Djelovanje karboksilnih kiselina na crveno obojenje cvjetova žutinice

Eight carboxylic acids were fed at 1-10000 pM to the flower pastes from fresh dyer’s saffron (Carthamus tinctorius L.) capitula and their effects on the red colouration investigated. Glyoxyllic acid, glycolic acid, oxaloacetic acid, 2-oxoglutaric acid and gluconic acid were found to be positive stimulators for the reaction, while succinic acid, malic acid and citric acid inhibited the colour change.Svojim ranijim istraživanjima autori su pokazali da usitnjeni cvjetovi žutinice (Carthamus tinctorius L.) poprime crvenu boju ako na njih djeluju otopine aminokiselina. Učinkovitost pojedine aminokiseline ovisi o tipu: kisele amino- kiseline bile su najučinkovitije, neutralne nešto manje, one s aromatičnim skupinama ili skupinama sa sumporom još manje, dok su bazične aminokiseline bile najmanje učinkovite. Za objašnjenje ovih rezultata bilo je potrebno da se ustanove još drugi metaboliti koji biokatalitički utječu na promjenu boje cvjetova. U ovom prilogu autori objavljuju podatke o promjenama boje nakon primjene karboksilnih kiselina. U tu svrhu istražili su djelovanje osam karboksilnih kiselina u koncentracijama od 1 - 10000 pM na kašu od zdrobljenih cvjetova žutinice (Carthamus tinctorius L.). Postignuti rezultati su pokazali da glioksilna, glikolna, oksalooc- tena, 2-oksoglutarna i glukonska kiselina pospješuju reakciju stvaranja crvenog bojila, dok jantarna, jabučna i limunska kiselina tu reakciju inhibiraju. U radu se navode točni podaci o materijalu, metodama rada i rezultatima koji su prikazani u preglednoj tabeli. Rezultate autori kratko komentiraju uz razmišljanja da bi kemijske strukture karboksilnih kiselina mogle biti uže povezane s procesima promjene bojila, iako je sam mehanizam reakcije zasad još nepoznat

Synthesis and reductive chemistry of bimetallic and trimetallic rare-earth metallocene hydrides with (C5H4SiMe3)1− ligands

The reductive chemistry of [Cp\u272Ln(μ–H)(THF)x]y [Ln = Y, Dy, Tb; Cp\u27 = (C5H4SiMe3)1−; x = 2, 0 and y = 2, 3] was examined to determine if these hydrides would be viable precursors for 4fn5d1 Ln2+ ions that could form 5d1-5d1 metal–metal bonded complexes. The hydrides were prepared by reaction of the chlorides, [Cp\u272Ln(μ–Cl)]2, 1-Ln, with allylmagnesium chloride to form the allyl complexes, [Cp\u272Y(η3–C3H5)(THF)], 2-Ln, which were hydrogenolyzed. The solvent-free reaction of solid 2-Ln with 60 psi of H2 gas in a Fischer-Porter apparatus produced, in the Y case, the trimetallic species, [Cp\u272Y(μ–H)]3, 3-Y, and in the Dy and Tb cases, the bimetallic complexes [Cp\u272Ln(μ–H)(THF)]2, 4-Ln (Ln = Dy, Tb). The latter complexes could be converted to 3-Dy and 3-Tb by heating under vacuum. Isopiestic data indicate that 3-Y solvates to 4-Y in THF. Reductions of 4-Y, 4-Dy, and 4-Tb with KC8 in the presence of a chelate such as 2.2.2-cryptand or 18-crown-6 all gave reaction products with intense dark colors characteristic of Ln2+ ions. In the yttrium case, with either chelating agent, the dark green product gives a rhombic EPR spectrum (g1 = 2.01, g2 = 1.99, g3 = 1.98, A = 24.1 G) at 77 K. However, the only crystallographically-characterizable products obtainable from these solutions were Ln3+polyhydride anion complexes of composition, [K(chelate)]{[Cp\u272Ln(μ–H)]3(μ–H)}

Cryptic Transcription Mediates Repression of Subtelomeric Metal Homeostasis Genes

Nonsense-mediated mRNA decay (NMD) prevents the accumulation of transcripts bearing premature termination codons. Here we show that Saccharomyces cerevisiae NMD mutants accumulate 5′–extended RNAs (CD-CUTs) of many subtelomeric genes. Using the subtelomeric ZRT1 and FIT3 genes activated in response to zinc and iron deficiency, respectively, we show that transcription of these CD-CUTs mediates repression at the bona fide promoters, by preventing premature binding of RNA polymerase II in conditions of metal repletion. Expression of the main ZRT1 CD-CUT is controlled by the histone deacetylase Rpd3p, showing that histone deacetylases can regulate expression of genes through modulation of the level of CD-CUTs. Analysis of binding of the transcriptional activator Zap1p and insertion of transcriptional terminators upstream from the Zap1p binding sites show that CD-CUT transcription or accumulation also interferes with binding of the transcriptional activator Zap1p. Consistent with this model, overexpressing Zap1p or using a constitutively active version of the Aft1p transcriptional activator rescues the induction defect of ZRT1 and FIT3 in NMD mutants. These results show that cryptic upstream sense transcription resulting in unstable transcripts degraded by NMD controls repression of a large number of genes located in subtelomeric regions, and in particular of many metal homeostasis genes

Serological Profiling of a Candida albicans Protein Microarray Reveals Permanent Host-Pathogen Interplay and Stage-Specific Responses during Candidemia

Candida albicans in the immunocompetent host is a benign member of the human microbiota. Though, when host physiology is disrupted, this commensal-host interaction can degenerate and lead to an opportunistic infection. Relatively little is known regarding the dynamics of C. albicans colonization and pathogenesis. We developed a C. albicans cell surface protein microarray to profile the immunoglobulin G response during commensal colonization and candidemia. The antibody response from the sera of patients with candidemia and our negative control groups indicate that the immunocompetent host exists in permanent host-pathogen interplay with commensal C. albicans. This report also identifies cell surface antigens that are specific to different phases (i.e. acute, early and mid convalescence) of candidemia. We identified a set of thirteen cell surface antigens capable of distinguishing acute candidemia from healthy individuals and uninfected hospital patients with commensal colonization. Interestingly, a large proportion of these cell surface antigens are involved in either oxidative stress or drug resistance. In addition, we identified 33 antigenic proteins that are enriched in convalescent sera of the candidemia patients. Intriguingly, we found within this subset an increase in antigens associated with heme-associated iron acquisition. These findings have important implications for the mechanisms of C. albicans colonization as well as the development of systemic infection

The genetic interaction network of CCW12, a Saccharomyces cerevisiae gene required for cell wall integrity during budding and formation of mating projections

<p>Abstract</p> <p>Background</p> <p>Mannoproteins construct the outer cover of the fungal cell wall. The covalently linked cell wall protein Ccw12p is an abundant mannoprotein. It is considered as crucial structural cell wall component since in baker's yeast the lack of <it>CCW12 </it>results in severe cell wall damage and reduced mating efficiency.</p> <p>Results</p> <p>In order to explore the function of <it>CCW12</it>, we performed a Synthetic Genetic Analysis (SGA) and identified genes that are essential in the absence of <it>CCW12</it>. The resulting interaction network identified 21 genes involved in cell wall integrity, chitin synthesis, cell polarity, vesicular transport and endocytosis. Among those are <it>PFD1</it>, <it>WHI3</it>, <it>SRN2</it>, <it>PAC10</it>, <it>FEN1 </it>and <it>YDR417C</it>, which have not been related to cell wall integrity before. We correlated our results with genetic interaction networks of genes involved in glucan and chitin synthesis. A core of genes essential to maintain cell integrity in response to cell wall stress was identified. In addition, we performed a large-scale transcriptional analysis and compared the transcriptional changes observed in mutant <it>ccw12</it>Δ with transcriptomes from studies investigating responses to constitutive or acute cell wall damage. We identified a set of genes that are highly induced in the majority of the mutants/conditions and are directly related to the cell wall integrity pathway and cell wall compensatory responses. Among those are <it>BCK1</it>, <it>CHS3</it>, <it>EDE1</it>, <it>PFD1</it>, <it>SLT2 </it>and <it>SLA1 </it>that were also identified in the SGA. In contrast, a specific feature of mutant <it>ccw12</it>Δ is the transcriptional repression of genes involved in mating. Physiological experiments substantiate this finding. Further, we demonstrate that Ccw12p is present at the cell periphery and highly concentrated at the presumptive budding site, around the bud, at the septum and at the tip of the mating projection.</p> <p>Conclusions</p> <p>The combination of high throughput screenings, phenotypic analyses and localization studies provides new insight into the function of Ccw12p. A compensatory response, culminating in cell wall remodelling and transport/recycling pathways is required to buffer the loss of <it>CCW12</it>. Moreover, the enrichment of Ccw12p in bud, septum and mating projection is consistent with a role of Ccw12p in preserving cell wall integrity at sites of active growth.</p> <p>The microarray data produced in this analysis have been submitted to NCBI GEO database and GSE22649 record was assigned.</p

Właściwości mechaniczne hybrydowych oraz nano-hybrydowych prętów FRP

The paper describes the recent developments of Hybrid Fibre-Reinforced Polymer (HFRP) and nano-Hybrid Fibre-Reinforced Polymer (nHFRP) bars manufactured using the pultrusion process. Hybridization of less expensive basalt fibres with carbon fibres leads to more sustainable alternative to Basalt-FRP (BFRP) bars and more economically-efficient alternative to Carbon-FRP (CFRP) bars. At the same time the properties of the proposed bars can be modified by changing the bars configuration. The New-Developed HFRP bars were subjected to tensile axial loading to investigate its structural behaviour. The effect of hybridization on tensile properties of HFRP bars was verified experimentally by comparing the results of tensile test of HFRP bars with non-hybrid BFRP bars. It is possible to improve and predict the final mechanical characteristics of HFRP bars through mechanical hybridization of constituents and their volume fractions before it will be produced. The analytical/numerical considerations and experimental testing showed the same tendency in obtained results. In pre-manufacturing phase it was set that for the final mechanical properties, the influence of bar configuration is less important than the influence of different volume fractions of fibres. In addition, it was assumed that the preferable location of carbon fibres will be in the core region due to technological problems. It is worth to mention that the difference in obtained strength characteristics between analytical and numerical considerations was very small, however the obtained results were much higher than results obtained experimentally. Authors suggested that lower results obtained experimentally can be explained by imperfect interphase development and therefore attempted to improve the chemical cohesion between constituents by adding nanosilica particles to matrix consistency.W artykule zostały przedstawione najnowsze postępy w zakresie zachowania mechanicznego hybrydowych prętów FRP (HFRP) oraz nano-hybrydowych (nHFRP) produkowanych w procesie pultruzji. Hybrydyzacja włókien bazaltowych z włóknami węglowymi prowadzi do bardziej zrównoważonej alternatywy dla prętów na bazie włókien bazaltowych (BFRP) i bardziej ekonomicznej alternatywy dla prętów FRP na bazie włókien węglowych (CFRP). Jednocześnie właściwości proponowanych prętów można modyfikować zmieniając ich konfigurację. Nowo opracowane pręty HFRP poddano obciążeniu osiowemu przy rozciąganiu, aby zbadać jego zachowanie strukturalne. Wpływ hybrydyzacji na właściwości mechaniczne prętów HFRP zweryfikowano doświadczalnie, porównując wyniki próby rozciągania prętów HFRP z niehybrydowymi prętami BFRP. Możliwa jest poprawa i przewidywanie końcowych właściwości mechanicznych prętów HFRP poprzez mechaniczną hybrydyzację składników i ich udziałów objętościowych przed ich wyprodukowaniem. Analityczne i numeryczne rozważania oraz badania eksperymentalne wykazały tę samą tendencję w uzyskanych wynikach. W fazie przedprodukcyjnej ustalono, że dla końcowych właściwości mechanicznych wpływ konfiguracji pręta jest mniej ważny niż wpływ różnych udziałów objętościowych włókien. Ponadto założono, że preferowane położenie włókien węglowych będzie zaproponowane bliżej rdzenia prętów ze względu na problemy technologiczne. Warto wspomnieć, że różnica w uzyskanych charakterystykach wytrzymałościowych między rozważaniami analitycznymi i numerycznymi była bardzo mała, jednak uzyskane wyniki były znacznie wyższe niż wyniki uzyskane eksperymentalnie. Autorzy sugerują, że niższe wyniki uzyskane eksperymentalnie można wyjaśnić niedoskonałym rozwojem interfazy i dlatego próbowano poprawić spójność chemiczną między składnikami przez dodanie cząstek nanokrzemionki do konsystencji matrycy

A systematic study of structure and E-H bond activation chemistry by sterically encumbered germylene complexes

A series of new germylene compounds has been synthesized offering systematic variation in the σ- and π- capabilities of the α-substituent, and differing levels of reactivity towards E-H bond activation (E = H, B, C, N, Si, Ge). Chloride metathesis utilizing (terphenyl)GeCl proves to be an effective synthetic route to complexes of the type (terphenyl)Ge(ERn) [1-6: ERn = NHDipp, CH(SiMe3)2, P(SiMe3)2, Si(SiMe3)3 or B(NDippCH)2; terphenyl = C6H3Mes2-2,6 = ArMes or C6H3Dipp2-2,6 = ArDipp], while the related complex {(Me3Si)2N}Ge{B(NDippCH)2} (8) can be accessed via an amide/boryl exchange route. Metrical parameters have been probed by X-ray crystallography, and are consistent with widening angles at the metal centre as more bulky and/or more electropositive substituents are employed. Thus, the widest germylene units (θ &gt; 110o ) are found to be associated with strongly σ-donating boryl or silyl ancillary donors. HOMO-LUMO gaps for the new germylene complexes have been appraised by DFT calculations. The aryl(boryl) -germylene system ArMesGe{B(NDippCH)2} (6-Mes), which features a wide C-Ge-B angle [110.4(1)°] and (albeit relatively weak) ancillary π-acceptor capabilities, has the smallest HOMO-LUMO gap (119 kJ mol-1 ). These features result in 6-Mes being remarkably reactive, undergoing facile intramolecular C-H activation involving one of the mesityl ortho-methyl groups. The related aryl(silyl)- germylene system, ArMesGe{Si(SiMe3)3} (5-Mes) has a marginally wider HOMO-LUMO gap (134 kJ mol-1 ), rendering it less labile towards decomposition, yet reactive enough to oxidatively cleave H2 and NH3 to give the corresponding dihydride and (amido)hydride. Mixed aryl/alkyl, aryl/amido and aryl/phosphido complexes are unreactive, but amido/boryl complex 8 is competent for the activation of E-H bonds (E = H, B, Si) to give hydrido, boryl and silyl products. The results of these reactivity studies imply that the use of the very strongly σ-donating boryl or silyl substituents is an effective strategy for rendering metallylene complexes competent for E-H bond activation. </p