Thermal cleavage of the fmoc protection group

The Fmoc protection group is among the most commonly used protection groups for the amino function. A fast method for the thermal deavage of this protection group under base-free conditions without the need for dibenzofulvene scavengers is presented. The advantages of this method include straightforward testability by means of a simple high-temperature NMR experiment, usually high yields, and good selectivity towards the BOC protection group and t-butyl ethers.     

Use of the SAW Sensor Electronic Nose for Detecting the Adulteration of Virgin Coconut Oil with RBD Palm Kernel Olein

An electronic nose (zNose™) was applied to the detection of adulteration of virgin coconut oil. The system, which is based on a surface acoustic wave sensor was used to generate a pattern of volatile compounds present in the samples. Virgin coconut oil was mixed with refined, bleached and deodorized palm kernel olein at a level of adulteration from 1 to 20% (wt/wt). Adulterant peaks were identified from the chromatogram profile and fitted to a curve using linear regression. The best relationship (R ² = 0.91) was obtained between the peak tentatively identified as methyl dodecanoate and the percentage of palm kernel olein added. Pearson’s correlation coefficients (r) of 0.92 and 0.89 were obtained between adulterant peak methyl dodecanoate and of the iodine and peroxide values, respectively. Principal component analysis (PCA) was used to differentiate between pure and adulterated samples. The PCA provided good differentiation of samples with 74% of the variation accounted for by PC 1 and 17% accounted for by PC 2. Pure samples formed a separate cluster from all of the adulterated samples.     

alpha,alpha-Cyclopentaneglycine dipeptides capped with biaryls as tachykinin NK(2) receptor antagonists

The NK(2) receptor belongs to the family of tachykinin neurotransmitters. It has been reported to be involved in several pathological conditions, and selective antagonists are potentially useful drugs for the treatment of asthma, irritable bowel syndrome, cystitis, and depression. Starting from in-house capped dipeptide libraries, we were able to identify a number of molecules with sub-nanomolar binding affinity for the hNK(2) receptor. All were characterized by a rigid core structure with a strong constraint induced by an alpha,alpha-cyclopentaneglycine fragment. Herein we report the further elaboration of three initial basic structures. The planar benzothiophene group was substituted with a series of biphenyl and heterobiphenyl moieties that are well tolerated in terms of receptor affinity. The new compounds also maintained good antagonist potency in an in vitro functional assay, and a number of them showed significant in vivo activity after intravenous administration in our guinea pig model.     

Growth inhibitory effects of liposome-associated 1-O-octadecyl-2-O-methyl-sn-glycero-3-phosphocholine

The growth inhibitory effects of 1-O-octadecyl-2-O-methyl-sn-glycero-3-phosphocholine (ET-18-OCH₃) and various liposome compositions of ET-18-OCH₃ were compared in a standardized growth inhibition assay utilizing a diverse tumor cell line panel including cell lines expressing multidrug resistance. ET-18-OCH₃ and ELL-12 (4∶3∶1∶2, dioleoylphosphatidylcholine/cholesterol/dioleoylphosphatidylethanolamine-glutaric acid/ET-18-OCH₃), an optimal liposomal ET-18-OCH₃ formulation, inhibited growth in the micromolar range in drug-sensitive and-resistant cells. In general, ET-18-OCH₃-liposomes were about twofold less growth inhibitory than ET-18-OCH₃. However, the known hemolytic effects of ET-18-OCH₃ were greatly reduced, up to 20 or more times, by liposome association. The effects of ET-18-OCH₃ and ELL-12 were compared in intracellular [Ca²⁺] modulation and DNA fragmentation assays. ET-18-OCH₃ elicited both concentration- and serum-dependent transient and permanent increases in intracellular [Ca²⁺]. In contrast, ELL-12 did not modulate intracellular [Ca²⁺]. ET-18-OCH₃ and ELL-12 similarly affected DNA fragmentation, which may be indicative of apoptosis. The results suggest that, although the specific growth inhibitory effects of ET-18-OCH₃ and ELL-12 are similar, associating ET-18-OCH₃ with stable well-characterized liposomes eliminates nonspecific cell membrane-associated lytic effects.     

Use of Biotinylated Ubiquitin for Analysis of Rat Brain Mitochondrial Proteome and Interactome

Applicability of in vitro biotinylated ubiquitin for evaluation of endogenous ubiquitin conjugation and analysis of ubiquitin-associated protein-protein interactions has been investigated. Incubation of rat brain mitochondria with biotinylated ubiquitin followed by affinity chromatography on avidin-agarose, intensive washing, tryptic digestion of proteins bound to the affinity sorbent and their mass spectrometry analysis resulted in reliable identification of 50 proteins belonging to mitochondrial and extramitochondrial compartments. Since all these proteins were bound to avidin-agarose only after preincubation of the mitochondrial fraction with biotinylated ubiquitin, they could therefore be referred to as specifically bound proteins. A search for specific ubiquitination signature masses revealed several extramitochondrial and intramitochondrial ubiquitinated proteins representing about 20% of total number of proteins bound to avidin-agarose. The interactome analysis suggests that the identified non-ubiquitinated proteins obviously form tight complexes either with ubiquitinated proteins or with their partners and/or mitochondrial membrane components. Results of the present study demonstrate that the use of biotinylated ubiquitin may be considered as the method of choice for in vitro evaluation of endogenous ubiquitin-conjugating machinery in particular subcellular organelles and changes in ubiquitin/organelle associated interactomes. This may be useful for evaluation of changes in interactomes induced by protein ubiquitination under norm and various brain pathologies.     

Promotion Effect of 2-Methylpiperidine on the Direct Desulfurization of Dibenzothiophene over NiMo/γ-Al2O3

The hydrodesulfurization (HDS) of dibenzothiophene (DBT) was studied at 300 °C, 4.8 MPa H₂ and 35 kPa H₂S in the presence of 0 to 6 kPa 2-methylpyridine and 2-methylpiperidine. 2-Methylpyridine suppressed the hydrogenation pathway by a factor of 6 to 30, depending on its partial pressure, and moderately inhibited the direct desulfurization pathway of the HDS of DBT (by a factor of 2 or less). 2-Methylpiperidine suppressed the hydrogenation by a factor of 10 to 50 but promoted the direct desulfurization of DBT at low partial pressures of 2-methylpiperidine. Both pathways were inhibited at high concentrations of 2-methylpiperidine. Structural and electronic factors may account for the promoting effect of 2-methylpiperidine.     

Flexible high-performance carbon nanotube integrated circuits

Carbon nanotube thin-film transistors are expected to enable the fabrication of high-performance, flexible and transparent devices using relatively simple techniques. However, as-grown nanotube networks usually contain both metallic and semiconducting nanotubes, which leads to a trade-off between charge-carrier mobility (which increases with greater metallic tube content) and on/off ratio (which decreases). Many approaches to separating metallic nanotubes from semiconducting nanotubes have been investigated, but most lead to contamination and shortening of the nanotubes, thus reducing performance. Here, we report the fabrication of high-performance thin-film transistors and integrated circuits on flexible and transparent substrates using floating-catalyst chemical vapour deposition followed by a simple gas-phase filtration and transfer process. The resulting nanotube network has a well-controlled density and a unique morphology, consisting of long (~10 μm) nanotubes connected by low-resistance Y-shaped junctions. The transistors simultaneously demonstrate a mobility of 35 cm(2) V(-1) s(-1) and an on/off ratio of 6 × 10(6). We also demonstrate flexible integrated circuits, including a 21-stage ring oscillator and master-slave delay flip-flops that are capable of sequential logic. Our fabrication procedure should prove to be scalable, for example, by using high-throughput printing techniques.     

Microbial fuel cell application in landfill leachate treatment

The feasibility of using microbial fuel cells (MFCs) in landfill leachate treatment and electricity production was assessed under high levels of nitrogen concentration (6033 mg NL(-1)) and conductivity (73,588 μS cm(-1)). An air-cathode MFC was used over a period of 155 days to treat urban landfill leachate. Up to 8.5 kg COD m(-3)d(-1) of biodegradable organic matter was removed at the same time as electricity (344 m Wm(-3)) was produced. Nitrogen compounds suffered transformations in the MFC. Ammonium was oxidized to nitrite using oxygen diffused from the membrane. However, at high free ammonia concentrations (around 900 mg N-NH(3)L(-1)), the activity of nitrifier microorganisms was inhibited. Ammonium reduction was also resulted from ammonium transfer through the membrane or from ammonia loss. High salinity content benefited the MFC performance increasing power production and decreasing the internal resistance.     

Propagation of longitudinal and bulk waves in shock-loaded transversally isotropic single crystals

The paper is present 3D numerical simulation data on elastoplastic deformation in auxetic single crystals with account of anisotropic pressure. The use of anisotropic pressure allows us to demonstrate the absence of shock wave splitting into an elastic precursor and a plastic wave in a Zn single crystal in the loading direction [0001]. This effect in Zn single crystals is observed in full-scale experiments at any loading rate in the [0001] direction. It is shown that anisotropic pressure should be entered into mathematical models of materials whose elastic properties are characterised by five and more independent elastic constants and hence by bulk compression anisotropy. The use of isotropic pressure in simulating the deformation of such materials leads to nonphysical results.