TME and cancer cells. Mechanical stress plays an important role in tumor growth and survival, with increasing implications for therapy design and drug delivery, but remains understudied in the context of PDT and PDT-based combinations. This review describes pharmacoengineering and bioengineering approaches in PDT to target cellular and noncellular components of the TME, as well as molecular targets on tumor and tumor-associated cells. Particular emphasis is placed on the role of mechanical stress in the context of targeted PDT regimens, and combinations, for primary and metastatic tumors.     

Energy Transfer in Aminonaphthalimide‐Boron‐Dipyrromethene (BODIPY) Dyads upon One‐ and Two‐Photon Excitation: Applications for Cellular Imaging

Aminonaphthalimide–BODIPY energy transfer cassettes were found to show very fast (k_EET≈10¹⁰–10¹¹ s^?1) and efficient BODIPY fluorescence sensitization. This was observed upon one‐ and two‐photon excitation, which extends the application range of the investigated bichromophoric dyads in terms of accessible excitation wavelengths. In comparison with the direct excitation of the BODIPY chromophore, the two‐photon absorption cross‐section δ of the dyads is significantly incremented by the presence of the aminonaphthalimide donor [δ≈10 GM for the BODIPY versus 19–26 GM in the dyad at λ_exc=840 nm; 1 GM (Goeppert–Mayer unit)=10^?50 cm⁴ s molecule^?1 photon^?1]. The electronic decoupling of the donor and acceptor, which is a precondition for the energy transfer cassette concept, was demonstrated by time‐dependent density functional theory calculations. The applicability of the new probes in the one‐ and two‐photon excitation mode was demonstrated in a proof‐of‐principle approach in the fluorescence imaging of HeLa cells. To the best of our knowledge, this is the first demonstration of the merging of multiphoton excitation with the energy transfer cassette concept for a BODIPY‐containing dyad.     

Silicone glue coated stainless steel wire for solid phase microextraction

A new solid phase microextraction (SPME) fiber based on high-temperature silicone glue coated on a stainless steel wire is presented. The fiber coating can be prepared easily in a few minutes, it is mechanically stable and exhibits relatively high thermal stability (up to 260 °C). The extraction properties of the fiber to benzene, toluene, ethylbenzene, and xylenes (BTEX) were examined using both direct and headspace SPME modes coupled to gas chromatography-flame ionization detection. The effects of the extraction and desorption parameters including extraction and desorption time, sampling and desorption temperature, and ionic strength on the extraction/desorption efficiency have been studied. For both headspace and direct SPME the calibration graphs were linear in the concentration range from 0.5 μg L⁻¹ to 10 mg L⁻¹ (R² > 0.996) and detection limits ranged from 0.07 to 0.24 μg L⁻¹. Single fiber repeatability and fiber-to-fiber reproducibility were less than 6.8 and 21.5%, respectively. Finally, headspace SPME was applied to determine BTEX in petrol station waste waters with spiked recoveries in the range of 89.7-105.2%.     

UPLC a Powerful Tool for the Separation of Imidazolium Ionic Liquid Cations

Ultra-performance liquid chromatography (UPLC) in reversed-phase (RP), ion pair (IP) and hydrophilic interaction chromatography (HILIC) has been investigated for the separation of imidazolium-based ionic liquid (IL) cations. Among the three stationary phases (i.e., C18, C8 and phenyl) studied under RP conditions the phenyl phase provided much stronger retention for the IL cations. Four acids (hydrochloric, methanesulfonic, perchloric and trifluoroacetic) as mobile phase additives were compared in light of their effects on the retention of IL cations. It was shown that the retention of all IL cations decreased upon acidification of the mobile phase, possibly due to suppression of residual silanol ionization. Very fast (~3 min) and efficient RP-UPLC separation of six cations was achieved by gradient elution with acetonitrile?Cwater mobile phase containing 2.5 mmol L^?1 perchloric acid. In IP-UPLC all solutes were well resolved in about 4 min by gradient elution with acetonitrile?Cwater mobile phase containing 1 mmol L^?1 sodium 1-octanesulfonate as ion pairing reagent. Finally, under HILIC conditions by using isocratic elution with acetonitrile?Cwater (85:15, v/v) mobile phase containing 5 mmol L^?1 ammonium formate (pH 3.2) the separation time was reduced to less than 2 min while maintaining excellent peak shapes and sufficient resolution. Compared to current LC systems UPLC allowed considerably faster separations with better peak shapes.     

Probing Reactivity of PQQ-Dependent Carbohydrate Dehydrogenases Using Artificial Electron Acceptor

The kinetic parameters of carbohydrate oxidation catalyzed by Acinetobacter calcoaceticus pyrroloquinoline quinone (PQQ)-dependent glucose dehydrogenase (GDH) and Escherichia coli PQQ-dependent aldose sugar dehydrogenase (ASDH) were determined using various electron acceptors. The radical cations of organic compounds and 2,6-dichlorophenolindophenol are the most reactive with both enzymes in presence of glucose. The reactivity of dioxygen with ASDH is low; the bimolecular constant k _ox = 660 M⁻¹ s⁻¹, while GDH reactivity with dioxygen is even less. The radical cation of 3-(10H-phenoxazin-10-yl)propionic acid was used as electron acceptor for reduced enzyme in the study of dehydrogenases carbohydrates specificity. Mono- and disaccharide reactivity with GDH is higher than the reactivity of oligosaccharides. For ASDH, the reactivity increased with the carbohydrate monomer number increase. The specificity of quinoproteins was compared with specificity of flavoprotein Microdochium nivale carbohydrate oxidase due to potential enzymes application for lactose oxidation.     

Synthesis and kinetic study on the thermal degradation of triblock copolymer of polycaprolactone‐poly (glycidyl nitrate)‐polycaprolactone (PCL‐PGN‐PCL) as an energetic binder

In this study, an energetic binder is synthesized via ring opening copolymerization of ε‐caprolactone with poly (glycidyl nitrate) (PGN) of low molecular weight (M_n = 1350 g mol^?1) as a macroinitiator to form triblock copolymer polycaprolactone‐PGN‐polycaprolactone (PCL‐PGN‐PCL) (M_n = 4128 g mol^?1). The effects of catalyst type and its concentration, reaction time, and solvent are investigated in this polymerization reaction. The resulting triblock copolymer is characterized by Fourier transform infrared spectroscopy (FT‐IR), nuclear magnetic resonance spectroscopy (NMR), gel permeation chromatography (GPC), differential scanning calorimetry (DSC), and thermal gravimetric analysis (TGA). The DSC result shows that the glass transition temperature of triblock copolymer (T_g = ?50°C) is lower than PGN (T_g = ?35°C). Also, the decomposition kinetics of this energetic binder is studied by DSC, TGA, and its derivative (DTG). An advanced isoconversional method is applied for kinetic analysis. Activation energy is calculated by Flynn‐Wall‐Ozawa (FWO) and Kissinger methods. The resulting activation energy from Kissinger method for the first and the second steps are 42.98 and 74.56 kJ mol^?1, respectively. Also, it is found from FWO results that the activation energy for the copolymer increases with degradation degree (α).     

A novel approach towards dethioacetalization reactions with H2O2-SOCl2 system

A simple and efficient protocol for the deprotection of dithioacetal,1,3-dithianes and 1,3-dithiolanes has been developed using H₂O₂-SOC1₂ reagent system.In addition to the absence of overoxidation products for oxidation-prone substrates,high chemoselectivity, the low cost and availability of the reagents,simplicity of the method,short reaction times,and excellent yields can also be considered as strong points for this method.     

Comparison and evaluation of derivatization methods for gas chromatographic determination of various propane-diols

Summary Phenylamino-propanediols were analysed by capillary gas chromatography as various derivatives. Trimethylsilyl and methylboronic acid derivatives were detected with a FID. The trifluoroacetyl derivatives were analysed using an ECD. The structure of the derivatives was confirmed by GC-MS. Presented at the 15th International Symposium on Chromatography, Nürnberg, October 1984     

Characterization of tungsten surfaces by simultaneous work function and secondary electron emission measurements.

The changes of the work function (Phi) and the secondary electron emission (SEE) of oxygen covered polycrystalline tungsten occurring after ion sputtering and heat treatments have been investigated. The chemical composition was analyzed by X-ray photoelectron spectroscopy (XPS), and the electron emission properties by work function spectroscopy (WFS). We observed in what manner the chemical changes of the surface are reflected in the work function and SEE. The simultaneous change of Phi and SEE in the case of oxygen covered tungsten have been pointed out and a direct relationship between them can be supposed.