All-trans-1-acyloxy-1,3-pentadiene-5 ols as reactive dienes in new intramolecular diels-alder reactions

The high reactivity of the $\text{all-trans}$-1-acyloxy-1,3-pentadiene-5-ols as dienes in intramolecular Diels-Alder reactions with maleic anhydride and fumaric acid ethylester monochloride is discussed.     

Regulation of plastic from a circular economy perspective

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Esters of 5-carboxyl-5-methyl-1-pyrroline N-oxide: a family of spin traps for superoxide

Apparent rate constants, at acidic pH and neutral pH for the reaction of a family of ester-containing 5-carboxyl-5-methyl-1-pyrroline N-oxides with superoxide (O2*-) were estimated, using ferricytochrome c as a competitive inhibitor. It was of interest to note that the rate constants were similar among the different nitrones and not that significantly different from that found for 5-(diethoxyphosphoryl)-5-dimethyl-1-pyrroline N-oxide. At acidic pH, the rate constant for spin trapping O2*- was 3-fold greater than that at physiological pH. Subsequent experiments determined the half-life of aminoxyls, derived from the reaction of these nitrones with O2*-. The EPR spectra were modeled by using a global analysis method. The results clearly demonstrated that EPR spectra of all the aminoxyls were inconsistent with a model that included a single gamma-hydrogen splitting. A better interpretation modeled them as two diastereomers with identical nitrogen splittings and slightly different beta-hydrogen splittings. Detailed line width analyses slightly favored an equal line width-unequal population ratio for the two diastereomers.     

Trace determination of volatile sulfur compounds by solid-phase microextraction and GC-MS

A method was developed for the simultaneous determination of the following nine volatile sulfur compounds in gas samples: carbon disulfide, carbonyl sulfide, ethyl sulfide, ethyl methyl sulfide, hydrogen sulfide, isopropanethiol, methanethiol, methyl disulfide and methyl sulfide. The target compounds were preconcentrated by solid-phase microextraction (SPME) and determined by gas chromatography combined with mass spectrometry. Experimental design was employed to optimize the extraction time and temperature and concurrent detection of the nine compounds was achieved by using an SPME fiber coated with Carboxen-polydimethylsiloxane (75 microns). Detection limits ranged from 1 ppt (v/v) for carbon disulfide to 350 ppt (v/v) for hydrogen sulfide and calibration functions were linear up to 20 ppb (v/v) for all the compounds investigated.     

A new flavonol glycoside and other flavonoids from the aerial parts of Taverniera aegyptiaca

Isolation of flavonoids from the aerial parts of Taverniera aegyptiaca Bioss. (Fabaceae) led to identification of one new flavonol glycoside, isorhamnetin-3-O-α-l-rhamnopyranosyl-(1→2)-α-l-arabinopyranoside (1), along with eleven compounds, which previously have not been isolated from this plant quercetin-3-O-α-l-rhamnopyranosyl-(1→2)-[α-l-rhamnopyranosyl-(1→6)-β-d-galactopyranoside] (2), isorhamnetin-3-O-α-l-arabinopyranoside (3), quercetin-3-O-α-l-rhamnopyranosyl-(1→6)-β-d-glucopyranoside (4), isorhamnetin-3-O-α-l-rhamnopyranosyl-(1→6)-β-d-glucopyranoside (7), isorhamnetin 3-O-α-l-rhamnopyranosyl-(1→2)-[α-l-rhamnopyranosyl-(1→6)-β-d-galactopyranoside] (8), isorhamnetin 3-O-α-l-rhamnopyranosyl-(1→2)-[α-l-rhamnopyranosyl-(1→6)-β-d-glucopyranoside] (9), kaempferol 3-O-α-l-rhamnopyranosyl-(1→2)-[α-l-rhamnopyranosyl-(1→6)-β-d-galactopyranoside] (10), isorhamnetin (11), 4,4′-dihydroxy-2′-methoxychalcone (12), formononetin (13) and calycosin (15)] and some compounds already known from this plant [quercetin-3-O-robinobioside (5), isorhamnetin-3-O-robinobioside (6), afrormosin (14) and odoratin (16)].     

Synthesis and Characterization of Multinanometer‐Sized Expanded Dendralenes with an iso‐Poly(triacetylene) Backbone

A series of [n]dendralenes (n =3, 4, 8, 3b – d (Fig. 1)) expanded with buta‐1,3‐diynediyl moieties between the CC bonds were prepared by repetitive acetylenic scaffolding of 3‐(cyclohexylidene)penta‐1,4‐diyne building blocks (Scheme). These remarkably unstable iso‐poly(triacetylene) (iso‐PTA) oligomers were characterized by ¹H‐ and ¹³C NMR (Fig. 3 and Table 1), IR, and UV/VIS (Figs. 4 and 6 and Table 2) spectroscopy, as well as mass spectrometry (Fig. 2). The expanded [8]dendralene contains 40 C(sp)‐ and C(sp²)‐atoms in the backbone and represents the longest iso‐PTA oligomer prepared to date. HOMO‐LUMO Gap energies were determined as a function of oligomeric length (Fig. 5 and Table 3), providing insight into the degree of π‐electron delocalization in these cross‐conjugated chromophores. A continous drop in the HOMO‐LUMO gap with increasing number of monomeric repeating units provides evidence that cross‐conjugation along the oligomeric backbone is effective to some extent. The limiting HOMO‐LUMO gap energy for an infinitely long, buta‐1,3‐diynediyl‐expanded dendralene was extrapolated to about 3.3–3.5 eV. The conformational preferences of the expanded dendralenes were analyzed in semi‐empirical calculations, revealing energetic preferences for planar or slightly twisted s‐cis and ‘U‐shaped' geometries.     

Base-Pairing Properties of Double-Headed Nucleotides

Nucleotides that contain two nucleobases (double-headed nucleotides) have the potential to condense the information of two separate nucleotides into one. This presupposes that both bases must successfully pair with a cognate strand. Here, double-headed nucleotides that feature cytosine, guanine, thymine, adenine, hypoxanthine, and diaminopurine linked to the C2′-position of an arabinose scaffold were developed and examined in full detail. These monomeric units were efficiently prepared by convergent synthesis and incorporated into DNA oligonucleotides by means of the automated phosphoramidite method. Their pairing efficiency was assessed by UV-based melting-temperature analysis in several contexts and extensive molecular dynamics studies. Altogether, the results show that these double-headed nucleotides have a well-defined structure and invariably behave as functional dinucleotide mimics in DNA duplexes.     

The complete 51V MAS NMR spectrum of surface vanadia nanoparticles on anatase (TiO2): vanadia surface structure of a DeNOx catalyst

The first observations of the complete manifold of spinning sidebands (ssbs) including both the central and satellite transitions in (51)V MAS NMR spectra of surface vanadia nanoparticles on titania in DeNO(x) catalysts are presented. (51)V quadrupole coupling and chemical shift anisotropy parameters for the dominating vanadia structure are determined from (51)V MAS NMR spectra recorded at 9.4 and 14.1 T. Based on correlations previously established between (51)V NMR parameters and crystal structure data for inorganic vanadates, the NMR data are consistent with vanadium in a distorted octahedral oxygen coordination environment for the so-called strongly bonded vanadia species on the surface. The investigation includes two vanadia-titania model catalysts and six industrial-type DeNO(x) catalysts.     

A stereochemical anomaly: the cyclised (R)-AMPA analogue (R)-3-hydroxy-4,5,6,7-tetrahydroisoxazolo[5,4-c]pyridine-5-carboxylic acid [(R)-5-HPCA] resembles (S)-AMPA at glutamate receptors

(RS)-3-Hydroxy-4,5,6,7-tetrahydroisoxazolo[5,4-c]pyridine-5-carboxylic acid (5-HPCA)(), which is a conformationally constrained cyclised analogue of AMPA has previously been described as causing glutamate receptor mediated excitations of spontaneously firing cat spinal interneurons in a similar fashion to AMPA. We have now prepared the enantiomers of through chiral chromatographic resolution of (RS)-3-(carboxymethoxy)-4,5,6,7-tetrahydroisoxazolo[5,4-c]pyridine-5-carboxylic acid () followed by a stereoconservative hydrolysis resulting in the enantiomers of with high enantiomeric excess (% ee [greater-than-or-equal] 99). The absolute configurations indicated by an X-ray analysis of (-)- monohydrate were confirmed by comparing observed and ab initio calculated electronic circular dichroism spectra and by stereoconservative synthesis of (S)- from (S)-AMPA, the pharmacologically active form of AMPA. The pharmacological effects at native and cloned (GluR1-4) AMPA receptors were shown to reside exclusively with (R)-(+)-, in striking contrast to the usual stereoselectivity trend among AMPA receptor agonists. The reasons for this anomalous behaviour became clear upon docking both enantiomers of to the agonist binding site of GluR2.     

Solid-phase synthesis of an apoptosis-inducing tetrapeptide mimicking the Smac protein

An approach for the solid-phase synthesis of apoptosis-inducing Smac peptidomimetics is presented. Using a Rink linker strategy, tetrapeptides mimicking the N-4-terminal residue of the Smac protein [(N-Me)AVPF sequence] were synthesized on PEGA resin in excellent purities and yields. Following two synthetic routes, a known tetrapeptide, incorporating a substituted proline, previously shown to exhibit excellent biological activity in vitro as well as low toxicity, was synthesized effectively on a solid support.