Reactions of 1,4-bis(tetrazole)benzenes: formation of long chain alkyl halides

The reactions of 1,4-bis[2-(tributylstannyl)tetrazol-5-yl]benzene with α,ω-dibromoalkanes were carried out in order to synthesise pendant alkyl halide derivatives of the parent bis-tetrazole. This led to the formation of several alkyl halide derivatives, substituted variously at N1 or N2 on the tetrazole ring. The crystal structures of 1,4-bis[(2-(4-bromobutyl)tetrazol-5-yl)]benzene (2-N,2-N′), 1,4-bis[(2-(4-bromobutyl)tetrazol-5-yl)]benzene (1-N,2-N′) and 1,4-bis[(2-(8-bromooctyl)tetrazol-5-yl)]benzene (2-N,2-N′) are reported. Further discussion involves the structure of 1,4-bis[2-(6-bromohexyl)-2H-tetrazol-5-yl]benzene (2-N,2-N′) previously reported.     

Efficient Chemical Protein Synthesis using Fmoc-Masked N-Terminal Cysteine in Peptide Thioester Segments

We report an operationally simple method to facilitate chemical protein synthesis by fully convergent and one-pot native chemical ligations utilizing the fluorenylmethyloxycarbonyl (Fmoc) moiety as an N-masking group of the N-terminal cysteine of the middle peptide thioester segment(s). The Fmoc group is stable to the harsh oxidative conditions frequently used to generate peptide thioesters from peptide hydrazide or o-aminoanilide. The ready availability of Fmoc-Cys(Trt)-OH, which is routinely used in Fmoc solid-phase peptide synthesis, where the Fmoc group is pre-installed on cysteine residue, minimizes additional steps required for the temporary protection of the N-terminal cysteinyl peptides. The Fmoc group is readily removed after ligation by short exposure (<7 min) to 20 % piperidine at pH 11 in aqueous conditions at room temperature. Subsequent native chemical ligation reactions can be performed in presence of piperidine in the same solution at pH 7.     

Hydroxyapatite coating on stainless steel pre-coated with bovine serum albumin at ambient conditions

A biomimetic process for coating of nanosized hydroxyapatite on stainless steel, which capitalises the dual nature of the protein bovine serum albumin in both metal binding and a strong affinity for calcium ions, has been developed. The novelty of the process lies in pre-conditioning the metallic surface using the above protein prior to its mineralization with hydroxyapatite at ambient conditions. The microporous morphology of these coatings may provide favourable solubility and resorbability as desired by many orthopaedic and orthodontic applications.     

Impact of Targeted Specific Antibiotic Delivery for Gut Microbiota Modulation on High-Fructose-Fed Rats

The objective of present investigation was to study the effect of gut microbiota alteration by oral administration of targeted delivery of pH sensitive cefdinir microspheres to high-fructose-fed (HFD) rats. Rats were fed with a high-fructose diet with or without cefdinir microsphere administration for 30 days. The fecal microbiota community, oral glucose tolerance, the markers of liver injury, plasma and hepatic lipids profile, and histological evaluation were investigated. The levels of blood glucose, liver injury markers, lipid profile in plasma and liver, and fat tissue were significantly increased in high-fructose-fed rats. However, after pH-sensitive cefdinir microsphere administration, the elevation of these parameters was significantly suppressed. Cef EL significantly lowered the increased AST (p?<?0.05) and ALT (p?<?0.001) levels in HFD group. There is a significant lower (p?<?0.01) AUC_glucose level in Cef EL group than HFD group The histological changes in the liver and the small and large intestines were more profound in HFD group as compared to cefdinir-treated HFD and control groups. Feeding of cefdinir microsphere sustained lactobacilli and bifidobacteria and significantly decreased (p?<?0.05) the number of Enterobacteriaceae induced by HFD. Experimental evidences demonstrated that the effectiveness of pH-specific cefdinir microsphere on reducing insulin resistance and development of metabolic changes in high-fructose-fed rats and suggested that it may be a promising therapeutic agent in treating type 2 diabetes. Intestinal-targeted antibiotic delivery needs to be further explored for its therapeutic applications.     

Photochemistry of desonide, a non-fluorinated steroidal anti-inflammatory drug

The photochemistry of anti-inflammatory drug desonide (De, 1) was studied in aerobic as well as in anaerobic condition with different irradiation wavelengths (254, 310 nm) in acetonitrile and 2-propanol. All photoproducts obtained were isolated and characterized on the basis of IR, (1)H-, (13)C-NMR spectroscopy and elemental analysis study. The products were: 11beta,21-dihydroxy-16alpha,17alpha-(1-methylethylidenedioxy)-1,5-cyclopregn-3-ene-2,20-dione 2 (254 nm), 11beta-hydroxy-16alpha,17alpha-(1-methylethylidenedioxy)androsta-1,4-diene-3-one 3 (310 nm/2-propanol), 17beta-hydroperoxy-11beta-hydroxy-16alpha,17alpha-(1-methylethylidenedioxy)androsta-1,4-diene-3-one 4 (310 nm/O(2)/2-propanol). Cyclohexadienone moiety in ring A and keto group at C(17) were found to be deeply modified by UV light therefore, loss of biological activity both during storage and in vivo can not be ruled out.     

Isolation and biological evaluation of chromone alkaloid dysoline,a new regioisomer of rohitukine from Dysoxylum binectariferum

The chromone alkaloid dysoline (1), a new regioisomer of rohitukine (2) along with rohitukine and rohitukine-N-oxide (3) were isolated from the stem barks of Dysoxylum binectariferum. The structure of dysoline (1) was determined by extensive 2D-NMR studies and the absolute configuration was established by NOESY and CD spectra. Dysoline (1) consisted of a 5,7-dihydroxy-2-methylchromone nucleus substituted with a 2′-hydroxylated N-Me piperidine ring at the C-6 position. Dysoline differs from rohitukine by the position of the piperidine ring on the chromone nucleus. Dysoline displayed promising cytotoxicity in HT1080 fibrosarcoma cells with an IC₅₀ of 0.21 μM, and also displayed significant inhibition of proinflammatory cytokines TNF-α and IL-6.     

Mesogenic properties and the effect of 1,2,4-trisubstitution on the central benzene nucleus of a three-ring mesogen

Four mesogenic homologous series have been synthesized by fixing a rigid 4-substituted phenylazo group to a resorcinol moiety. In series I and II, one phenolic -OH group is esterified by 4-n-alkoxybenzoyl groups; in series III and IV both the phenolic -OH groups are esterified by 4-n-alkoxybenzoyl groups. All the homologues of series III and IV exhibit low melting smectic C phases. Monoesters of series I and II, having free lateral hydroxy group with strong hydrogen bonding, exhibit high temperature nematic phases. The effect of different substituents on mesomorphic properties is discussed. One homologue of series III was doped with a chiral dopant and its spontaneous polarization evaluated.     

Synthesis,crystal structures and magnetic behaviors of two dicyanamide bridged di- and polynuclear complexes of cobalt(II) derived from 2,4,6-tris(2-pyridyl)1,3,5-triazine and imidazole

Two new dicyanamido-bridged di- and polynuclear complexes of Co(II), [Co(dca)(tptz)(H₂O)]₂·2(ClO₄) (1) and [Co(dca)₂(imz)₂]_n (2) [dca, dicyanamide; tptz, 2,4,6-tris(2-pyridyl)1,3,5-triazine; and imz, imidazole] have been synthesized and characterized structurally, as well as magnetically. The X-ray single crystal structure determination of complex 1 shows that two symmetry related octahedral Co(II) ions are separated by dca ligand and other coordination sites are satisfied by tptz and aquo ligands. Each dinuclear unit is associated with each other by intramolecular hydrogen bonding interactions, giving rise to a 1D chain structure. On the other hand complex 2 is a 1D coordination polymer having [Co(II)(imz)₂] units connected by double bridging dca ligands. These 1D chains interact through face-to-face π–π stacking interactions of the imz rings extending the dimensionality to a 2D supramolecular network. The variable temperature (300–2 K) magnetic measurements of both compounds reveal that dicyanamide exhibits a weak antiferromagnetic interaction between the metal centers.     

Stimuli‐Responsive Naphthalene Diimide as Invisible Ink: A Rewritable Fluorescent Platform for Anti‐Counterfeiting

Herein, we report an approach to combat counterfeiting and storage of valuable information based on the solid‐state fluorescence switching behavior of isoniazid functionalized naphthalene diimide (ISO_NDI) in response to an external stimuli (i. e., HCl vapor). The unique feature of ISO_NDI is further utilized to develop an invisible ink (ISO_NDI‐PVA) with commercial polymer polyvinyl alcohol (PVA). A solid‐state fluorescence recovery was observed while loading with HCl vapors. This exclusive property of the material could be applied directly as a security ink for confidential data storage purpose. Based on above strategy, we successfully realized the rewritable application by using ISO_NDI‐PVA ink and confirm its practical efficacy on various substrates by creating different patterns. The solid‐state fluorescence switching behavior of ISO_NDI‐PVA ink exhibited reversible on/off signal for multiple cycles under the influence of HCl/NH₃ vapors. Mechanistic investigation supports a clear participation of intermolecular charge transfer (ICT) phenomenon in the solid‐state fluorescence switching property. The ease of fabricating the ink with invisible to visible characteristics in response to HCl vapors provides new opportunities for exploring the application of ISO_NDI‐PVA as invisible ink for targeted security applications.     

233Pa(2nth, f ) cross-section determination using a fission track technique

The νp process is a primary nucleosynthesis process which occurs in core-collapse supernovae. An essential role in this process is being played by electron antineutrinos. They generate, by absorption on protons, a supply of neutrons which, by (n, p) reactions, allow to overcome waiting point nuclei with rather long beta-decay and proton-capture lifetimes. The synthesis of heavy elements by the νp process depends sensitively on the $\bar \nu _e$ luminosity and spectrum. As has been shown recently, the latter are affected by collective neutrino flavor oscillations which can swap the $\bar \nu _e$ and $\bar \nu _{\mu ,\tau }$ spectra above a certain split energy. Assuming such a swap scenario, we have studied the impact of collective neutrino flavor oscillations on the νp-process nucleosynthesis. Our results show that the production of light p-nuclei up to mass number A = 108 is very sensitive to collective neutrino oscillations.