Mechanistic study of quinone-polyalcohol interaction through cyclic voltammetry

The electrochemistry of some quinones has been focused to determine the mode of interaction in presence of polyalcohols. Three compounds of each family (benzoquinones, naphthoquinones and anthraquinones) were investigated through cyclic voltammetry in the presence of ethylene glycol (a diol)) and glycerol (a triol) in dichloromethane and acetonitrile at 25°C. The observed positive shift in both the waves of the quinone with successive addition of alcohol was attributed to hydrogen bonding in the quinone-alcohol couple. “Two electron one step” electron transfer mechanism was proposed for the increase in the first wave height at the expense of second. The depletion of the first anodic wave at higher concentration of polyalcohol was rationalized in terms of protonation-deprotonation mechanism. A prior peak observed in the presence of glycerol was ascribed to the hydrogen bonding of the alcohol with neutral quinone. The difference in basicity strength within a family as well as among the three quinone families was also addressed in view of the interaction effectiveness.     

Chemical and thermal stability of isotypic metal-organic frameworks: effect of metal ions

Chemical and thermal stabilities of isotypic metal-organic frameworks (MOFs) like Al-BDC (Al-benzenedicarboxylate called MIL-53-Al), Cr-BDC (MIL-53-Cr) and V-BDC (MIL-47-V), after purification to remove uncoordinated organic linkers, have been compared to understand the effect of the central metal ions on the stabilities of the porous MOF-type materials. Chemical stability to acids, bases, and water decreases in the order of Cr-BDC>Al-BDC>V-BDC, suggesting stability increases with increasing inertness of the central metal ions. However, thermal stability decreases in the order of Al-BDC>Cr-BDC> V-BDC, and this tendency may be explained by the strength of the metal-oxygen bond in common oxides like Al(2)O(3), Cr(2)O(3), and V(2)O(5). In order to evaluate precisely the stability of a MOF, it is necessary to remove uncoordinated organic linkers that are located in the pores of the MOF, because a filled MOF may be more stable than the same MOF after purification.     

Grob fragmentation of norbornyl α-diketones: a route to α-ketoenols and aromatic compounds

An efficient acid-catalyzed Grob fragmentation of symmetrical and asymmetrically substituted norbornyl α-diketones to the corresponding six-membered α-ketoenols is reported. The regio- and stereochemical outcome of the Grob fragmentation of C2 mono- and disubstituted α-diketones was investigated. A single regioisomer resulting from a favorable half-chair intermediate was normally observed. A departure from the normal course was noticed for C2 disubstituted α-diketones possessing an exo-methyl and an endo-methoxycarbonyl derivative, giving the opposite regioisomers due to initial formation of the hemiketal. The bromo analogues of the C2 disubstituted α-diketones furnished an unusual byproduct, which appears to have been formed through highly reactive fused four-membered bicyclo[2.2.0]hexane intermediates. A plausible mechanistic proposal involving the gem-dihalo intermediate, which in one case was actually isolated as its BF(2)-complex, is outlined. The fragmentation protocol was applied to various norbornyl substrates including bis-α-diketone derivatives. The methodology was successfully utilized for the synthesis of substituted aromatic compounds.     

Spectrophotometric Determination of Thorium with Disodium Salt of Arsenazo-III in Perchloric Acid

A rapid and sensitive spectrophotometric method has been developed for the determination of thorium using 0.04% Arsenazo-III in a 2M perchloric acid solution. Absorbance was measured in 1 cm cell and the complex has a sensitive absorption peak at 654 nm. The complex is formed instantly in perchloric acid and remains stable for 45 minutes with constant absorbance. Beer's law is obeyed in the range 1–60 g·g^–1 of thorium concentration with a molar absorptivity at 654 nm = 3.07·10⁵ M^–1·cm^–1 at 24±2°C. The foreign ions interference in thorium determination have been checked. The cations were tested at >60-fold excess of thorium, Mn(II), Fe(III), Co(II) and Ni(II) interfere negatively, whereas only Ce(III) has increased the absorbance. Among the anions, cyanide, phosphate, thiocyanate and acetate at 150-fold excess of thorium cause significant interference. However, thorium can bedetermined in the presence of nitrate, chloride, oxalate, tartrate, ascorbate, thiosulphate and citrate. The method has been applied on certified reference material for thorium determination after extractive separation and the result was found in good agreement with the certified value. The method has been also applied successfully to determine thorium at g·g^–1 level in local ore samples with a precision of ±0.04%.     

Unexpected nitrosyl-group bending in six-coordinate [M(NO)](6) sigma-bonded aryl(iron) and -(ruthenium) porphyrins.

The six-coordinate nitrosyl sigma-bonded aryl(iron) and -(ruthenium) porphyrin complexes (OEP)Fe(NO)(p-C(6)H(4)F) and (OEP)Ru(NO)(p-C(6)H(4)F) (OEP = octaethylporphyrinato dianion) have been synthesized and characterized. Single-crystal X-ray structure determinations reveal an unprecedented bending and tilting of the MNO group for both [MNO](6) species as well as significant lengthening of trans axial bond distances. In (OEP)Fe(NO)(p-C(6)H(4)F) the Fe-N-O angle is 157.4(2) degrees, the nitrosyl nitrogen atom is tilted off of the normal to the heme plane by 9.2 degrees, Fe-N(NO) = 1.728(2) A, and Fe-C(aryl) = 2.040(3) A. In (OEP)Ru(NO)(p-C(6)H(4)F) the Ru-N-O angle is 154.9(3) degrees, the nitrosyl nitrogen atom is tilted off of the heme normal by 10.8 degrees, Ru-N(NO) = 1.807(3) A, and Ru-C(aryl) = 2.111(3) A. We show that these structural features are intrinsic to the molecules and are imposed by the strongly sigma-donating aryl ligand trans to the nitrosyl. Density functional-based calculations reproduce the structural distortions observed in the parent (OEP)Fe(NO)(p-C(6)H(4)F) and, combined with the results of extended Hückel calculations, show that the observed bending and tilting of the FeNO group indeed represent a low-energy conformation. We have identified specific orbital interactions that favor the unexpected bending and tilting of the FeNO group. The aryl ligand also affects the Fe-NO pi-bonding as measured by infrared and (57)Fe M?ssbauer spectroscopies. The solid-state nitrosyl stretching frequencies for the iron complex (1791 cm(-)(1)) and the ruthenium complex (1773 cm(-)(1)) are significantly reduced compared to their respective [MNO](6) counterparts. The M?ssbauer data for (OEP)Fe(NO)(p-C(6)H(4)F) yield the quadrupole splitting parameter +0.57 mm/s and the isomer shift 0.14 mm/s at 4.2 K. The results of our study show, for the first time, that bent Fe-N-O linkages are possible in formally ferric nitrosyl porphyrins.     

Tris(2‐aminoethyl)amine‐based ferrocene‐terminated dendrimers as burning rate catalysts for ammonium perchlorate‐based propellant decomposition

Ferrocene‐based derivatives show potential application as burning rate catalysts (BRCs) for solid composite propellants. However, migration problems of simple ferrocene‐based derivatives limit their application as BRCs in solid composite propellants. To overcome the migration problems of ferrocene‐based BRCs and to enhance the burning rate of ammonium perchlorate (AP)‐based propellants, zero‐ to second‐generation tris(2‐aminoethyl)amine‐based ferrocene‐terminated dendrimers (G0, G1 and G2) were synthesized. The structures of G0, G1 and G2 were confirmed using ¹H NMR, Fourier transform infrared and UV–visible spectroscopies. The electrochemical behavior of G0, G1 and G2 was investigated using cyclic voltammetry. It was found that G0, G1 and G2 showed redox behavior due to the presence of ferrocene and this redox behavior was diffusion controlled over the investigated scan range. The burning rate catalytic effect of G0, G1 and G2 on thermal decomposition of AP was investigated using thermogravimetry and differential thermogravimetry. G0, G1 and G2 showed good catalytic effect on the thermal decomposition of AP. Anti‐migration studies showed that migration of G0, G1 and G2 was much slower than that of 2,2‐bis(ethylferrocenyl)propane (catocene) and ferrocene.     

A Jocic-type approach for a practical and scalable synthesis of pyrrolonaphthoxazepine (PNOX)-based potent proapoptotic agents

We developed a Jocic-type protocol for the construction of the pyrrolonaphthoxazepine (PNOX) core. After an initial investigation based on the isolation of a trichloromethyl carbinol derivative, we shifted our attention towards a multicomponent single-step protocol. Screening of a variety of bases and solvents led to the identification of the optimum conditions for the preparation of the key α-aryloxy carboxylic acids to undergo intramolecular cyclization. The novel chemical route significantly improved overall yields for the preparation of PNOX-based compounds and was successfully extended to the preparation of 1,4-benzoxazinone-based templates.     

Physicochemical Investigation of HDDP Azomethine Dye as Turn-On Fluorescent Chemosensor for High Selectivity and Sensitivity of Al<Superscript>3+</Superscript> Ions

4-[(2-Hydroxy-naphthalen-1-ylmethylene)-amino]-1,5-dimethyl-2-phenyl-1,2-dihydro-pyrazol-3-one (HDDP) was synthesized by the reaction of 4-amino-1,5-dimethyl-2-phenyl-1,2-dihydro-3H-pyrazol-3-one with 2-hydroxy-l-naphthaldehyde. The structure was confirmed by the IR, ¹H-NMR, ¹³C-NMR, and EI-MS spectra and elemental analysis. Physicochemical parameters of the HDDP such as extinction coefficient, oscillator strength, transition dipole moment, Stokes shift, and fluorescence quantum yield in different solvents were studied on the basis of polarities. The interactions of various metal ions with HDDP were also studied using steady state fluorescence measurements. The emission profile reveals that it acts as off–on type fluorescent chemosensor for selective and sensitive detection of Al³⁺ ions. Complexation stoichiometry and mechanism of enhancement were determined from a Benesi–Hildebrand plot.     

生物催化进展:从计算到代谢工程（英文）

经过数次技术研究和超常创新战略的大发展,生物催化逐渐达到工业化水平,从而受到人们特别的关注.基于酶值,通过生物途径生产高附加值化合物和精细工业化学品成为人们最感兴趣的领域之一.更广泛的众多生物化学路线可由酶催化来实现,其中还有一些酶尚未被人们发现.另一方面,由于非同源底物和某些化学过程所必需的苛刻条件,导致酶催化过程的效率低、稳定性差,因而限制了生物催化的应用.因此,开发具有多催化特征、更高效率和稳定性的绿色催化剂,成为生物催化的重中之重.计算科学、代谢工程、合成生物,以及机器学习路线的运用为新催化剂的工程化提供了新方法.本文重点介绍了合成生物学和代谢工程在催化中的作用,讨论了用于催化的机器学习算法和如何选择一种预测蛋白质-配体相互作用的算法;为了预测键合和催化功能,综述了分子对接的重要性;最后给出了结束语、未来挑战和前景展望.     

Uranyl ion adsorption studies on synthesized phosphoryl functionalised MWCNTs: a mechanistic approach

Nickel hydroxide solubility has been studied in this work in different cementitious systems. Our results indicate that once Glenium^® 27, cement superplasticizer admixture, is added to water and then mixed with cement, this polymeric material is stabilized and not released back to the aqueous solution, with negligible effects on the mobility of nickel. Contrary to that, when Glenium^® 27 is added directly in solution at high dosages, an important effect is observed on nickel behaviour. Thermodynamic calculations indicate that the effect of such component on Ni is likely the effect that other small organics could have over this element.