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International audience; Doping of transition metals within a semiconductor quantum dot (QD) has a high impact on the optical and magnetic properties of the QD. In this study, we report the synthesis of Mn 2+-doped Ag−In−Ga−Zn−S (Mn:AIGZS) QDs via thermolysis of a dithiocarbamate complex of Ag + , In 3+ , Ga 3+ , and Zn 2+ and of Mn(stearate) 2 in oleylamine. The influence of the Mn 2+ loading on the photoluminescence (PL) and magnetic properties of the dots are investigated. Mn:AIGZS QDs exhibit a diameter of ca. 2 nm, a high PL quantum yield (up to 41.3% for a 2.5% doping in Mn 2+), and robust photo-and colloidal stabilities. The optical properties of Mn:AIGZS QDs are preserved upon transfer into water using the glutathione tetramethylammonium ligand. At the same time, Mn:AIGZS QDs exhibit high relaxivity (r 1 = 0.15 mM −1 s −1 and r 2 = 0.57 mM −1 s −1 at 298 K and 2.34 T), which shows their potential applicability for bimodal PL/magnetic resonance imaging (MRI) probes.

We present results on the photothermal (PT) and heat conductive properties of nanogranular silicon (Si) films synthesized by evaporation of colloidal droplets (drop-casting) of 100 ± 50 nm-sized crystalline Si nanoparticles (NP) deposited on glass substrates. Simulations of the absorbed light intensity and photo-induced temperature distribution across the Si NP films were carried out by using the Finite difference time domain (FDTD) and finite element mesh (FEM) modeling and the obtained data were compared with the local temperatures measured by micro-Raman spectroscopy and then was used for determining the heat conductivities k in the films of various thicknesses. The cubic-to-hexagonal phase transition in Si NP films caused by laser-induced heating was found to be heavily influenced by the film thickness and heat-conductive properties of glass substrate, on which the films were deposited. The k values in drop-casted Si nanogranular films were found to be in the range of lowest k of other types of nanostructurely voided Si films due to enhanced phonon scattering across inherently voided topology, weak NP-NP and NP-substrate interface bonding within nanogranular Si films.

International audience; A single source molecular precursor synthesis of new quinary Ag-In-Ga-Zn-S (AIGZS) QDs is presented. Dithiocarbamate complexes with varied Ag/In/Ga/Zn ratios were prepared from AgNO3, In(NO3)3, Ga(NO3)3 and Zn(diethyldithiocarbamate)2. The thermal decomposition of these complexes at 220°C in oleylamine produces AIGZS QDs emitting from the visible to the near-infrared region and with photoluminescence quantum yields (PL QYs) up to 48.3%. For AIGZS QDs prepared with a (Ag + In + Ga)/Zn molar ratio of 1, intragap states likely involving Ag + ions are responsible of the PL emission and the PL lifetime could reach 278 ns. A marked increase of the PL lifetime (up to 915 ns) was observed when decreasing the (Ag + In + Ga)/Zn molar ratio to 0.5. The optical properties of AIGZS QDs could be maintained after transfer in aqueous solution. AIGZS should be of high potential for various applications due to their PL emission tunability and high PL QYs.

International audience; Chemical alterations in DNA induced by genotoxic factors can have a complex nature such as bulky DNA adducts, interstrand DNA cross-links (ICLs), and clustered DNA lesions (including double-strand breaks, DSB). Complex DNA damage (CDD) has a complex character/structure as compared to singular lesions like randomly distributed abasic sites, deaminated, alkylated, and oxidized DNA bases. CDD is thought to be critical since they are more challenging to repair than singular lesions. Although CDD naturally constitutes a relatively minor fraction of the overall DNA damage induced by free radicals, DNA cross-linking agents, and ionizing radiation, if left unrepaired, these lesions cause a number of serious consequences, such as gross chromosomal rearrangements and genome instability. If not tightly controlled, the repair of ICLs and clustered bi-stranded oxidized bases via DNA excision repair will either inhibit initial steps of repair or produce persistent chromosomal breaks and consequently be lethal for the cells. Biochemical and genetic evidences indicate that the removal of CDD requires concurrent involvement of a number of distinct DNA repair pathways including poly(ADP-ribose) polymerase (PARP)-mediated DNA strand break repair, base excision repair (BER), nucleotide incision repair (NIR), global genome and transcription coupled nucleotide excision repair (GG-NER and TC-NER, respectively), mismatch repair (MMR), homologous recombination (HR), non-homologous end joining (NHEJ), and translesion DNA synthesis (TLS) pathways. In this review, we describe the role of DNA glycosylase-mediated BER pathway in the removal of complex DNA lesions.

International audience; Background and Objective: Adulteration of dairy products by substitution of milk fat by vegetable oil is common in the Eurasian Economic Union. The objective of the paper is to investigate the potential adulteration of the fat and to test the more convenient methods of detection, i.e., determination of fatty acids or sterols profiles in commercial butter and cream. Materials and Methods: Ten samples of commercial butter and 8 samples of commercial sour cream were collected on the national market of Kazakhstan. The analyses involved the original sour cream and butter without any modification (deep-freezing) and were achieved within the shelf-life period. The fatty acid composition was analyzed by GS-FID and Sterol fractions were analyzed by GS-MS. Statistical analysis was achieved by principal components analysis (PCA), Pearson types, Kruskal-Wallis test. Results: Sixty percent of the butter samples contained traces of phytosterols and one sample contained up to 78% $-sitosterol. In sour cream samples, only three contained 100% cholesterol while two contained more than 60% sitosterol. The detection of fat adulteration by analyzing the fatty acids patterns is convenient in case of massive substitution of milk fat, but a discrete substitution does not modify the fatty acids profiles leading to misinterpretation. Conclusion: The results exhort to give preference to sterol profile determination as an official method to detect fat adulteration in dairy products. This is even more important as the current standard used in Central Asia based on some fatty acids ratios can lead to incorrect conclusions.

Cytotoxicity of fluorescent carbon fluoroxide (CFO) nanoparticles (NPs) was studied in a label-free manner on several cancer and non-cancer cell lines. A direct cytotoxic effect of the CFO NPs was clearly observed by a suppression of cell proliferation. The real-time measurement of cell activities allowed to quantify the impact of the uptaken NPs on cell proliferation and after washout of the NPs from the cell culture medium. The results show more toxic effects of the CFO NPs on cancer than on non-cancer cell lines. The notion of NPs biocompatibility must be related to a maximum concentration value of the NPs acceptable for a given cell type. Furthermore, the cytotoxicity effects of NPs should be studied not only during their direct exposure to cells but also after their washout from the culture medium., Nanoletters, 11 (12), ISSN:2079-4991

International audience; A novel sensing system was designed for pH measurements based on the enhanced and quenched photoluminescence (PL) and UV–Vis absorption of the diluted water solutions of F-, O-, and N-containing carbon nanoparticles (FON-CNPs). These FON-CNPs were solvothermally synthesized, dissolved, ultra-filtrated, and separated by thin-layer chromatography. The total fluorine content in them was found to be 1.2–1.5 mmol per gram. Their TGA showed a total weight loss of 52.7% because of the thermal decomposition and detachment of the surface groups and the partial burning of the functionalized shell on the carbon core at temperatures below 1200 °C. TEM and Raman data confirmed the presence of graphitic structures in the carbon core. From the results of ATR FTIR and UV–Vis spectroscopies, we showed that a carbon shell incorporates different functional groups covering the carbon core. The surface groups of the carbon shell include carboxyl, phenolic, and carbonyl groups. Heterocyclic N-containing and amino groups and trifluoromethyl groups supporting the hydrophobicity were also found. We suggested the possible reasons for the pH responses obtained with the sensing system considering them dependent on the de-protonation of functional groups with pH change.

Proteins from the poly(ADP-ribose) polymerase (PARP) family, such as PARP1 and PARP2, use NAD+as a substrate to catalyze the synthesis of polymeric chains consisting of ADP-ribose units covalently attached to an acceptor molecule. PARP1 and PARP2 are viewed as DNA damage sensors that, upon binding to strand breaks, poly(ADP-ribosyl)ate themselves and nuclear acceptor proteins. The flowering plantArabidopsis thalianacontains three genes encoding homologs of mammalian PARPs:atPARP1,atPARP2, andatPARP3. Both atPARP1 and atPARP2 contain poly(ADP-ribosyl)ating activity; however, it is unknown whether they could covalently modify DNA by ADP-ribosylating the strand break termini. Here, we report that similar to their mammalian counterparts, the plant atPARP1 and atPARP2 proteins ADP-ribosylate 5′-terminal phosphate residues in duplex DNA oligonucleotides and plasmid containing at least two closely spaced DNA strand breaks. AtPARP1 preferentially catalyzes covalent attachment of ADP-ribose units to the ends of recessed DNA duplexes containing 5′-phosphate, whereas atPARP2 preferentially ADP-ribosylates the nicked and gapped DNA duplexes containing the terminal 5′-phosphate. Similar to their mammalian counterparts, the plant PARP-catalyzed DNA ADP-ribosylation is particularly sensitive to the distance that separates two strand breaks in the same DNA molecule, 1.5 and 1 or 2 turns of helix for atPARP1 and atPARP2, respectively. PAR glycohydrolase (PARG) restored native DNA structure by hydrolyzing the PAR–DNA adducts generated by atPARPs. Biochemical and mass spectrometry analyses of the PAR–DNA adducts showed that atPARPs utilize phosphorylated DNA termini as an alternative to protein acceptor residues to catalyze PAR chain synthesisviaphosphodiester bond formation between C1′ of ADP-ribose and a phosphate residue of the terminal nucleotide in DNA fragment. Taken together, these data establish the presence of a new type of DNA-modifying activity inArabidopsisPARPs, suggesting a possible role of DNA ADP-ribosylation in DNA damage signaling and repair of terrestrial plants.

International audience; The transfer of POPs in food of animal origin has been studied by a meta-analysis of 28 peer-reviewed articles using transfer rate (TR) for milk and eggs and bioconcentration factors (BCF) for eligible tissues after establishing an adapted methodology. TRs of the most toxic PCDD/Fs into milk were generally elevated and even higher into eggs. BCFs in excreting adult animals varied widely between studies complicating to hierarchize tissues or congeners, even if liver and fat seemed to bioconcentrate more than lean tissues. Short time studies have clearly shown low BCFs contrarily to field studies showing the highest BCFs. The BCFs of PCDD/Fs in growing animals were higher in liver than in fat or muscle. In contrast to easily bioconcentrating hexachlorinated congeners, octa- and heptachlorinated congeners barely bioconcentrate. PCB transfer into milk and eggs was systematically high for very lipophilic congeners. Highly ortho-chlorinated PCBs were transferred >50% into milk and eggs and even >70% for congeners 123 and 167 into eggs. BCFs of the most toxic PCBs 126 and 169 were significantly higher than for less toxic congeners. BCFs seem generally low in PBDEs except congeners 47, 153 and 154. DDT and its metabolites showed high bioconcentration. Differences between tissues appeared but were masked by a study effect. In addition to some methodologic recommendations, this analysis showed the high transfer of POPs into eggs, milk and liver when animals were exposed justifying a strong monitoring in areas with POP exposure.

The group of persistent organic pollutants (POPs) are particularly dangerous for the environment and by consequence for human health because of the risk to be transmitted in the food chain. Among them, the urgent problem of obsolete and forbidden organochlorinated pesticides (OCPs) needs a rigorous management in many countries, including Kazakhstan. The aim of our study was to evaluate the effect of pesticides content in food products on the genetic status and health of the population living on the contaminated areas near destroyed warehouses for OCPs (4 villages of Talgar district and 1 control site, Almaty region). The food products sampled in Taukaraturyk (control site), and in 4 villages where non-utilized obsolete pesticides were discovered: Beskainar, Kyzylkairat, Amangeldy, and Belbulak. The contents of 24 pesticides in food products from plant (apples, pears, tomatoes, cucumbers, sweet peppers) and animal (beef meat, cow milk, honey) origin, that grown in places of localization of non-utilized OCPs, were determined, sometimes in high and unacceptably high concentrations (before 2500 times over MRL). In pears, the pesticides content (especially DDT, γ-HCH, β-HCH, endosulfan, and aldrin pesticide group), was higher than in other fruits. Among vegetables, the highest levels of all groups of pesticide were found in cucumbers. Beef meat samples demonstrated increased contents of β-HCH, γ-HCH, endrin and dieldrin. In cow milk samples only the high concentration of dieldrin was found. The content of pesticides in meat was 4–5 times higher than in milk. The medical examinations, carried out among the cohorts living around the polluted by pesticides territories and control cohort from ecologically favorable village, showed that there were more individuals with high and middle levels of somatic health in the control group than in groups exposed to OCPs. The long-term effect of the pesticide contamination of the environment on genetic status of the population was assessed by chromosomal aberration (CA) frequencies. The highest level of chromosomal aberrations was identified for the examined residents of Kyzylkairat (41%) and Belbulak (38%), a high level in Amangeldy (12%), and middle level in Beskainar (6.5%). The association between the CA frequency, health status and the pesticides contents in food were assessed by a Spearman rank correlation. The low indicators of somatic health status were strictly associated with high levels of CA, and good health status indicates that the CA rates did not exceed the spontaneous level of mutagenesis. The strongest correlation was shown between high levels of chromosomal aberrations and the content of different pesticides in pears (Cr = 0.979–0.467), tomatoes (Cr = 0.877–0.476), cucumbers (Cr = 0.975–0.553) and meat (Cr = 0.839–0.368). The obtained results highlight the need to improve health protection by increasing the public awareness to the security of the storage of obsolete OCPs in order to strengthen food safety by efficient control services.

International audience; Mare milk has been consumed for thousands of years in Central Asia and neighbouring regions. Its composition is similar to human milk, but different from cows’ milk. Fermentation with lactic acid bacteria and yeasts leads to the production of a traditional drink called qymyz. Qymyz, which is a symbol of good health, is a central part of the national cuisine and of the traditional cycle of horse husbandry, as well as playing a role in the cultural identity of Central Asian people. Mare milk, along with qymyz, has been reported to have a wide range of therapeutic effects. In this article, the authors have compiled information on mare milk composition, qymyz production and the therapeutic effects of mare milk and its products.

Germination is a process of seed sprouting that facilitates embryo growth. The breakdown of reserved starch in the endosperm into simple sugars is essential for seed germination and subsequent seedling growth. At the early stage of germination, gibberellic acid (GA) activates transcription factor GAMYB to promote de novo synthesis of isoforms of α-amylase in the aleurone layer and scutellar epithelium of the embryo. Here, we demonstrate that wheat germination is regulated by plant target of rapamycin (TOR) signaling. TOR is a central component of the essential-nutrient–dependent pathway controlling cell growth in all eukaryotes. It is known that rapamycin, a highly specific allosteric inhibitor of TOR, is effective in yeast and animal cells but ineffective in most of higher plants likely owing to structural differences in ubiquitous rapamycin receptor FKBP12. The action of rapamycin on wheat growth has not been studied. Our data show that rapamycin inhibits germination of wheat seeds and of their isolated embryos in a dose-dependent manner. The involvement of Triticum aestivum TOR (TaTOR) in wheat germination was consistent with the suppression of wheat embryo growth by specific inhibitors of the TOR kinase: pp242 or torin1. Rapamycin or torin1 interfered with GA function in germination because of a potent inhibitory effect on α-amylase and GAMYB gene expression. The TOR inhibitors selectively targeted the GA-dependent gene expression, whereas expression of the abscisic acid-dependent ABI5 gene was not affected by either rapamycin or torin1. To determine whether the TaTOR kinase activation takes place during wheat germination, we examined phosphorylation of a ribosomal protein, T. aestivum S6 kinase 1 (TaS6K1; a substrate of TOR). The phosphorylation of serine 467 (S467) in a hydrophobic motif on TaS6K1 was induced in a process of germination triggered by GA. Moreover, the germination-induced phosphorylation of TaS6K1 on S467 was dependent on TaTOR and was inhibited by rapamycin or torin1. Besides, a gibberellin biosynthesis inhibitor (paclobutrazol; PBZ) blocked not only α-amylase gene expression but also TaS6K1 phosphorylation in wheat embryos. Thus, a hormonal action of GA turns on the synthesis of α-amylase in wheat germination via activation of the TaTOR–S6K1 signaling pathway.

International audience; Self-organized Titanium dioxide (TiO2) nanotubes grown on Ti grid acting as anode for Li-ion microbatteries were prepared via an electrochemical anodization. By tuning the anodization time, the morphology and length of the nanotubes were investigated by scanning electron microscope. When the anodization time reached 1.5 h, the TiO2nts/Ti grid anode showed a well-defined nanotubes, which are stable, well-adherent ~90 nm with a length of 1.9 ± 0.1 μm. Due to their high surface utilization, surface area, and material loading per unit area, TiO2nts/Ti grid anode using polymer electrolyte exhibited a high areal capacity of 376 μAh cm−2 at C/10 rate and a stable discharge plateau at 1.8 V without using a polymer binder and conductive additive. The storage capacity of the TiO2nts/Ti grid after 10 cycles is 15 times higher compared to previous reports using planar Ti foils.

Mn-Doped quantum dots (QDs) are of high interest for numerous applications like solar cells, optoelectronics, optosensing, or bioimaging. Here, we report the preparation of quaternary (AgInS2)x(MnS)y(ZnS)1−x−y QDs, thereafter noted Mn : AIZS via a thermally induced decomposition of Ag, In, Zn and Mn precursors in the presence of oleylamine and dodecanethiol. The Mn : AIZS QDs have an average diameter of 3.5 nm and their XRD patterns can be indexed with the orthorhombic phase of AgInS2. The incorporation of Mn2+ ions in the AIZS crystal lattice results in a red-shift of the photoluminescence (PL) emission maximum depending on the Mn2+ content. The PL quantum yields decrease upon loading with Mn2+ but remained high (53–31%) until 50% theoretical loading in Mn2+. Steady state, PL excitation and time-resolved PL measurements suggest that Mn2+-dependent trap states are involved in the PL emission. Mn : AIZS QDs exhibit also magnetic properties. In addition, Mn : AIZS QDs can easily be transferred to the aqueous phase using the PMAO amphiphilic polymer without alteration of their optical properties (PL quantum yield up to 51%), revealing their high potential for biological applications.

International audience; In this paper, the electrochemical reduction of indium on a glassy carbon electrode (GCE) in a chloride electrolyte in the presence of tetrabutylammonium chloride (TBACh) was studied using the rotating disk electrode method, chronoamperometry and scanning electron microscopy. It was found that the addition of TBACh inhibits the electroreduction of indium by increasing the activation energy of the process by 17 kJ mol-1 , and also shows leveling action at its low concentrations. The diffusion coefficient of indium (III) ions found from Levich equation at 25°C, was 4.93× 10-6 cm 2 s-1. The In 3+ diffusion coefficient determined using the Levich equation are consistent with the values determined by the Cottrell law and universal Stokes-Einstein equation. The addition of 10-4 M TBACh to the electrolyte reduces the diffusion coefficient to 2.13× 10-6 cm 2 s-1. Manuscript_9f996fd397815e746fb670bc4bfea5eb 2 The type of crystallization corresponding to the progressive 3D nucleation with diffusion control has been established. Using the Scharifker-Hills, Scharifker-Mostany and Mirkin-Nilov-Heerman-Tarallo models nucleation parameters were calculated, which correlate well with the results of scanning electron microscopy. Addition of TBACh increases the nucleation rate at-0.90 V from 9.19× 10 6 cm-2 s-1 to 48.09× 10 6 cm-2 s-1 and reduces the average radius of grains of indium coatings from 18.0 μm to 6.8 μm.

International audience; Chlordecone (Kepone) (CLD) is a highly persistent pesticide formerly used in the French West Indies. High levels of this pesticide are still found in soils and represent a subsequent source of contamination for outdoor-reared animals which may ingest involuntary non negligible amounts of soil. In that context, sequestering matrices like activated carbons (ACs) may be used to efficiently decrease the bioavailability of such organic pollutants. The present study intends to assess the respective efficiency of two sequestering strategies where two different ACs were provided either via feed incorporation or via soil amendment. This study involved 20 piglets randomly distributed into 5 experimental groups (4 replicates). All groups were exposed to 10 mu g of CLD per kg of BW per day during 10 days via a contaminated soil. In both "Soil-ACs" treatment groups, the contaminated soil was amended by 2% (mass basis) of one of the two ACs. The two "Feed-ACs" groups received the contaminated soil and one dough ball containing 0.5% (mass basis) of one of the ACs. The piglets were then euthanized before collection of pericaudal adipose tissue and the whole liver and CLD analysis. A significant decrease of CLD concentrations in liver and adipose tissue was observed only in the "Soil-ACs" groups in comparison with the control group (P < 0.001). This decrease was particularly important for the coconut shell activated carbon where relative bioavailability was found lower than 1.8% for both tissues.

Hydrogen generation rate is one of the most important parameters which must be considered for the development of engineering solutions in the field of hydrogen energy applications. In this paper, the kinetics of hydrogen generation from oxidation of hydrogenated porous silicon nanopowders in water are analyzed in detail. The splitting of the Si-H bonds of the nanopowders and water molecules during the oxidation reaction results in powerful hydrogen generation. The described technology is shown to be perfectly tunable and allows us to manage the kinetics by: (i) varying size distribution and porosity of silicon nanoparticles, (ii) chemical composition of oxidizing solutions, (iii) ambient temperature. In particular, hydrogen release below 0 &deg, C is one of the significant advantages of such a technological way of performing hydrogen generation.

International audience; We report the electrodeposition of polymer electrolyte (PMMA-PEG) in porous lithium nickel manganese oxide (LiNi0.5Mn1.5O4) cathode layer by cyclic voltammetry. The cathode-electrolyte interface of the polymer-coated LNMO electrode has been characterized by scanning electron microscopy and electrochemical techniques. Electrochemical measurements consisting of galvanostatic cycling tests and electrochemical impedance spectroscopy revealed a significant improvement of the capacity values and the increase of the operating voltage. These effects are attributed to the total filling of pores by the electrodeposited polymer that contributes to improve the reversible insertion of Li+. A complete all-solid-state microbattery consisting of electropolymerized LNMO as the cathode, a thin polymer layer as the electrolyte, and TiO2 nanotubes as the anode has been successfully fabricated and tested.

International audience; This work describes the performance of poly(ethylene-co-vinyl acetate) (EVA) copolymer and modified poly(ethylene-co-vinyl acetate) (EVA-M) as pour point reducer. Commercially available EVA copolymer modified with sodium hydroxide in methanol. Partially hydrolyzed EVA was obtained and Fourier Transform InfraRed (FTIR) analysis of the modified EVA was recorded. The modified and unmodified EVA was used to crude oil of South Turgai, Kazakhstan, in order to improve the flowability of the crude oil. According to the rheological behavior of oils in the South Turgai, the findings showed that modified EVA lowered the dynamic viscosity greater compared to unmodified EVA and heat treatment. Dynamic viscosities and yield points of different oils with various temperatures with using EVA and EVA-M were studied systematically. Finally microphotograph of crystal structures two oils with using EVA and EVA-M, under same conditions, were compared and discussed.

International audience; Oxidatively generated guanine radical cations in DNA can undergo various nucleophilic reactions including the formation of C8-guanine cross-links with adjacent or nearby N3-thymines in DNA in the presence of O$_2$. The G*[C8-N3]T* lesions have been identified in the DNA of human cells exposed to oxidative stress, and are most likely genotoxic if not removed by cellular defense mechanisms. It has been shown that the G*[C8-N3]T* lesions are substrates of nucleotide excision repair in human cell extracts. Cleavage at the sites of the lesions was also observed but not further investigated (Ding et al. (2012) $Nucleic$ $Acids$ $Res.$ 40, 2506-2517). Using a panel of eukaryotic and prokaryotic bifunctional DNA glycosylases/lyases (NEIL1, Nei, Fpg, Nth, and NTH1) and apurinic/apyrimidinic (AP) endonucleases (Apn1, APE1, and Nfo), the analysis of cleavage fragments by PAGE and MALDI-TOF/MS show that the G*[C8-N3]T* lesions in 17-mer duplexes are incised on either side of G*, that none of the recovered cleavage fragments contain G*, and that T* is converted to a normal T in the 3'-fragment cleavage products. The abilities of the DNA glycosylases to incise the DNA strand adjacent to G*, while this base is initially cross-linked with T*, is a surprising observation and an indication of the versatility of these base excision repair proteins.

Apurinic/apyrimidinic (AP) endonucleases are key enzymes involved in the repair of abasic sites and DNA strand breaks. Pathogenic bacteria Mycobacterium tuberculosis contains two AP endonucleases: MtbXthA and MtbNfo members of the exonuclease III and endonuclease IV families, which are exemplified by Escherichia coli Xth and Nfo, respectively. It has been shown that both MtbXthA and MtbNfo contain AP endonuclease and 3'→5' exonuclease activities. However, it remains unclear whether these enzymes hold 3'-repair phosphodiesterase and nucleotide incision repair (NIR) activities. Here, we report that both mycobacterial enzymes have 3'-repair phosphodiesterase and 3'-phosphatase, and MtbNfo contains in addition a very weak NIR activity. Interestingly, depending on pH, both enzymes require different concentrations of divalent cations: 0.5mM MnCl2 at pH 7.6 and 10 mM at pH 6.5. MtbXthA requires a low ionic strength and 37 °C, while MtbNfo requires high ionic strength (200 mM KCl) and has a temperature optimum at 60 °C. Point mutation analysis showed that D180 and N182 in MtbXthA and H206 and E129 in MtbNfo are critical for enzymes activities. The steady-state kinetic parameters indicate that MtbXthA removes 3'-blocking sugar-phosphate and 3'-phosphate moieties at DNA strand breaks with an extremely high efficiency (kcat/KM=440 and 1280 μM(-1)∙min(-1), respectively), while MtbNfo exhibits much lower 3'-repair activities (kcat/KM=0.26 and 0.65 μM(-1)∙min(-1), respectively). Surprisingly, both MtbXthA and MtbNfo exhibited very weak AP site cleavage activities, with kinetic parameters 100- and 300-fold lower, respectively, as compared with the results reported previously. Expression of MtbXthA and MtbNfo reduced the sensitivity of AP endonuclease-deficient E. coli xth nfo strain to methylmethanesulfonate and H2O2 to various degrees. Taken together, these data establish the DNA substrate specificity of M. tuberculosis AP endonucleases and suggest their possible role in the repair of oxidative DNA damage generated by endogenous and host- imposed factors.

The generative potential, depositional environment and thermal maturity of organic-rich rocks from the eastern part of Precaspian and Pre-Uralian Basins (Kazakhstan) were determined by Rock–Eval and molecular analyses. Source rocks of the Precaspian and Pre-Uralian Basins were deposited in a marine environment. Late Carboniferous deposits from the slope located west of the Janajol Platform and the Pre-Uralian Basin contain Type II algal kerogen in limestones. Early and Mid-Visean and Early Permian turbidites contain Type III kerogen composed of terrestrial plants transported and deposited by turbidity currents, or a mixture of Types II and III kerogens. Source rocks from the Carboniferous and most of the Early Permian were deposited in a reducing environment, favouring organic matter preservation; however, the continental influence increases towards the eastern areas in the Pre-Uralian Basin and the Suture zone. The onset of the oil window occurs at a depth of 3200–4000 m. In Early Permian rocks, thermal maturity increases from the west in the Precaspian Basin to the east in the Pre-Uralian Basin and the Suture zone under the Urals Nappe. The Carboniferous rocks in the Precaspian Basin are of lower thermal maturity than the Early Permian rocks of the Pre-Uralian Basin. A multivariate statistical principal components analysis (PCA) using source dependent biomarker parameters suggests that Visean oil correlates with Visean source rocks from the west, the Late Carboniferous oil from the Janajol Platform correlates with Late Carboniferous source rocks from the Pre-Uralian Basin, and the Early Permian oil in the Precaspian is probably a mixture of oil from Early Permian and deeper Early and Late Carboniferous source rocks. Oil from a suprasaliferous reservoir (Late Permian) is close in composition to the Early Permian oil. Models of palaeotemperatures and genesis of hydrocarbons in two sections are consistent with the migration of oil and gas from greater depth and from the suture zone under the thrust of Urals to the west.