Can be Azo Dyes Obtained by Grinding under Solvent‐Free Conditions?

The solid‐solid reactions of some electron‐donors with sulfanilic acid in the presence of solid sodium nitrite afford azo dyes by self‐catalyzed diazotization of sulfanilic acid (2) under solvent‐free conditions with moderate yields. Also the reactions of some electron‐donors with diazotization of o‐nitroaniline (5), m‐nitroaniline (6) and p‐nitroaniline (7) in the presence of solid sodium nitrite catalyzed by p‐toluenesulfonic acid (PTSA) afford azo dyes under solvent‐free conditions in good yields. This new method totally avoids the use of acids, alkalies, and toxic and/or expensive solvents in diazotization and diazo coupling reactions.     

Novel approach to the synthesis of 1,3-diazapyrenes

Methods have been developed for the synthesis of 1,3-diazapyrenes based on the reactions of perimidines with ethoxymethylene-1,3-dicarbonyl compounds and also 6(7)-benzoyl(acetyl, formyl)perimidines with carbonyl compounds in PPA. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 79–82, January, 2009.     

Sensitive DNA biosensor improved by Luteolin copper(II) as indicator based on silver nanoparticles and carbon nanotubes modified electrode

A novel and sensitive electrochemical DNA biosensor has been developed for the detection of DNA hybridization. The biosensor was proposed by using copper(II) complex of Luteolin C₃₀H₁₈CuO₁₂ (CuL₂) as an electroactive indicator based on silver nanoparticles and multi-walled carbon nanotubes (Ag/MWCNTs) modified glassy carbon electrode (GCE). In this method, the 4-aminobenzoic acid (4-ABA) and Ag nanoparticles were covalently grafted on MWCNTs to form Ag/4-ABA/MWCNTs. The proposed method dramatically increased DNA attachment quantity and complementary ssDNA detection sensitivity for its large surface area and good charge-transport characteristics. DNA hybridization detection was performed using CuL₂ as an electroactive indicator. The CuL₂ was synthesized and characterized using elemental analysis (EA) and IR spectroscopy. Cyclic voltammetry (CV) and fluorescence spectroscopy were used to investigate the interaction between CuL₂ and ds-oligonucleotides (dsDNA). It was revealed that CuL₂ presented high electrochemical activity on GCE, and it could be intercalated into the double helices of dsDNA. The target ssDNA of the human hepatitis B virus (HBV) was quantified in a linear range from 3.23 × 10⁻¹² to 5.31 × 10⁻⁹ M (r = 0.9983). A detection limit of 6.46 × 10⁻¹³ M (3σ, n = 11) was achieved.     

The Curtius rearrangement of some organic azides: A DFT mechanistic study

The reaction mechanism for the thermal Curtius reaction of formyl azide has been investigated using B3LYP/6‐311+G(d,p). It is found that, while the synisomer undergoes nitrogen elimination via a concerted mechanism, yielding isocyanic acid directly, the anti‐isomer cannot undergo reaction via the concerted mechanism and first eliminates nitrogen, yielding oxazirene, via a transition state which is higher in energy than that for the concerted mechanism. Singlet formyl nitrene does not exist as an independent moiety. Rather, the strong N? O interaction yields the cyclic isomer oxazirene. The isomerization of oxazirene to isocyanic acid goes through a transition state which is even higher in energy than that for nitrogen elimination. It is hence proposed that this reaction should take place via the concerted mechanism only, the anti‐isomer undergoing isomerization first to the syn isomer since the activation barrier for this step is very small. The same mechanism is found to prevail for acetyl and benzoyl azide. These findings are in accord with all experimental data. © 2008 Wiley Periodicals, Inc. Int J Quantum Chem, 2009     

Thermo- and pH-sensitive comb-type grafted poly(N,N-diethylacrylamide-co-acrylic acid) hydrogels with rapid response behaviors

Poly(N,N-diethylacrylamide) with a terminal hydroxyl end group (PDEA-OH) was synthesized by radical telomerization of N,N-diethylacrylamide (DEA) monomer using 2-hydroxyethanethiol as a chain transfer agent. Macromonomer of thermo-sensitive PDEA was synthesized by condensation reaction of PDEA-OH with acryloyl chloride. The macromonomer was characterized by FTIR and ¹H NMR, and the molecular weight was determined by GPC. Thermo- and pH-sensitive comb-type grafted poly(N,N-diethylacrylamide-co-acrylic acid) (PDEA-co-AA) hydrogels (GHs) were successfully prepared by grafting PDEA chains with freely mobile ends onto the backbone of a cross-linked (PDEA-co-AA) network. The results showed that the deswelling behavior of the hydrogels was dependent on the test temperature. At 45 °C (beneath the VPTT of the hydrogels), both the normal-type hydrogels (NHs) and comb-type grafted P(DEA-co-AA) hydrogels had lower deswelling rates. While at 60 °C (far beyond the VPTT of the hydrogels), the deswelling rates of the GHs were faster than that of the NHs. Furthermore, pulsatile stimuli-responsive studies indicated that the GHs had excellent thermo-reversibility and were superior to the NHs in the magnitude of their swelling ratios to temperature changes. However, the reversibility to pH changes was poor for both the NHs and the GHs.     

Novel Flame‐Retardant and Thermally Stable Poly(Amide‐imide)s Based on Bicyclo[2,2,2]oct‐7‐Ene‐2,3,5,6‐Tetracarboxylic Diimide and Phosphine Oxide in the Main Chain: Synthesis and Characterization

Six novel poly(amide‐imide)s PAIs 5a‐f were synthesized through the direct polycondensation reaction of six chiral N,N′‐(bicyclo[2,2,2]oct‐7‐ene‐tetracarboxylic)‐bis‐L‐amino acids 3a‐f with bis(3‐amino phenyl) phenyl phosphine oxide 4 in a medium consisting of N‐methyl‐2‐pyrrolidone (NMP), triphenyl phosphite (TPP), calcium chloride (CaCl₂) and pyridine. The polymerization reaction produced a series of flame‐retardant and thermally stable poly(amide‐imide)s 5a‐f with high yield and good inherent viscosity of 0.39–0.83 dLg^?1. The resultant polymers were fully characterized by means of FTIR, ¹H NMR spectroscopy, elemental analyses, inherent viscosity, specific rotation and solubility tests. Thermal properties and flame retardant behavior of the PAIs 5a‐f were investigated using thermal gravimetric analysis (TGA and DTG) and limited oxygen index (LOI). Data obtained by thermal analysis (TGA and DTG) revealed that these polymers show good thermal stability. Furthermore, high char yields in TGA and good LOI values indicated that resultant polymers exhibited good flame retardant properties. N,N′‐(bicyclo[2,2,2]oct‐7‐ene‐tetracarboxylic)‐bis‐L‐amino acids 3a‐f were prepared in quantitative yields by the condensation reaction of bicyclo[2,2,2]oct‐7‐ene‐2,3,5,6‐tetracarboxylic dianhydride 1 with L‐alanine 2a , L‐valine 2b , L‐leucine 2c , L‐isoleucine 2d , L‐phenyl alanine 2e and L‐2‐aminobutyric acid 2f in acetic acid solution. These polymers can be potentially utilized in flame retardant thermoplastic materials.     

Direct electrosynthesis and characterization of a new soluble polyfluorene derivative containing carboxyl group in boron trifluoride diethyl etherate

High-quality poly(fluorene-9-acetic acid) (PFAA), a new soluble polyfluorene derivative, was synthesized electrochemically by direct anodic oxidation of fluorene-9-acetic acid (FAA) in boron trifluoride diethyl etherate (BFEE) containing a certain amount of trifluoroacetic acid (TFA). This electrolyte enables facile anodic oxidation of FAA monomer at lower potential (1.05 V vs. SCE). PFAA films with conductivity of 0.53 S cm⁻¹ obtained from this medium showed better redox activity and thermal stability in relation to unsoluble poly(fluorene-9-carboxylic acid). Fluorescent spectral studies indicate that PFAA film with high fluorescence quantum yields and photochemical stability is a good blue-light emitter. The structure and morphology of the polymer were studied by UV–vis, FT-IR, ¹H NMR spectra and scanning electron microscopy, respectively.     

Dispersive liquid–liquid–liquid microextraction combined with liquid chromatography for the determination of chlorophenoxy acid herbicides in aqueous samples

A novel sample preparation method “Dispersive liquid–liquid–liquid microextraction” (DLLLME) was developed in this study. DLLLME was combined with liquid chromatography system to determine chlorophenoxy acid herbicide in aqueous samples. DLLLME is a rapid and environmentally friendly sample pretreatment method. In this study, 25 μL of 1,1,2,2-tetrachloroethane was added to the sample solution and the targeted analytes were extracted from the donor phase by manually shaking for 90 s. The organic phase was separated from the donor phase by centrifugation and was transferred into an insert. Acceptor phase was added to this insert. The analytes were then back-extracted into the acceptor phase by mixing the organic and acceptor phases by pumping those two solutions with a syringe plunger. After centrifugation, the organic phase was settled and removed with a microsyringe. The acceptor phase was injected into the UPLC system by auto sampler. Fine droplets were formed by shaking and pumping with the syringe plunger in DLLLME. The large interfacial area provided good extraction efficiency and shortened the extraction time needed. Conventional LLLME requires an extraction time of 40–60 min; an extraction time of approximately 2 min is sufficient with DLLLME. The DLLLME technique shows good linearity (r² ≥ 0.999), good repeatability (RSD: 4.0–12.2% for tap water; 5.7–8.5% for river water) and high sensitivity (LODs: 0.10–0.60 μg/L for tap water; 0.11–0.95 μg/L for river water).     

Fast method for monitoring phospholipase A2 activity by liquid chromatography–electrospray ionization mass spectrometry

A new liquid chromatography–electrospray ionization mass spectrometry (LC–ESI-MS) method for the fast determination of phospholipase A₂ (PLA₂) activity has been developed. For the first time, the method allows the parallel detection of glycerophosphatidylcholine (GroPCho) as PLA₂ substrate as well as of its products fatty acid (FA) and lyso-GroPCho. ESI-MS was carried out in negative ion mode, detecting the FA as [M − H]⁻ ions and the lyso-GroPCho and GroPCho as acetate adducts [M + Ac]⁻. Utilizing a fast gradient on a short C₅-modified silica gel column with 3 μm particles, five GroPChos, five FAs and six lyso-GroPChos could be separated according to their chain length in less than 3 min. A very high average chromatographic efficiency of 41,200 theoretical plates (plate height 0.5 μm) was achieved for the separation of the GroPChos. The method was applied for monitoring the release of arachidonic acid (20:4 FA) and 1-stearoyl-lyso-sn-GroPCho (18:0 GroPCho) from unilamellar vesicles of 1-stearoyl-2-arachidonoyl-sn-GroPCho (18:0/20:4 GroPCho). With a limit of detection of 0.5 pmol (total amount injected on column) for the FAs and lyso-GroPChos and 1.5 pmol for the GroPChos as well as a linear range of 1.5 decades, the method has proven to be suitable for the monitoring of different secretory PLA₂ (sPLA₂) conversions. Furthermore, it was applied to screen a small library of PLA₂ inhibitors for their activity towards sPLA₂ type V and snake venom of Bothrops moojeni. In both cases, active samples could be directly identified. With its short analysis time, its high chromatographic efficiency and the parallel detection of substrate and all products, the developed LC–ESI-MS method is well suited for the analysis of PLA₂ activity.