Gas‐phase basicity of 2‐furaldehyde

2‐Furaldehyde (2‐FA), also known as furfural or 2‐furancarboxaldehyde, is an heterocyclic aldehyde that can be obtained from the thermal dehydration of pentose monosaccharides. This molecule can be considered as an important sustainable intermediate for the preparation of a great variety of chemicals, pharmaceuticals and furan‐based polymers. Despite the great importance of this molecule, its gas‐phase basicity (GB) has never been measured. In this work, the GB of 2‐FA was determined by the extended Cooks's kinetic method from electrospray ionization triple quadrupole tandem mass spectrometric experiments along with theoretical calculations. As expected, computational results identify the aldehydic oxygen atom of 2‐FA as the preferred protonation site. The geometries of O‐O‐cis and O‐O‐trans 2‐FA and of their six different protomers were calculated at the B3LYP/aug‐TZV(d,p) level of theory; proton affinity (PA) values were also calculated at the G3(MP2, CCSD(T)) level of theory. The experimental PA was estimated to be 847.9 ± 3.8 kJ mol^?1, the protonation entropy 115.1 ± 5.03 J mol^?1 K^?1 and the GB 813.6 ± 4.08 kJ mol^?1 at 298 K. From the PA value, a ΔH°_f of 533.0 ± 12.4 kJ mol^?1 for protonated 2‐FA was derived. Copyright © 2012 John Wiley & Sons, Ltd.     

Effect of pulse duration on KrF laser treatment of a polyethersulfone film: cell culture study

KrF laser processing of polyethersulfone (PES) films at three different pulse durations regarding to the change in biocompatibility is presented with cell culture study. Various microstructure and chemistry results were obtained on the surface upon laser irradiation. It is shown that nanoscale hydrophilic ripples significantly affect the adhesion of L929 cells on the surface.     

Synthesis of 4-aminoguaiazulene and its δ-lactam derivatives

A method for nitrogen insertion into guaiazulene hydrocarbons is developed. A one-pot reaction of 7-isopropyl-1-methylazulene-4-carboxylic acid, diphenylphosphoryl azide, and an alcohol (MeOH, ^tBuOH or BnOH) affords the corresponding carbamates. Deprotection of benzyl (7-isopropyl-1-methylazulen-4-yl)carbamate under basic conditions gave 4-aminoguaiazulene, which undergoes ring annulation reactions with 1,2-dicarbonyl reagents to yield tricyclic δ-lactams.     

Dynamics of solvent-free grafted nanoparticles

The diffusivity and structural relaxation characteristics of oligomer-grafted nanoparticles have been investigated with simulations of a previously proposed coarse-grained model at atmospheric pressure. Solvent-free, polymer-grafted nanoparticles as well as grafted nanoparticles in a melt were compared to a reference system of bare (ungrafted) particles in a melt. Whereas longer chains lead to a larger hydrodynamic radius and lower relative diffusivity for grafted particles in a melt, bulk solvent-free nanoparticles with longer chains have higher relative diffusivities than their short chain counterparts. Solvent-free nanoparticles with short chains undergo a glass transition as indicated by a vanishing diffusivity, diverging structural relaxation time and the formation of body-centered-cubic-like order. Nanoparticles with longer chains exhibit a more gradual increase in the structural relaxation time with decreasing temperature and concomitantly increasing particle volume fraction. The diffusivity of the long chain nanoparticles exhibits a minimum at an intermediate temperature and volume fraction where the polymer brushes of neighboring particles overlap, but must stretch to fill the interparticle space.     

Enzymatic synthesis of N-acylethanolamines: direct method for the aminolysis of esters

Immobilized Candida antarctica (Novozyme 435) catalyzed synthesis of N-acylethanolamines is described. Treatment of methyl esters with lipase and amines yielded the desired amides within 2-24 h with yields ranging from 41% to 98%.     

Synthesis and characterization of a compact tricyclic resorcinol from (+)- and (−)-3-pinanol

Resorcinol derivatives are important building blocks in the synthesis of natural products and pharmaceutical compounds including cannabinoids. Here we describe the synthesis and the structural characterization of a key resorcinol which carries a fully restricted bridged bicyclic group. We also report a potential mechanism for the acid catalyzed condensation of (+)- or (−)-3-pinanol with 2,6-dimethoxyphenol. The synthesized resorcinol facilitates the development of novel conformationally restricted cannabinoid analogs.     

"Common synthetic scaffolds" in the synthesis of structurally diverse natural products

Selected natural products have long been considered as desirable targets for total synthesis due to their unique biological properties and their challenging structural complexity. Laboratory synthesis of natural compounds usually relies on target-oriented synthesis, involving the production, isolation and purification of successive intermediates, requiring multiple steps to arrive to the final product. A far more economical approach using common synthetic scaffolds that can be readily transformed through biomimetic-like pathways to a range of structurally diverse natural products has been evolved in the last decade, leading synthesis to new directions. This tutorial review critically presents the hallmarks in this field.     

Molecular basis of Celmer's rules: stereochemistry of catalysis by isolated ketoreductase domains from modular polyketide synthases

A system is reported for the recombinant expression of individual ketoreductase (KR) domains from modular polyketide synthases (PKSs) and scrutiny of their intrinsic specificity and stereospecificity toward surrogate diketide substrates. The eryKR(1) and the tylKR(1) domains, derived from the first extension module of the erythromycin PKS and the tylosin PKS, respectively, both catalyzed reduction of (2R, S)-2-methyl-3-oxopentanoic acid N-acetylcysteamine thioester, with complete stereoselectivity and stereospecificity, even though the substrate is not tethered to an acyl carrier protein or an intact PKS multienzyme. In contrast, and to varying degrees, the isolated enzymes eryKR(2), eryKR(5), and eryKR(6) exercised poorer control over substrate selection and the stereochemical course of ketoreduction. These data, together with modeling of diketide binding to KR(1) and KR(2), demonstrate the fine energetic balance between alternative modes of presentation of ketoacylthioester substrates to KR active sites.     

Topological genericity of nowhere differentiable functions in the disc algebra

In this paper we introduce a class of functions contained in the disc algebra \({\mathcal{A}(D)}\) . We study functions \({f \in \mathcal{A}(D)}\) which have the property that the continuous periodic function \({u = {\rm Re}f|_{\mathbb{T}}}\) , where \({\mathbb{T}}\) is the unit circle, is nowhere differentiable. We prove that this class is non-empty and instead, generically, every function \({f \in \mathcal{A}(D)}\) has the above property. Afterwards, we strengthen this result by proving that, generically, for every function \({f \in \mathcal{A}(D)}\) , both continuous periodic functions \({u = {\rm Re}f|_\mathbb{T}}\) and \({\tilde{u} = {\rm Im}f|_\mathbb{T}}\) are nowhere differentiable. We avoid any use of the Weierstrass function and we mainly use Baire’s Category Theorem.     

Open vessel mode microwave-assisted synthesis of 2-oxazolines from carboxylic acids

Microwave-assisted synthesis of 2-oxazolines from carboxylic acids using the open vessel technique is described. This efficient method involves direct condensation of carboxylic acids with excess 2-amino-2-methyl-1-propanol at 170 °C to give the corresponding 2-oxazolines in moderate to excellent yields.