Chemical modification of crystal-like mesoporous phenylene-silica with amino group

Amination of phenylene moieties in crystal-like mesoporous silica hybridized with phenylene is successfully achieved with close to 28% conversion of phenylene by a two-step chemical transformation process while preserving both the ordered mesostructure and crystal-like molecular scale periodicity of the parent material.     

Development and validation of an RP-HPLC method for the estimation of adenosine and related purines in brain tissues of rats

A new, rapid and sensitive RP-HPLC method with UV spectrophotometric detection was developed and validated for the concomitant estimation of adenosine and related purines in rat brain tissue preparations. The HPLC system consisted of C-18 column with UV-photodiode-array detection ranging from 210 to 400 nm, facilitating the online confirmation of peak purity. The column temperature was maintained at 30 degrees C and the injection volume was 20 muL. Elution with an isocratic mobile phase consisting of water/methanol/acetonitrile (88:5:7 by volume) at a flow rate of 0.8 mL/min yielded sharp, utmost-resolved peaks of adenosine (Ade), inosine (Ino), hypoxanthine (Hypoxan) and adenine (Adn) within 10 min. The method was validated with respect to the linearity, accuracy, precision, sensitivity, selectivity and stability. The method was also employed to estimate the naturally occurring purines in discrete regions of rat brain. A new protocol developed for tissue preparation utilizing H(2)SO(4) and Tris buffer gave well-resolved peaks and high component recoveries (>96%) which eliminated the need of an internal standard. The results show that the method for the determination of Ade, Ino, Hypoxan and Adn by RP-HPLC described here has good linearity, accuracy, precision, sensitivity, selectivity and is simple and rapid to perform.     

Homoselenacalix[4]arenes: synthetic exploration and metallosupramolecular chemistry

Homoselenacalix[4]arenes were synthesized by a [2 + 2] reductive coupling protocol favouring the cyclotetramers. The inner and outer-rim decoration was varied and a bicyclic derivative was prepared by a similar one-pot procedure. Conformational analysis in solution and the solid state showed noticeable differences between the homoselenacalix[4]arenes and the analogous homothiacalix[4]arenes and provided insight into the metal binding potential of the Se-bridged macrocycles. The homoselenacalix[4]arenes were found to bind Ag(I). Complexation was visualized in the solid state and different packing networks were formed depending on the counter ions applied.     

PtCl2-catalyzed benzannulation of nickel(II) 2,3-dialkynylporphyrins to form unusual phenanthroporphyrins

Reaction of Ni(II) 2,3-dibromo-5,10,15,20-tetraphenylporphyrin with substituted stannyl alkynes generates substituted 2,3-dialkynylporphyrins in good yields. Thermolysis of these motifs with stoichiometric or even catalytic equivalents of PtCl₂ yields unusual phenanthroporphyrins with only small amounts of the established picenoporphyrin or other side products.     

High repetition rate mid-infrared generation with singly resonant optical parametric oscillator using multi-grating periodically poled MgO:LiNbO3

A high repetition rate mid-infrared singly resonant optical parametric oscillator (OPO) using MgO-doped multi-grating periodically poled LiNbO₃ (MgO:PPLN) is demonstrated. A 1064 nm Q-switched Nd:YVO₄ laser at 10 kHz repetition rate and pulse width of 17.8 ns was used to pump the OPO. The period of the quasi-phase matched (QPM) grating in the multi-grating MgO:PPLN chip varied from 25.5 to 31.5 μm in steps of 0.5 μm. This corresponds to the generation of a signal beam from 1.37 to 1.64 μm and an idler beam from 3.0 to 4.8 μm, respectively. A maximum signal power of 250 mW and idler power of 140 mW has been obtained with an input pump beam of power 1.92 W, for a grating period of 30.5 μm. A maximum optic-optic conversion efficiency of 20% and 7.4% in the idler has been observed. It has been observed that the output power increases as the period of the grating increases.     

Synthesis of 2-Arylpyrimido[4,5-b]porphyrins via Cyclization Reaction with Ammonia

A facile synthetic strategy for the synthesis of a new series of β,β’-fused 2-arylpyrimido[4,5-b]porphyrins has been developed by using condensation cyclization reaction with ammonia. 2-Aroylamino-3-formylporphyrins were synthesized from 2-aroylaminoporphyrins under Vilsmeier–Haack reaction conditions, which were then efficiently converted to the corresponding 2-arylpyrimido[4,5-b]-5,10,15,20-tetrakis(4-chlorophenyl)-porphyrins via a condensation cyclization reaction. The nickel(II), copper(II), free-base and zinc(II) analogues of 2-arylpyrimido[4,5-b]porphyrins were successfully synthesized in 65–72 % yields and structurally characterized on the basis of spectral data analysis. On photophysical evaluation, 2-arylpyrimido[4,5-b]porphyrins demonstrated a 12–19 nm bathochromic shift in their electronic absorption spectra and up to 10 nm red shift in their emission spectra as compared to the simple meso-(tetrakis(4-chlorophenyl))porphyrins due to the extended π-conjugation.