Upper rim appended hybrid calixarenes via click chemistry

We report the application of "click" chemistry for the synthesis of hybrid calixarenes appended on the upper rim with carbohydrate and N,C-protected alpha-amino acids. The chemoselective N- or C-deprotection of the alpha-amino acids and their subsequent transformation into dipeptides is described. The first example of a chemo-enzymatic synthesis on upper rim derived calix[4]arenes using trans-sialidase affords sialylated lactose calix[4]arenes. Our innovative chemo-enzymatic process paves the way for further applications.     

A modified route to unsymmetrically substituted triphenylenes,new functionalised derivatives and twins,and the smallest reported triphenylene mesogen

ABSTRACT

We report the unexpected observation of columnar mesophase formation in a simple 2,7-dibromotetramethoxytriphenylene – by far the most lightly substituted discotic mesogen in this class. This derivative was prepared alongside the 3,6-dibromotriphenylene isomer to demonstrate an alternative, modified synthetic strategy that permits late-stage interchange of alkyl chain substituents. The new method is employed alongside the original route to deliver several new materials, including a conjugated ferrocene–triphenylene–ferrocene triad, a BODIPY–triphenylene–BODIPY triad and a new nematic twin linked through imine bridges.     

Equalizer technology followed by DIGE‐based proteomics for detection of cellular proteins in artificial peritoneal dialysis effluents

Peritoneal dialysis effluent (PDE) represents a rich pool of potential biomarkers for monitoring disease and therapy. Until now, proteomic studies have been hindered by the plasma‐like composition of the PDE. Beads covered with a peptide library are a promising approach to remove high abundant proteins and concentrate the sample in one step. In this study, a novel approach for proteomic biomarker identification in PDEs consisting of a depletion and concentration step followed by 2D gel based protein quantification was established. To prove this experimental concept a model system of artificial PDEs was established by spiking unused peritoneal dialysis (PD) fluids with cellular proteins reflecting control conditions or cell stress. Using this procedure, we were able to reduce the amount of high abundant plasma proteins and concentrate low abundant proteins while preserving changes in abundance of proteins with cellular origin. The alterations in abundance of the investigated marker for cell stress, the heat shock proteins, showed similar abundance profiles in the artificial PDE as in pure cell culture samples. Our results demonstrate the efficacy of this system in detecting subtle changes in cellular protein expression triggered by unphysiological stress stimuli typical in PD, which could serve as biomarkers. Further studies using patients’ PDE will be necessary to prove the concept in clinical PD and to assess whether this technique is also informative regarding enriching low abundant plasma derived protein biomarker in the PDE.     

CO(2) capture by a task-specific ionic liquid

Reaction of 1-butyl imidazole with 3-bromopropylamine hydrobromide, followed by workup and anion exchange, yields a new room temperature ionic liquid incorporating a cation with an appended amine group. The new ionic liquid reacts reversibly with CO2, reversibly sequestering the gas as a carbamate salt. The new ionic liquid, which can be repeatedly recycled in this role, is comparable in efficiency for CO2 capture to commercial amine sequestering reagents, and yet is nonvolatile and does not require water to function.     

Annihilation rates of positrons on aromatic molecules

We have measured positron annihilation rates for a selection of hydrocarbon molecules based on six carbon atoms, including substituted benzenes. These measurements illustrate the importance of molecular symmetry in determining the annihilation rate.     

The influence of large-scale seafloor slope and average bottom sound speed on low-grazing-angle monostatic acoustic scattering

Variations in large-scale seafloor slope and average seabed sound speed account for a significant portion of the variations in scattering intensity observed in low-grazing-angle monostatic reverberation. Numerical modeling using a finite-difference solution to the elastic wave equation is used to quantify the effect of these large-scale parameters in interpretations of reverberation data. For hard rough seafloor (e.g., basalt), the results of the modeling suggest that the monostatic backscattering strength increases with increasing large-scale seafloor slope up to a slope of about 15 degrees dipping toward the incident direction. Once the grazing angle of the incident wavefield exceeds the critical grazing angle for the flat reference seafloor the backscattering intensity increases only slowly with increasing grazing angle. Similarly, average subseafloor sound speed has a significant effect. Seafloor with low sound speeds characteristic of soft bottoms (e.g., sediment) generate significantly weaker backscatter signals than seafloor with sound speeds characteristic of hard bottoms (e.g., basalt). The difference is that the shear waves can always be passed into soft bottoms because even for a flat seafloor there is no shear wave critical grazing angle.     

A tandem metal carbene cyclization-cycloaddition approach to the pseudolaric acids

An approach toward the synthesis of the antifungal and cytotoxic pseudolaric acids based on the tandem metal carbene cyclization-cycloaddition reaction is described. Using this strategy, the advanced intermediate 3a bearing three of the four stereocenters of the target molecules has been synthesized. The substrate-controlled diastereoselectivity of the tandem carbene cyclization-cycloaddition was preferential for the undesired diastereomer, but reagent control through the use of Hashimoto's chiral rhodium catalyst Rh(2)(S-BPTV)(4) reversed the selectivity in favor of 3a. Ring opening of the oxabicyclic nucleus to give a hydroxycycloheptene has been demonstrated in a model study.     

Catalytic enantioselective [3 + 2]-cycloadditions of diazoketone-derived aryl-substituted carbonyl ylides

An evaluation of alpha-aryl-alpha-diazodiones in tandem carbonyl ylide formation-enantioselective [3 + 2]-cycloaddition reactions is described. Such substrates were designed to allow investigation of the electronic characteristics of the dipole upon asymmetric induction. Intramolecular cycloadditions (with a tethered alkene dipolarophile) were found to occur in good to quantitative yields, with a difference in ee exhibited by the two electronically different diazodiones 8 and 9. Intermolecular cycloadditions using diazodiones 12 and 13 with DMAD and arylacetylenes 16-18 again demonstrated that electronics play a key role in determining the outcome of the cycloaddition reactions. Enantioselectivities of up to 76% were observed.