Methods for direct determination of mitomycin C in aqueous solutions and in urine

Stripping voltammetry (SV) is used to quantitatively determine concentrations of the anti-neoplastic drug mitomycin C (MMC) alone and in mixtures with 5-fluorouracil and cisplatin, both of which are used in combined chemotherapy with MMC. If the accumulation is performed at the potentials of MMC reduction (-0.35 V vs. SCE), reduced MMC is strongly adsorbed at the electrode. It is possible to prepare a MMC-modified electrode, which, after a washing step, is transferred to the background electrolyte to determine MMC by voltammetry. This procedure, which is termed transfer stripping voltammetry (TSV), helps to eliminate interferences and can be applied for a direct determination of MMC alone or in mixtures with other drugs in urine

A Single Conserved Amino Acid Residue as a Critical Context-Specific Determinant of the Differential Ability of Mdm2 and MdmX RING Domains to Dimerize

Mdm2 and MdmX are related proteins serving in the form of the Mdm2 homodimer or Mdm2/MdmX heterodimer as an E3 ubiquitin ligase for the tumor suppressor p53. The dimerization is required for the E3 activity and is mediated by the conserved RING domains present in both proteins, but only the RING domain of Mdm2 can form homodimers efficiently. We performed a systematic mutational analysis of human Mdm2, exchanging parts of the RING with the corresponding MdmX sequence, to identify the molecular determinants of this difference. Mdm2 can also promote MdmX degradation, and we identified several mutations blocking it. They were located mainly at the Mdm2/E2 interface and did not disrupt the MdmX-Mdm2 interaction. Surprisingly, some mutations of the Mdm2/E2 interface inhibited MdmX degradation, which is mediated by the Mdm2/MdmX heterodimer, but did not affect p53 degradation, mediated by the Mdm2 homodimer. Only one mutant, replacing a conserved cysteine 449 with asparagine (C449N), disrupted the ability of Mdm2 to dimerize with MdmX. When we introduced the cysteine residue into the corresponding site in MdmX, the RING domain became capable of forming dimers with other MdmX molecules in vivo, suggesting that one conserved amino acid residue in the RINGs of Mdm2 and MdmX could serve as the determinant of the differential ability of these domains to form dimers and their E3 activity. In immunoprecipitations, however, the homodimerization of MdmX could be observed only when the asparagine residue was replaced with cysteine in both RINGs. This result suggested that heterocomplexes consisting of one mutated MdmX RING with cysteine and one wild-type MdmX RING with asparagine might be less stable, despite being readily detectable in the cell-based assay. Moreover, Mdm2 C449N blocked Mdm2-MdmX heterodimerization but did not disrupt the ability of Mdm2 homodimer to promote p53 degradation, suggesting that the effect of the conserved cysteine and asparagine residues on dimerization was context-specific. Collectively, our results indicate that the effects of individual exchanges of conserved residues between Mdm2 and MdmX RING domains might be context-specific, supporting the hypothesis that Mdm2 RING homodimers and Mdm2-MdmX heterodimers may not be entirely structurally equivalent, despite their apparent similarity

Efficient energy transport in an organic semiconductor mediated by transient exciton delocalization.

Efficient energy transport is desirable in organic semiconductor (OSC) devices. However, photogenerated excitons in OSC films mostly occupy highly localized states, limiting exciton diffusion coefficients to below ~10-2 cm2/s and diffusion lengths below ~50 nm. We use ultrafast optical microscopy and nonadiabatic molecular dynamics simulations to study well-ordered poly(3-hexylthiophene) nanofiber films prepared using living crystallization-driven self-assembly, and reveal a highly efficient energy transport regime: transient exciton delocalization, where energy exchange with vibrational modes allows excitons to temporarily re-access spatially extended states under equilibrium conditions. We show that this enables exciton diffusion constants up to 1.1 ± 0.1 cm2/s and diffusion lengths of 300 ± 50 nm. Our results reveal the dynamic interplay between localized and delocalized exciton configurations at equilibrium conditions, calling for a re-evaluation of exciton dynamics and suggesting design rules to engineer efficient energy transport in OSC device architectures not based on restrictive bulk heterojunctions

A 41,500 year-old decorated ivory pendant from Stajnia Cave (Poland)

Evidence of mobiliary art and body augmentation are associated with the cultural innovations introduced by Homo sapiens at the beginning of the Upper Paleolithic. Here, we report the discovery of the oldest known human-modified punctate ornament, a decorated ivory pendant from the Paleolithic layers at Stajnia Cave in Poland. We describe the features of this unique piece, as well as the stratigraphic context and the details of its chronometric dating. The Stajnia Cave plate is a personal 'jewellery' object that was created 41,500 calendar years ago (directly radiocarbon dated). It is the oldest known of its kind in Eurasia and it establishes a new starting date for a tradition directly connected to the spread of modern Homo sapiens in Europe

Genotyping a second growth coast redwood forest : a high throughput methodology

The idea that excitonic (electronic) coherences are of fundamental importance to natural photosynthesis gained popularity when slowly dephasing quantum beats (QBs) were observed in the two-dimensional electronic spectra of the Fenna–Matthews–Olson (FMO) complex at 77 K. These were assigned to superpositions of excitonic states, a controversial interpretation, as the strong chromophore–environment interactions in the complex suggest fast dephasing. Although it has been pointed out that vibrational motion produces similar spectral signatures, a concrete assignment of these oscillatory signals to distinct physical processes is still lacking. Here we revisit the coherence dynamics of the FMO complex using polarization-controlled two-dimensional electronic spectroscopy, supported by theoretical modelling. We show that the long-lived QBs are exclusively vibrational in origin, whereas the dephasing of the electronic coherences is completed within 240 fs even at 77 K. We further find that specific vibrational coherences are produced via vibronically coupled excited states. The presence of such states suggests that vibronic coupling is relevant for photosynthetic energy transfer

Determination of Specific Electrocatalytic Sites in the Oxidation of Small Molecules on Crystalline Metal Surfaces

The identification of active sites in electrocatalytic reactions is part of the elucidation of mechanisms of catalyzed reactions on solid surfaces. However, this is not an easy task, even for apparently simple reactions, as we sometimes think the oxidation of adsorbed CO is. For surfaces consisting of non-equivalent sites, the recognition of specific active sites must consider the influence that facets, as is the steps/defect on the surface of the catalyst, cause in its neighbors; one has to consider the electrochemical environment under which the “active sites” lie on the surface, meaning that defects/steps on the surface do not partake in chemistry by themselves. In this paper, we outline the recent efforts in understanding the close relationships between site-specific and the overall rate and/or selectivity of electrocatalytic reactions. We analyze hydrogen adsorption/desorption, and electro-oxidation of CO, methanol, and ammonia. The classical topic of asymmetric electrocatalysis on kinked surfaces is also addressed for glucose electro-oxidation. The article takes into account selected existing data combined with our original works.M.J.S.F. is grateful to PNPD/CAPES (Brazil). J.M.F. thanks the MCINN (FEDER, Spain) project-CTQ-2016-76221-P

Facile preparation of a cellulose microfibers–exfoliated graphite composite: a robust sensor for determining dopamine in biological samples

© 2017, Springer Science+Business Media B.V. A simple and robust dopamine (DA) sensor was developed using a cellulose microfibers (CMF)–exfoliated graphite composite-modified screen-printed carbon electrode (SPCE) for the first time. The graphite-CMF composite was prepared by sonication of pristine graphite in CMF solution and was characterized by high-resolution scanning electron microscopy, Fourier transform, infrared, and Raman spectroscopy. The cyclic voltammetry results reveal that the graphite-CMF composite modified SPCE has superior electrocatalytic activity against oxidation of dopamine than SPCE modified with pristine graphite and CMF. The presence of large edge plane defects on exfoliated graphite and abundant oxygen functional groups of CMF enhance electrocatalytic activity and decrease potential to oxidize DA. Differential pulse voltammetry was used to quantify DA using the graphite-CMF composite-modified SPCE and demonstrated a linear response for DA detection in the range of 0.06–134.5 µM. The sensor shows a detection limit at 10 nM with an appropriate sensitivity and displays appropriate recovery of DA in human serum samples with good repeatability. Sensor selectivity is demonstrated in the presence of 50-fold concentrations of potentially active interfering compounds including ascorbic acid, uric acid, and dihydroxybenzene isomers

Dynamic and role of cytosekeletal proteins in mammalian sperm cells

The cytoskeleton of sperm head consists of resistant structural proteins of the nucleus and of perinuclear theca, which are largely rosponsible for the shaping of the nucleus. three mahjor cyteskeletal proteins, actin, tzubnulin and spectrin, are present in the head of mammalian spermatohzoa. Maoreober, the mictotubular cytoskeleton also contains other dynamic proteins, which have a morphological function within the cell and which are responsible for cell signalling processes

Dynamic and role of cytosekeletal proteins in mammalian sperm cells

The cytoskeleton of sperm head consists of resistant structural proteins of the nucleus and of perinuclear theca, which are largely rosponsible for the shaping of the nucleus. three mahjor cyteskeletal proteins, actin, tzubnulin and spectrin, are present in the head of mammalian spermatohzoa. Maoreober, the mictotubular cytoskeleton also contains other dynamic proteins, which have a morphological function within the cell and which are responsible for cell signalling processes