Nonlinear Effects and a Cascade of Radical Events Leading to Laser-Specific Generation of Active Oxygen Species

Laser photolysis of benzoyl radical precursors (such as PhCOC[OH]R₂) in oxygen-containing solutions leads to a laser-specific cascade of oxidative events in which benzoyl peroxyl radicals undergo self-reaction, ultimately leading to the sequential formation of benzoyloxyl, phenyl and phenyl peroxyl radicals. Thus, photoreactions producing benzoyl (PheO) radicals lead to PhĊO under conditions where benzoyl radicals do not decarbonylate. These reactions require the high-intensity conditions that can only be achieved under pulsed laser excitation; yet, they do not involve any multiphoton processes. Type I mechanisms of this type may be of importance as new laser-based therapeutic technologies are developed.     

The first example of a nitrile hydratase model complex that reversibly binds nitriles

Nitrile hydratase (NHase) is an iron-containing metalloenzyme that converts nitriles to amides. The mechanism by which this biochemical reaction occurs is unknown. One mechanism that has been proposed involves nucleophilic attack of an Fe-bound nitrile by water (or hydroxide). Reported herein is a five-coordinate model compound ([Fe(III)(S(2)(Me2)N(3)(Et,Pr))](+)) containing Fe(III) in an environment resembling that of NHase, which reversibly binds a variety of nitriles, alcohols, amines, and thiocyanate. XAS shows that five-coordinate [Fe(III)(S(2)(Me2)N(3)(Et,Pr))](+) reacts with both methanol and acetonitrile to afford a six-coordinate solvent-bound complex. Competitive binding studies demonstrate that MeCN preferentially binds over ROH, suggesting that nitriles would be capable of displacing the H(2)O coordinated to the iron site of NHase. Thermodynamic parameters were determined for acetonitrile (DeltaH = -6.2(+/-0.2) kcal/mol, DeltaS = -29.4(+/-0.8) eu), benzonitrile (-4.2(+/-0.6) kcal/mol, DeltaS = -18(+/-3) eu), and pyridine (DeltaH = -8(+/-1) kcal/mol, DeltaS = -41(+/-6) eu) binding to [Fe(III)(S(2)(Me2)N(3)(Et,Pr))](+) using variable-temperature electronic absorption spectroscopy. Ligand exchange kinetics were examined for acetonitrile, iso-propylnitrile, benzonitrile, and 4-tert-butylpyridine using (13)C NMR line-broadening analysis, at a variety of temperatures. Activation parameters for ligand exchange were determined to be DeltaH(+ +) = 7.1(+/-0.8) kcal/mol, DeltaS(+ +) = -10(+/-1) eu (acetonitrile), DeltaH(+ +) = 5.4(+/-0.6) kcal/mol, DeltaS(+ +) = -17(+/-2) eu (iso-propionitrile), DeltaH(+ +) = 4.9(+/-0.8) kcal/mol, DeltaS(+ +) = -20(+/-3) eu (benzonitrile), and DeltaH(+ +) = 4.7(+/-1.4) kcal/mol DeltaS(+ +) = -18(+/-2) eu (4-tert-butylpyridine). The thermodynamic parameters for pyridine binding to a related complex, [Fe(III)(S(2)(Me2)N(3)(Pr,Pr))](+) (DeltaH = -5.9(+/-0.8) kcal/mol, DeltaS = -24(+/-3) eu), are also reported, as well as kinetic parameters for 4-tert-butylpyridine exchange (DeltaH(+ +) = 3.1(+/-0.8) kcal/mol, DeltaS(+ +) = -25(+/-3) eu). These data show for the first time that, when it is contained in a ligand environment similar to that of NHase, Fe(III) is capable of forming a stable complex with nitriles. Also, the rates of ligand exchange demonstrate that low-spin Fe(III) in this ligand environment is more labile than expected. Furthermore, comparison of [Fe(III)(S(2)(Me2)N(3)(Et,Pr))](+) and [Fe(III)(S(2)(Me2)N(3)(Pr,Pr))](+) demonstrates how minor distortions induced by ligand constraints can dramatically alter the reactivity of a metal complex.     

Composition-controlled synthesis of bimetallic gold-silver nanoparticles

This paper reports findings of an investigation of the synthesis of monolayer-capped binary gold-silver (AuAg) bimetallic nanoparticles that is aimed at understanding the control factors governing the formation of the bimetallic compositions. The synthesis of alkanethiolate-capped AuAg nanoparticles was carried out using two related synthetic protocols using aqueous sodium borohydride as a reducing agent. One involves a two-phase reduction of AuCl(4)(-), which is dissolved in organic solution, and Ag(+), which is dissolved in aqueous solution. The other protocol involves a two-phase reduction of AuCl(4)(-) and AgBr(2)(-), both of which are dissolved in the same organic solution. AuAg nanoparticles of 2-3 nm core sizes with different compositions in the range of 0-100% Au have been synthesized. The two synthetic routes were compared in terms of bimetallic composition and size properties. Our new findings have allowed us to establish the correlation between synthetic feeding of metals and metal compositions in the bimetallic nanoparticles, which have important implications to the exploration of gold-based bimetallic nanoparticles for constructing sensing and catalytic nanomaterials.     

Current perspectives on quinazolines with potent biological activities: A review

Quinazoline is a heterocyclic compound having biological activities. It is aromatic in nature having bicyclic structure containing benzene ring and pyrimidine ring. Quinazoline and its derivatives are found to have wide range of biological activities that is anticancer, analgesic, antimicrobial, antihypertensive, anticonvulsant, antimalarial, antitumor, and anti-tubercular activities. The purpose of this review is to highlight the recent researches made by researchers on various biological activities of quinazoline derivatives on different targets.     

Intramolecular Cyclization Reactions of N-Alkylaryl-and N,N-Dialkylarylureas with Aldehydes

The reactions of N-alkylaryl-and N, N′-dialkylarylureas with aldehydes in acidic medium leads to the synthesis of N-carbamoyltetrahydro-isoquinolines and tetrahydro-1,3,5-oxadiazin-4-ones (urons) depending on the structure of starting compounds and the reaction conditions.     

The Ligand‐Based Quintuple Bond‐Shortening Concept and Some of Its Limitations

Herein, the ligand‐based concept of shortening quintuple bonds and some of its limitations are reported. In dichromium–diguanidinato complexes, the length of the quintuple bond can be influenced by the substituent at the central carbon atom of the used ligand. The guanidinato ligand with a 2,6‐dimethylpiperidine backbone was found to be the optimal ligand. The reduction of its chromium(II) chloride–ate complex gave a quintuply bonded bimetallic complex with a Cr? Cr distance of 1.7056 (12) Å. Its metal–metal distance, the shortest observed in any stable compound yet, is of essentially the same length as that of the longest alkane C? C bond (1.704 (4) Å). Both molecules, the alkane and the Cr complex, are of remarkable stability. Furthermore, an unsupported Cr^I dimer with an effective bond order (EBO) of 1.25 between the two metal atoms, indicated by CASSCF/CASPT2 calculations, was isolated as a by‐product. The formation of this by‐product indicates that with a certain bulk of the guanidinato ligand, other coordination isomers become relevant. Over‐reduction takes place, and a chromium–arene sandwich complex structurally related to the classic dibenzene chromium complex was observed, even when bulkier substituents are introduced at the central carbon atom of the used guanidinato ligand.     

Size‐Selective Encapsulation of Hydrophobic Guests by Self‐Assembled M4L6 Cobalt and Nickel Cages

Subtle differences in metal–ligand bond lengths between a series of [M₄L₆]^4? tetrahedral cages, where M=Fe^II, Co^II, or Ni^II, were observed to result in substantial differences in affinity for hydrophobic guests in water. Changing the metal ion from iron(II) to cobalt(II) or nickel(II) increases the size of the interior cavity of the cage and allows encapsulation of larger guest molecules. NMR spectroscopy was used to study the recognition properties of the iron(II) and cobalt(II) cages towards small hydrophobic guests in water, and single‐crystal X‐ray diffraction was used to study the solid‐state complexes of the iron(II) and nickel(II) cages.