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The first enantioselective [12 + 2] cycloaddition has been developed for the construction of a chiral cycl[3.2.2]azine core, a tricyclic moiety with a central ring-junction nitrogen atom, by an operationally simple one-step organocatalytic process. The reaction concept builds upon aminocatalytically generated 12π-components derived from 5H-benzo[a]pyrrolizine-3-carbaldehydes reacting with different electron-deficient 2π-components and affording the complex scaffold of benzo[a]cycl[3.2.2]azine (indolizino[3,4,5-ab]isoindole) with excellent enantio- A nd diastereoselectivity in good yields. The developed reaction is robust toward diverse substituent patterns and has been extended to different classes of electron-deficient 2π-components by minor variations in reaction setup. The obtained [12 + 2] cycloadducts are electron-deficient in nature, and their reaction with nucleophiles have been demonstrated. The enantioselective [12 + 2] cycloaddition with α,β-unsaturated aldehydes as the electron-deficient 2π-components relies upon an unconventional, simple aminocatalyst. In order to understand the high stereoselectivity of the [12 + 2] cycloaddition for this simple catalyst, combined experimental and computational investigations were performed. The investigations point to activation of both the 5H-benzo[a]pyrrolizine-3-carbaldehyde and the α,β-unsaturated aldehyde by the aminocatalyst and that the reaction proceeds by a stepwise cycloaddition, where especially the ring-closure is crucial for the stereochemical outcome. For other electron-deficient 2π-components, such as α,β-unsaturated ketoesters and nitroolefins, a more sterically demanding aminocatalyst has been applied and the corresponding [12 + 2] cycloadducts are obtained with excellent stereoselectivity. The [12 + 2] cycloaddition with vinyl sulfones afforded fully unsaturated systems, which display photoluminescence properties and for which quantum yields have been evaluated.

The interaction of V(IV) and V(V) with succinic acid was investigated by affinity capillary electrophore- sis (ACE) in aqueous acid solutions at pH values 1.5, 2.0 and 2.4, and different ligand concentra- tions. V(IV) and V(V) form protonated complexes with succinic acid ligand at this pH range. The loga- rithms of the stability constants, measured at 0.1 mol L-1 (NaClO4 /HClO4) ionic strength and 25 °C, are logβ111 =7.4 ± 0.2 and logβ122 =14.1 ± 0.5 for V(IV), and logβ111=7.3 ± 0.1 for V(V), respectively. The stability constant values, extrapolated to zero ionic strength with the Davies equation, are logβ°111=8.3 ± 0.2 and logβ°122 =15.6 ± 0.5 for V(IV) and logβ°111 =7.9 ± 0.1 for V(V). The application of ACE to the simultaneous equilibria of V(IV) and V(V) (injection of two analytes) was also attempted. When the results were compared with those obtained when introducing only one analyte in the capillary, using the traditional version of the method, similar stability constants and precision are obtained. The possibility of studying two analytes simultaneously decreases the time needed for the determination of the constants ; this feature is especially valuable when working with hazardous materials or when only small quantities of ligand are available.

Both military and civilian vehicles are prone to fire, with severe potential consequences in terms of material and life losses. Vehicles generally contain highly combustible and flammable materials, such as gasoline, lubricants, oil, electronic devices, rubber, plastics, and so on. At the same time, fire ignition sources are present in vehicles in electronic devices, friction, heat, etc. Fire ignition can also be caused by external sources, especially in military applications (aggression on the vehicle). Thus, appropriate measures and fire-fighting systems should be implemented to mitigate the risk of fire in military and civilian vehicles to ensure passenger safety and preserve the vehicles' mobility. Halon was previously commonly used as a fire-fighting agent in military and civilian vehicles but is currently phased out due to environmental issues. In this context, this paper aims to review the research advances and progress over the last 50 years in fire-fighting systems and agents employed in both civilian and military vehicles for land, sea, and air applications.

The abundance and distribution of dissolved Re (DRe) were determined in the freshwater part of the Krka River (Croatia), which drains a karst landscape, and in the salinity gradient of its highly stratified estuary. Due to the low DRe concentration, a batch procedure consisting of a pre-concentration step using an anion exchange resin (Dowex) and analysis of DRe in 8 M HNO3 eluate using high-resolution inductively coupled plasma mass spectrometry (HR ICP-MS) was applied. Due to potentially inconsistent recoveries, which ranged from 60 to 87%, quantification was performed using the isotope dilution technique (ID). DRe concentrations in the Krka River increased downstream, from 6.2 pM at the spring site to 11.9 pM upstream of the estuary region. Weathering of the surrounding carbonate lithology is assumed to be the source of the natural Re. Two specific anomalies were registered: a strong increase in DRe concentration due to anthropogenic input near the town of Knin (27.5 pM) and a decrease at a downstream site caused by subsurface input of freshwater from the Zrmanja River, resulting in a relatively low DRe concentration (8.5 pM). In the estuarine region, a near- conservative behavior of DRe was found in the salinity gradient of the upper surface layer, with DRe concentrations ranging from 18 to 38 pM. Anthropogenic input was suspected within the estuarine segment near the urban area, causing a small positive deviation from the conservative line. In the bottom seawater layer, a minor decrease in DRe concentration in the most upstream estuarine regions was apparent, implying weak scavenging of Re

Edoxaban is used for venous thromboembolism (VTE) treatment. Real-life data are lacking about its use in long-term therapy. We aimed to assess the efficacy and the safety of edoxaban for long-term VTE treatment in a real-life setting. Patients with VTE included in the Registro Informatizado Enfermedad TromboEmbólica (RIETE) registry, receiving edoxaban 60 or 30 mg daily were prospectively followed up to validate the benefit of using different dosages. The main outcome was the composite of VTE recurrences or major bleeding in patients with or without criteria for dose reduction. Multivariable analysis to identify predictors for the composite outcome was performed. From October 2015 to November 2019, 562 patients received edoxaban for long-term therapy. Most (94%) of the 416 patients not meeting criteria for dose reduction received 60 mg daily, and 92 patients meeting criteria (63%) received 30 mg daily. During treatment, two patients developed recurrent VTE, six had major bleeding and nine died (2 from fatal bleeding). Among patients not meeting criteria for dose reduction, those receiving 30 mg daily had a higher rate of the composite event (hazard ratio (HR) 8.37; 95% confidence interval (CI) 1.12–42.4) and a significant higher mortality rate (HR 31.1; 95% CI 4.63–262) than those receiving 60 mg. Among patients meeting criteria for dose reduction, those receiving 60 mg daily had no events, and a nonsignificantly higher mortality rate (HR 5.04; 95% CI 0.54–133) than those receiving 30 mg daily. In conclusion, edoxaban seems to be effective and safe for long-term VTE treatment in real life. Criteria for dose reduction should be reformulated., No funding was received for this work

Aim: To investigate the feasibility of producing biogas from anaerobic co-digestion of cotton yarn wastes (CY) and human urine (HU) using fresh cow dung as the inoculum. Study Design: Anaerobic co-digestion of CY waste and HU and CY waste alone were done using batch reactors. Place and Duration of Study: CY were collected from Rivatex Eastern Africa Limited, Eldoret, Kenya while fresh cow manure used as inoculum was collected from a farm at Moi University, Eldoret, Kenya. Human urine sample was collected in a clean sterile container at Moi University hostel, Eldoret, Kenya. The experimental set up and analyses were performed at Chemical and Process Engineering Laboratory, Moi University, Kenya between January 2020 and May 2020. Methodology: CY, HU and fresh cow dung were subjected to physicochemical analysis. Batch anaerobic co-digestion of CY and HU, and CY alone were carried out under ambient temperature (25 ± 3 ) conditions for 95 days and 37 days, respectively. Results: The CY contained 90.46% total solids, 77.12% volatile solids and 9.54% moisture content while the corresponding values for HU were 2.9%, 58.5% and 97.1%, respectively. CY had a high carbon to nitrogen ratio. The biogas yield from anaerobic co-digestion was 35.6% more than digestion of CY alone. The highest daily biogas production for co-digestion and digestion of CY alone were 330 mL and 386 mL on day 12 and 21, respectively. The total biogas yield when CY co-digested for 95 days was 10,125 mL which decreased to 6,519 mL without co-digestion after 37 days. Conclusion: Our results showed that co-digestion produced more biogas than digestion of CY alone. Conclusively, the presence of HU during anaerobic digestion of CY enhanced the biogas production by more than 35.6% demonstrating that HU could be an effective waste for co-digestion of solid wastes such as CY. Further research should focus on monitoring parameters like temperature, buffering capacity and fatty acid levels to ensure optimal efficiency and maximum biogas yield.

Direct (hetero)arylation polymerization (DHAP) shows great promise for simple, cheap, and environmentally benign preparation of conjugated polymers, but seems to involve a lack of selectivity when different aromatic C–H bonds are present. We report that some time-controlled DHAP reactions can yield well-defined and processable semiconducting polymers. Following these procedures, various aromatic compounds have been efficiently polymerized, including 2,7-dibromofluorene, 2,7-dibromocarbazole, 1,4-dibromobenzene, bithiophene, dithienyl-benzothiadiazole, and diketopyrrolopyrrole derivatives. All resulting polymers have shown comparable, if not slightly better, properties than their Stille- and Suzuki-synthesized analogs. These findings (re)open the door for the low-cost production of many conjugated polymers for plastic electronics.

Combined chromatographic and spectral analysis was used to analyse V redox conversion in the aqueous solution in the presence of several biologicaly and environmentally important thiols: L-cysteine, thioacetic acid and ethanethiol. The L-cysteine proved to be most powerful reducens of V(V), followed with thioacetic acid and ethanethiol.

The reduction of vanadate (+V) in the presence of 3-mercaptopropionic acid was studied using a chromatographic method for the determination of vanadate (+V) versus vanadyl (+IV) species. Ion chromatography was combined with spectrophotometric investigation of the absorption properties of the solution. The chromatographic method for the separation of vanadate (+V) and vanadyl (+IV) was carried out with an anion exchange column. In the initial reaction mixture containing vanadate (+V) and 3-mercaptopropionic acid, ethylenediaminetetraacetic acid – EDTA was added in an excessive amount relative to the concentration of reactants in the solution. After the ligand exchange reaction, the added EDTA terminates the reduction, allowing redox speciation in the solutions. A strong pH dependence of the reduction rates in the investigated solution was observed. The vanadate reduction seems to proceed in 2 steps: 1) formation of the intermediate vanadate (+V)- thioester ; 2) reduction reaction and formation of the vanadyl (+IV)-thiol complex. The obtained results strongly suggest that the reaction of vanadate (+V)-thioester formation is proton catalyzed. It was observed that the overall reduction rates are pH dependent due to the complex vanadate (+V) solution speciation and changes in the ionic form of 3-mercaptopropionic acid.

An efficient and exceptionally stereoselective synthesis of chiral cycl[3.2.2]azines has been realized by means of the rational design and utilization of novel (E)-3-benzylidene-3H-pyrrolizines in iminium-ion-catalyzed [8+2] cycloaddition reactions. The presented protocol allows for the incorporation of diverse enals, including cinnamaldehydes, enolizable aldehydes, and substrates of extended conjugation. The obtained products contain both an electron-rich alkenyl pyrrole moiety and an electron-deficient carbaldehyde substituent, and both moieties can undergo selective transformations with retention of the stereochemical information established in the [8+2] cycloaddition.

Diketopyrrolopyrrole-based (DPP-based) polymers are a very important class of materials for both organic solar cells (OSCs) and organic field-effect transistors (OFETs). Here we report an optimised synthesis of fluorinated dithienyl-diketopyrrolopyrrole (fDT-DPP) and three new highly fluorinated fDT-DPP-based materials obtained from direct heteroarylation polymerization (DHAP). This study confirms the properties of the fluorine atom in a polymer, activation of the α-position hydrogen on thiophene moieties, decreasing HOMO and LUMO energy, lower bandgaps and modification of the solubility and morphology of the materials.

BACKGROUND The effects of a dietary supplementation with the vegetable omega-3 α-linolenic acid (ALA) on cardiovascular homeostasis are unclear. In this context, it would be interesting to assess the effects of camelina oil. OBJECTIVE This study aimed to assess the cardiovascular and metabolic effects of camelina oil in hypertensive patients with metabolic syndrome. METHODS In a double-blind placebo-controlled randomized study, treated essential hypertensive patients with metabolic syndrome received during 6 months either cyclodextrin-complexed camelina oil containing ≈ 1.5 g ALA/day (n = 40), or an isocaloric placebo (n = 41), consisting in the same quantity of cyclodextrins and wheat starch. Anthropometric data, plasma lipids, glycemia, insulinemia, creatininemia, thiobarbituric acid reactive substances, high-sensitivity C-reactive protein, and n-3, n-6 and n-9 fatty acids in erythrocyte membranes were measured. Peripheral and central blood pressures, arterial stiffness, carotid intima-media thickness and brachial artery endothelium-dependent flow-mediated dilatation and endothelium-independent dilatation were assessed. RESULTS Compared to placebo, camelina oil increased ALA (mean ± SD: 0 ± 0.04 vs. 0.08 ± 0.06%, P

Biological lignin valorization has emerged as a major solution for sustainable and cost-effective biorefineries. However, current biorefineries yield lignin with inadequate fractionation for bioconversion, yet substantial changes of these biorefinery designs to focus on lignin could jeopardize carbohydrate efficiency and increase capital costs. We resolve the dilemma by designing ‘plug-in processes of lignin’ with the integration of leading pretreatment technologies. Substantial improvement of lignin bioconversion and synergistic enhancement of carbohydrate processing are achieved by solubilizing lignin via lowering molecular weight and increasing hydrophilic groups, addressing the dilemma of lignin- or carbohydrate-first scenarios. The plug-in processes of lignin could enable minimum polyhydroxyalkanoate selling price at as low as $6.18/kg. The results highlight the potential to achieve commercial production of polyhydroxyalkanoates as a co-product of cellulosic ethanol. Here, we show that the plug-in processes of lignin could transform biorefinery design toward sustainability by promoting carbon efficiency and optimizing the total capital cost., The current biorefineries yield lignin with inadequate fractionation for bioconversion, yet substantial changes of these biorefinery designs could jeopardize carbohydrate efficiency and increase capital costs. Here the authors resolve the dilemma by designing ‘plug-in processes of lignin’ to enable economic waste valorization.

The concentration and isotopic composition of uranium (δ238U, 234U/238U activity ratio) in combination with traditional isotopes (δ18O, δ13C) were examined as potential tracers of authigenic carbonate formation in a karst aquifer. The U concentration and 234U/238U activity ratios in the tufa-precipitating sections of two connected karst rivers (Krka and Zrmanja, Croatia) decreased downstream in water and in precipitated carbonate due to active self-purification processes, i.e. adsorption of isotopically lighter U(VI) on mineral particles, sedimentation and co-precipitation with carbonate. The isotopic composition of carbonate in tufa mostly resembled the 234U/238U activity ratio and the δ238U values of dissolved U in water but was also affected by the presence of detrital carbonate flushed into the river from soil and weathered bedrock. This interpretation was supported by the δ18O and δ13C values of tufa, which were shifted out of equilibrium with river water and dissolved in organic carbon and in their isotopic signature, which showed the presence of lithic carbonate. Large fluctuations of the δ238U values of water, leachable U (eluted in acetic acid buffered with Na-acetate) and residual U fraction could not be fully explained by available data due to the overlapping U isotopic signatures of leachable (mainly carbonate) and residual fractions of soil, bedrock and tufa. Therefore, a long-term, systematic, seasonal and event-based observation of the isotopic composition of dissolved and suspended particulate U in water is necessary. Nevertheless, the U isotopes were found to have the potential to be used as identifiers of authigenic carbonate and the storage of CO2 in terrestrial river sediments, to improve knowledge on fluxes within local and global biogeochemical carbon cycle.

The conclusions of the European Food Safety Authority (EFSA) following the peer review of the initial risk assessments carried out by the competent authorities of the rapporteur Member State, the Netherlands and co‐rapporteur Member State, Greece, for the pesticide active substance potassium hydrogen carbonate and the considerations as regards the inclusion of the substance in Annex IV of Regulation (EC) No 396/2005 are reported. The context of the peer review was that required by Commission Implementing Regulation (EU) No 844/2012, as amended by Commission Implementing Regulation (EU) No 2018/1659. The conclusions were reached on the basis of the evaluation of the representative uses of potassium hydrogen carbonate as a fungicide on strawberry, wine and table grapes, pome fruits, stone fruits, ornamentals and cucurbits. The reliable end points, appropriate for use in regulatory risk assessment, are presented. Missing information identified as being required by the regulatory framework is listed. Concerns are not identified.

The abundance and distribution of dissolved Re (DRe) has been determined in the freshwater part of the Krka River (Croatia), draining the karstic carbonate landscape, as well as in the salinity gradient of its highly stratified estuary. Due to low DRe concentration, the batch procedure consisting of pre-concentration step using an anion exchange resin (Dovex) and analysis of DRe in 8 M HNO 3 eluate using a high resolution inductively coupled plasma mass spectrometry (HR ICP-MS) was adopted. Due to the potential inconsistent recoveries, ranging from 60% to 87%, the quantification was performed by using the isotope dilution (ID) technique. The DRe concentration in the Krka River basically increased in the downstream direction, with the 6.2 pM at the spring site, reaching 11.9 pM before the estuarine region. The weathering of the surrounding carbonate lithology is assumed as the source of natural Re. The two specific anomalies were registered: a strong increase in DRe concentration due to the anthropogenic input near the town of Knin (27.5 pM) and a decrease at downstream site caused by the subterranean input of freshwater of the Zrmanja River leading to relatively low DRe concentration (8.5 pM). In the estuarine segment, a near-conservative behavior of DRe was found in the salinity gradient of the upper surface layer, with the DRe concentration ranging from 18 to 38 pM. An anthropogenic supply was suggested within the estuarine segment close to the urban area causing a small positive deviation from the conservative line. In the bottom seawater layer, a minor decrease of DRe concentration in the most upstream estuarine regions was evidenced, implying a potential weak scavenging of Re.

Previous studies have shown that Mannheimia haemolytica A2 is the principal microorganism causing pneumonic mannheimiosis, a major bacterial respiratory disease among sheep and goats. The effect of this bacteria on the respiratory system is well-established. However, its effect on the reproductive physiology remains unclear. Therefore, this study aimed to determine the alterations in the level of pro-inflammatory cytokines and testosterone hormone post-inoculation with M. haemolytica serotype A2 and its lipopolysaccharide (LPS) endotoxin which were hypothesized to affect the reproductive functions of bucks. Twelve clinically healthy adult male goats were divided equally into three groups. Goats in group 1 were treated with 2 ml of sterile phosphate-buffered saline (PBS) pH 7.0 intranasally (negative control), group 2 with 2 ml of 109 colony-forming unit (CFU) of M. haemolytica serotype A2 intranasally (positive control), and group 3 were treated with 2 ml of lipopolysaccharide extracted from 109 CFU of M. haemolytica serotype A2 intravenously. Following inoculation, blood samples were collected via jugular venipuncture into plain tubes at pre-determined intervals for serum collection to determine the concentration of interleukin (IL)-1β, IL6, tumor necrosis factor (TNF)-α, and testosterone hormone by using commercial ELISA test kits. Results from this study demonstrated that the inoculation of M. haemolytica A2 and its LPS increases the concentration of pro-inflammatory cytokines but decreases the concentration of testosterone hormone in challenged animals at most time points throughout the 56 days experimental period (p < 0.05). This study suggests that the M. haemolytica A2 and its LPS could alter the concentration of pro-inflammatory cytokines and testosterone hormone, which in turn, may negatively affect the reproductive functions of bucks.

The conclusions of EFSA following the peer review of the initial risk assessments carried out by the competent authorities of the rapporteur Member State Spain and co‐rapporteur Member State Hungary for the pesticide active substance calcium carbonate are reported. The context of the peer review was that required by Commission Implementing Regulation (EU) No 844/2012, as amended by Commission Implementing Regulation (EU) No 2018/1659. The conclusions were reached on the basis of the evaluation of the representative uses of calcium carbonate as a repellent on deciduous and coniferous trees in forestry. The reliable end points, appropriate for use in regulatory risk assessment, are presented. Missing information identified as being required by the regulatory framework is listed. No concerns were identified.

Background: In a 2013 survey, we reported distinct discrepancies in delivery of tuberculosis (TB) and HIV services in eastern Europe (EE) vs. western Europe (WE). Objectives: To verify the differences in TB and HIV services in EE vs. WE. Methods: Twenty-three sites completed a survey in 2018 (EE, 14; WE, nine; 88% response rate). Results were compared across as well as within the two regions. When possible, results were compared with the 2013 survey. Results: Delivery of healthcare was significantly less integrated in EE: provision of TB and HIV services at one site (36% in EE vs. 89% in WE; P = 0.034), and continued TB follow-up in one location (42% vs. 100%; P = 0.007). Although access to TB diagnostics, standard TB and HIV drugs was generally good, fewer sites in EE reported unlimited access to rifabutin/multi-drug-resistant TB (MDR-TB) drugs, HIV integrase inhibitors and opioid substitution therapy (OST). Compared with 2013, routine usage of GeneXpert was more common in EE in 2018 (54% vs. 92%; P = 0.073), as was access to moxifloxacin (46% vs. 91%; P = 0.033), linezolid (31% vs. 64%; P = 0.217), and bedaquiline (0% vs. 25%; P = 0.217). Integration of TB and HIV services (46% vs. 39%; P = 1.000) and provision of OST to patients with opioid dependency (54% vs. 46%; P = 0.695) remained unchanged. Conclusion: Delivery of TB and HIV healthcare, including integration of TB and HIV care and access to MDR-TB drugs, still differs between WE and EE, as well as between individual EE sites.

Background Similar to biofuels, numerous chemicals produced from petroleum resources can also be made from biomass. In this research we investigate cradle to biorefinery exit gate life cycle impacts of producing acetic acid from poplar biomass using a bioconversion process. A key step in developing acetic acid for commercial markets is producing a product with 99.8% purity. This process has been shown to be potentially energy intensive and in this work two distillation and liquid–liquid extraction methods are evaluated to produce glacial bio-acetic acid. Method one uses ethyl acetate for extraction. Method two uses alamine and diisobutyl ketone. Additionally two different options for meeting energy demands at the biorefinery are modeled. Option one involves burning lignin and natural gas onsite to meet heat/steam and electricity demands. Option two uses only natural gas onsite to meet heat/steam demands, purchases electricity from the grid to meet biorefinery needs, and sells lignin from the poplar biomass as a co-product to a coal burning power plant to be co-fired with coal. System expansion is used to account for by-products and co-products for the main life cycle assessment. Allocation assessments are also performed to compare the life cycle tradeoffs of using system expansion, mass allocation, or economic allocation for bio-acetic acid production. Finally, a sensitivity analysis is conducted to determine potential effects of a decrease in the fermentation of glucose to acetic acid. Results Global warming potential (GWP) and fossil fuel use (FFU) for ethyl acetate extraction range from 1000–2500 kg CO2 eq. and 32–56 GJ per tonne of acetic acid, respectively. Alamine and diisobutyl ketone extraction method GWP and FFU ranges from −370–180 kg CO2 eq. and 15−25 GJ per tonne of acetic acid, respectively. Conclusions Overall the alamine/diisobutyl ketone extraction method results in lower GWP and FFU values compared to the ethyl acetate extraction method. Only the alamine/diisobutyl extraction method finds GWP and FFU values lower than those of petroleum based acetic acid. For both extraction methods, exporting lignin as a co-product produced larger GWPs and FFU values compared to burning the lignin at the biorefinery.

The conclusions of EFSA following the peer review of the initial risk assessments carried out by the competent authorities of the rapporteur Member State Austria and co‐rapporteur Member State Italy for the pesticide active substance captan are reported and the confirmatory data following the Article 12 of Regulation (EC) No 396/2005 as well. The context of the peer review was that required by Commission Implementing Regulation (EU) No 844/2012, as amended by Commission Implementing Regulation (EU) No 2018/1659. The conclusions were reached on the basis of the evaluation of the representative uses of captan as a fungicide on pome fruit, peaches and nectarines, plums, cherry, tomato, strawberries (field use) and strawberries (greenhouse application). The reliable end points, appropriate for use in regulatory risk assessment, are presented. Missing information identified as being required by the regulatory framework is listed. Concerns are identified.

The conclusions of EFSA following the peer review of the initial risk assessments carried out by the competent authority of the rapporteur Member State France for the pesticide active substance dimethyl disulfide are reported. The context of the peer review was that required by Regulation (EC) No 1107/2009 of the European Parliament and of the Council. The conclusions were reached on the basis of the evaluation of the representative uses of dimethyl disulfide as a nematicide, fungicide and herbicide on carrot (field use) and on tomato (greenhouse application). The reliable endpoints, appropriate for use in regulatory risk assessment, are presented. Missing information identified as being required by the regulatory framework is listed. Concerns are identified.

The conclusions of EFSA following the peer review of the initial risk assessments carried out by the competent authority of the rapporteur Member State, the United Kingdom, for the pesticide active substance asulam and the assessment of applications for maximum residue levels (MRLs) are reported. The context of the peer review was that required by Regulation (EC) No 1107/2009 of the European Parliament and of the Council. The conclusions were reached on the basis of the evaluation of the representative use of asulam (variant evaluated asulam‐sodium) as a herbicide on spinach and tulip, hyacinth and lily for bulb production. MRLs were assessed in spinach. The reliable endpoints, appropriate for use in regulatory risk assessment and the proposed MRLs, are presented. Missing information identified as being required by the regulatory framework is listed. Concerns are identified.

The conclusions of EFSA following the peer review of the initial risk assessments carried out by the competent authorities of the rapporteur Member State the United Kingdom and co‐rapporteur Member State Germany for the pesticide active substance methiocarb are reported. The context of the peer review was that required by Commission Implementing Regulation (EU) No 844/2012. The conclusions were reached on the basis of the evaluation of the representative use of methiocarb as an insecticide and a bird repellent on maize. The reliable end points, appropriate for use in regulatory risk assessment, are presented. Missing information identified as being required by the regulatory framework is listed. Concerns are identified.

Influence of 50 keV boron ion implantation on the optical and structural properties of aliphatic PMMA and aromatic PET polymers has been studied. Samples were implanted with various fluences ranging from 1 × 1015 to 5 × 1016 B+ cm−2 at normal incidences. The intensity of most of the fundamental bands of these polymers, appearing in Raman and FTIR spectra, decreases significantly pointing towards structural rearrangement as an effect of low energy B+ implantation. UV–visible spectroscopy reveals significant increase in the value of disorder content (Urbach energy) and refractive index with increasing implantation dose for both the polymers. The decline in optical energy gap is found to be 22.3% for PMMA and 11.3% for PET due to B+ implantation. The degree of structural and optical modifications is more in PMMA in comparison to PET besides having same electronic to nuclear energy loss ratio. Both the chain scissioning and cross-linking mechanisms play significant role in the modification of the structure and properties of PMMA while chain scissioning is dominant in PET for the same. Such ion beam induced alteration in optical and structural properties makes these polymers ideal for making optical sensors, sun glasses, UV blocking devices and intraocular lenses etc.

An alternative carbonation technique was studied with normal concrete (NC) and concrete blended with natural zeolite (ZC) samples under an artificial environment with the help of carbonated...

We report anharmonic characteristics of cubic Scandium Oxide (Sc2O3) and hexagonal Neodymium Oxide (Nd2O3) through temperature dependent phonon mode variation in the temperature range 80–440 K. The samples were characterized as nanocrystalline and stoichiometric with crystallite sizes of 31 nm for Sc2O3 and 59 nm for Nd2O3. Under ambient conditions, Sc2O3 was found to have 10 phonon modes out of expected 22 Raman modes while Nd2O3 showed all 4 predicted phonon modes. The temperature dependent shift in wavenumber of Raman modes and broadening of the phonon modes has been analysed in light of thermal and anharmonic effects. The lattice expansion and strong anharmonic interactions were observed with an increase in temperature that resulted in measurable phonon softening. However, both samples were found to have stable phases within the studied temperature range. The total anharmonicity and anharmonic parameters along with phonon lifetimes are estimated. For the most intense phonon modes of Sc2O3 and Nd2O3, the total anharmonicity is calculated as − 3.44 × 10−5 K−1 and − 5+.47 × 10−5 K−1 respectively. The estimated anharmonic constants revealed the predominance of the three phonon process for decay as a function of temperature.

The present study reports a structural change of subchondral bone samples obtained from the patients who suffer from osteoarthritic knee (OA). The structural study was undertaken by comparison between controlled patients aged below 50 years old and OA patients aged over 50 years old. By employing Synchrotron-based X-ray fluorescence (SR-XRF) and X-ray absorption spectroscopy (XAS) techniques including X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS), the evidence of bone changes in term of Calcium–Phosphorus (Ca–P) contents were revealed. SR-XRF results excited at 2350 eV for P elements were used to clearly identify the amount of phosphorus contents in subchondral bone structure. The result showed the P contents in patients aged above 50 years old (OA) are lower than controlled patients. The depth information obtaining from both XANES and EXAFS results at P K-edge is related to electron transitions and structural modification especially around P ions at different ages. Lower Ca–P proportions which are caused the osteoporosis were obviously found in the elder patients. In addition, the majority amorphous structure of Ca–P is mainly found in all bone samples.

Highly regioregular poly(3-hexylthiophene) derivatives with varying degrees of fluorine substitution on the thiophene moieties have been demonstrated in photovoltaic devices and characterized using ultraviolet and inverse photoelectron spectroscopy. As fluorine content is increased, an increase in ionization energy of 0.3 eV is observed for 50% fluorination compared to non-fluorinated poly(3-hexylthiophene). The electron affinity is observed to increase to a lesser extent with increased fluorination, consistent with a systematic increase in the optical bandgaps of up to 0.12 eV. Bulk heterojunction photovoltaic devices made from polymer:PC 61 BM blends achieve power conversion efficiencies of 3%, however film morphologies measured using atomic force microscopy indicate that strong phase separation with increasing fluorination limits device performance. UV–vis spectra of thin films of the fluorinated materials exhibit a long tail in the red, extending to longer wavelengths than non-fluorinated poly(3-hexylthiophene). Photovoltaic devices similarly exhibit non-zero quantum efficiency in this region. This behavior has been attributed to a low energy, interchain charge transfer state.

Osteoarthritis (OA) is characterized by degeneration of articular cartilage and thickening of subchondral bone. The present study investigated the changing of biochemical components of cartilage and bone compared between normal and OA people. Using Synchrotron-based X-ray fluorescence (SR-XRF) and X-ray absorption spectroscopy (XAS) techniquesincluding X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) were employed for the bone changes in kneeosteoarthritisstudies. The bone samples were collected from various osteoarthritis patients with both male and female in the ages range between 20 and 74 years old. SR-XRF results excited at 4240 eV for Ca elements show a majority three main groups, based on their XRF intensities, 20–36 years, 40–60 years and over 70 years, respectively. By employing XAS techniques, XANES features can be used to clearly explain in term of electronic transitions occurring in bone samples which are affected from osteoarthritis symptoms. Moreover, a structural change around Ca ions in bone samples is obviously obtained by EXAFS results indicating an increase of Ca-amorphous phase when the ages increase.

Diketopyrrolopyrrole (DPP) derivatives are among the most efficient materials studied for both polymer solar cells (PSCs) and organic field-effect transistors (OFETs) applications. We report here the synthesis of new fluorinated dithienyldiketopyrrolopyrrole (fDT-DPP) monomers suitable for direct heteroarylation polymerization. fDT-DPP copolymers were then prepared to probe the effect of the fluorination. It was found that they feature deeper HOMO energy levels and smaller bandgaps than their non-fluorinated analogues. Moreover, some fDT-DPP copolymers show ambipolar behavior when tested in OFETs. For example, P2 shows hole mobility up to 0.8 cm2 V–1 s–1 and electron mobility up to 0.5 cm2 V–1 s–1. Inverted PSCs with power conversion efficiency (PCE) up to 7.5% were also obtained for P5. These results reported here (OFETs and PSCs) confirm that the fluorination of dithienyl-DPP moieties improves the performance of organic electronics devices. This study is also evidencing the strength of the direct hetero...

Short rotation coppice (SRC) is a promising plantation system because it provides inexpensive feedstock for biorefineries. This study investigated the conversion of 2-year-old first rotation SRC poplar into bio-oil via fast pyrolysis. The impact of leaf removal was studied by comparing the yields and compositions of bio-oil from no-leaf coppice (NLC) and whole tree coppice (WTC). Leaf removal did not affect the bio-oil yield of SRC poplar samples (∼55%) but lowered the char yield from 19.7% to 13.6% and increased the gas yield from 14.3% to 17.7%. The chemical compositions of bio-oils, char, and noncondensable gases obtained from WTC and NLC were different. Leaf removal changed the elemental composition of the bio-oil. The bio-oil from WTC had higher H (9.1%) and O (64.8%) but lower C (25.3%) than that from NLC. Consequently, leaf removal increased the higher heating value (HHV) of bio-oil by 2.1 MJ/kg (16.0%). On the basis of the results of the current research and our previous study, the energy recovery...

The incorporation of fluorine atoms along the conjugated polymer backbone is an effective strategy to tune the electro-optical properties of donor–acceptor based copolymers. We report here an efficient way to synthesize and purify new mono-fluorinated thiophene derivatives for the synthesis of fluorinated dithienobenzothiadiazole (DTBT) comonomers. It was observed that the reactivity and regioselectivity of the direct (hetero)arylation polymerization (DHAP) were modified upon the amount and the positioning of the fluorine atoms on the DTBT moiety. Indeed, the polymerization time went from 66 h (for non-fluorinated DTBT, M1) to only 11 min (for tetra-fluorinated DTBT, M2). In addition to enhanced reactivity, the degree of fluorination of the flanking thiophene of the DTBT moiety also modulates the electro-optical properties, lowering both the bandgap and stabilizing the ionization energy level. Indeed, P1 (with non-fluorinated flanking thiophene) has a bandgap of 1.73 eV and an ionization energy (IE) of 4....

Pairing a taste with either internal pain (e.g., from hypertonic saline injection) or nausea (e.g., from LiCl administration) will reduce subsequent consumption of that taste. Here we examine the responses to a taste paired with either hypertonic saline or LiCl using the analysis of licking microstructure (mean lick cluster size: Experiments 1-3), taste reactivity (examining the distribution of appetitive and aversive orofacial responses: Experiments 2-3), and immobility (as a measure of fear: Experiments 2-3). At both high (10 ml/kg 0.15 M LiCl, 10 ml/kg 1.5 M NaCl) and low dose levels (2 ml/kg 0.15 M LiCl, 4 ml/kg 1.5 M NaCl), pairing a taste with either LiCl-induced nausea or internal pain produced by hypertonic NaCl caused reductions in voluntary consumption, in appetitive taste reactivity responses, and in lick cluster size. However, only pairing with LiCl resulted in conditioned aversive taste reactivity responses to the taste. In contrast, pairing with hypertonic NaCl resulted in the taste eliciting higher levels of immobility (reflecting fear) than did pairing the taste with LiCl. The clearly dissociable effects of LiCl and hypertonic saline on aversive taste reactivity and fear responses, despite equivalent effects on consumption, demonstrates selective conditioning effects between internal pain and nausea. (PsycINFO Database Record

The molybdenum (Mo) and uranium (U) isotope compositions recorded in carbonate rich sediments are emerging as promising paleo-redox proxies. However, the effects of early diagenetic effects within the sediments on these isotope systems are not well constrained. We examined the Mo and U isotopic systematics in anoxic carbonate rich sediments in a semi enclosed karstic marine lake (Malo Jezero) of the Island of Mljet, Adriatic Sea.\ud Measurements of water column redox behavior in the lake since the 1950s, have shown a transition from anoxic-sulfidic conditions in the deeper water column to more oxic conditions and anoxia refined to the sediment and pore-waters. A 50 cm long sediment core from the deepest part of the lake, show a transition from moderate to high authigenic Mo and U accumulation with depth, consistent with the changing lake redox environment in the past. In the deep euxinic part of the core, the authigenic Mo and U are isotopically lighter and heavier, respectively, than seawater, following similar systematics as observed in other modern euxinic basins, with high, but non-quantitative, Mo and U uptake into the sediments.\ud Based on Bahamas bank carbonate sediments, it has been suggested that the 238U/235U ratio is ~+0.25‰ higher compared to seawater from the effects of early carbonate sediment diagenesis and this carbonate vs. seawater off-set is applicable to carbonate rich sediments across the geological past. The shallower part of lake sediment core was deposited under similar redox conditions as the Bahamas sediments, and these sediments show an average 238U/235U ratio + 0.31 ± 0.01‰ (2SE) higher than seawater. Although the average 238U/235U ratios for these two carbonate rich settings are similar, caution is necessary when inferring seawater 238U/235U compositions from such sediments, as they contain U from different sources (e.g. diagenetic uptake and carbonate-bound). The Mo isotope compositions within the same Malo Jezero sediments are variable but approaches the seawater composition at low pore-water H2S concentrations. This show the potential of using the Mo isotope composition from carbonate rich sediments to infer the seawater composition, however, further work is required to establish the link between the Mo isotope composition and the chemistry of the pore water environment.

Quantification of colorimetric assays with smartphones is being increasingly reported. However, a complete characterization of the performance of existing color spaces and single-color channels for optimum color/intensity change quantification is absent. Moreover, it has not been ascertained if it is necessary to utilize existing color spaces to reach optimal assay quantification. In this study, a randomized channel approach was adapted utilizing all single channels from RGB, HSV, and CieLab color space and all nonrepeating random combinations of two and three channels of these color spaces. Assays based on color or intensity change using pH strips and gold or carbon black nanoparticle-containing paper strips were optimized using this approach. Several novel channel combinations showed great promise, in terms of prediction error and interphone variation reduction, outperforming RGB, HSV, and CieLab color spaces. These novel combinations were used in a custom-developed smartphone application that performed automated background subtraction and polynomial regression for the quantification of a lateral flow assay for the detection of goat milk adulteration with cow milk and for pH prediction in soil. For the lateral flow assay the channel combination BSA was found optimum (mean average error = 36% ± 6%; R2 = 0.97). For the soil pH assay the channel combination RLC was found optimum (mean average error = 1.31% ± 0.02%; R2 = 0.997). The study has shown that nonclassical channel combinations for colorimetric quantification of specific assays are very promising and should be considered for smartphone-based analysis.

Purpose We conducted this investigation in order to develop a simple method for the determination of bioavailable vanadium and its speciation within sediments. Materials and methods The developed method is based on the determination of acid-extractable vanadium, as this fraction is presumably bioavailable, and its subsequent speciation using IC–UV/Vis (ionic chromatography with an ultraviolet-visible detector). A published procedure for vanadium speciation in pore water was further optimized in order to separate V(IV) and V(V) species using column EDTA derivatization on sediment samples. The analytical approach was applied in order to assess acid-extractable vanadium and its speciation within estuary sediments of the Krka River at the Dalmatian coast of Croatia. Results and discussion The results imply that the majority of vanadium within estuary sediments is in the form of less soluble fraction while the acid-extractable fraction comprises approximately 40% of the total vanadium present. In contrast, open sea sediment (station K4) was completely dominated by the acid-extractable vanadium. The extracted vanadium is in the form of V (IV). Conclusions Ion-exchange chromatography with an UV/Vis detector is a promising analytical method for vanadium speciation, however, further optimization of the conditions (improvement of the sequential extraction procedure) is needed in order to assess speciation also within other vanadium sedimentary fraction

Missiles are usually difficult to attack a land target or a surface ship that is equipped with a RADAR. Therefore, technology needs to be developed on missiles so that they are not detected by enemy RADAR. One of these technologies is the provision of RADAR absorbing material on missiles. Nickel ferrite is a cheap material that has high permeability, high resistivity, and high magnetic saturation, so it can be used as RADAR absorbing material. Chitosan is a biopolymer that is polycationic or possessing lots of positive charges from the nitrogen group. These polycationic properties tend to classify chitosan into dielectric materials. Materials with high dielectric properties will be able to absorb electromagnetic waves. Nickel ferrite and Chitosan are combined to make a cheap composite and has a prospect to be a RADAR absorbing material on missile.

Chemical weathering of silicate rock is one of the major long-term sinks of atmospheric CO2. While several radiogenic isotope systems (e.g. Nd, Pb, Os) in the authigenic component of marine sediments show temporal patterns that could be interpreted in terms of fluctuations in chemical weathering rate over glacial cycles, recent work using beryllium isotopes suggests little such variation. However, our knowledge of the sources of 9Be to the oceans is incomplete. Here, we address some of the gaps in knowledge with new data on Be in Croatian and Scottish rivers and estuaries, as well as with mixing experiments between Amazon tributaries and ocean water. The new data, combined with data from the literature, confirm that riverine Be is only marginally affected by carbonate weathering, which only accounts for 0.4–1.5% of dissolved riverine Be fluxes. The behavior of Be in estuaries is highly variable, with some estuaries showing removal and others addition. Based on the available data, about 55% of dissolved riverine Be is removed in estuaries, with complexation by both organic vs. inorganic ligands appearing to exert a strong control on the specific behavior in a given estuary. Beryllium complexation with organic material facilitates transport across estuaries, whereas the presence of inorganic complexants results in loss. Presence of both ligand types may lead to stronger non-conservative behavior than the presence of only one. Combining different approaches for estimating the dissolved riverine Be flux and estuarine removal, we calculate that 13–30% (4–48% error range) of the marine 9Be input is derived from riverine dissolved loads, and 70–87% (53–96% error range) from other sources like desorption from particulate matter and release from shelf sediments. It seems likely that this 13–30% of the marine Be input would respond quickly to changes in continental weathering rates, instantaneously impacting marine Be isotopes. However, the exact response of marine Be isotopes to changes in continental weathering rates also depends on the timescale of Be release from the riverine particulate pool stored in sediments on continental margins.

The conclusions of the EFSA following the peer review of the initial risk assessments carried out by the competent authorities of the rapporteur Member State, Norway, and co-rapporteur Member State, the Netherlands, for the pesticide active substance benfluralin are reported. The context of the peer review was that required by Commission Implementing Regulation (EU) No 844/2012. The conclusions were reached on the basis of the evaluation of the representative uses of benfluralin as a herbicide on chicory and lettuce and updated following the request from Commission to review the risk assessment as regards birds and mammals and aquatic organisms. The reliable end points, appropriate for use in regulatory risk assessment, are presented. Missing information identified as being required by the regulatory framework is listed. Concerns are identified.

The conclusions of EFSA following the peer review of the initial risk assessments carried out by the competent authorities of the rapporteur Member State the Netherlands and co‐rapporteur Member State Spain for the pesticide active substance pyriproxyfen and the assessment of applications for maximum residue levels (MRLs) are reported. The context of the peer review was that required by Commission Implementing Regulation (EU) No 844/2012. The conclusions were reached on the basis of the evaluation of the representative uses of pyriproxyfen as an insecticide on citrus fruit, pome fruit (apple, pears), tomatoes, ornamentals (field use) and tomatoes, ornamentals (greenhouse application). MRLs were assessed in citrus fruits. The reliable end points, appropriate for use in regulatory risk assessment and the proposed MRLs, are presented. Missing information identified as being required by the regulatory framework is listed. Concerns are identified.

An improved methodology was developed for V redox speciation in estuarine waters using a hyphenated technique consisting of ion chromatograph (IC) with an anion exchange column and a high-resolution inductively coupled plasma mass spectrometer (HR ICP-MS). This approach enables the direct determination of V(V), whereas reduced species (mainly V(IV)) are calculated by subtracting V(V) concentrations from the measured total V concentration. Based on the “on-column” V(V) chelation mechanism by EDTA, with the eluent composed of 40 mmol L−1 ammonium bicarbonate, 40 mmol L−1 ammonium sulphate, 8 mmol L−1 ethylenediaminetetraacetic acid and 3% acetonitrile, the method was successfully used for analyses of V redox speciation in samples taken in the vertical salinity gradient of the highly stratified Krka River estuary. Due to the matrix effects causing different sensitivities, a standard addition method was used for V(V) quantification purposes. The limit of detection (LOD) was also found to be matrix related: 101.68 ng L−1 in the seawater and 30.56 µg L−1 in the freshwater. Performed stability tests showed that V redox speciation is preserved at least 7 days in un-treated samples, possibly due to the stabilization of V-reduced species with natural organic matter (NOM). The dominant V form in the analysed samples was V(V) with the reduced V(IV) accounting for up to 26% of the total dissolved pool. The concentration of V(IV) was found to correlate negatively with the oxygen concentration. Significant removal of dissolved V was detected in oxygen depleted zones possibly related to the particle scavenging.

New phosphine-based ligands and DFT calculations for defect-free conjugated polymers by direct (hetero)arylation polymerization (DHAP)., Direct (hetero)arylation polymerization (DHAP) has emerged as a valuable and atom-economical alternative to traditional cross-coupling methods for the synthesis of low-cost and efficient conjugated polymers for organic electronics. However, when applied to the synthesis of certain (hetero)arene-based materials, a lack of C–H bond selectivity has been observed. To prevent such undesirable side-reactions, we report the design and synthesis of new, bulky, phosphine-based ligands that significantly enhance selectivity of the DHAP process for both halogenated and non-halogenated electron-rich and electron-deficient thiophene-based comonomers. To better understand the selectivity issues, density functional theory (DFT) calculations have been performed on various halogenated and non-halogenated electron-rich and electron-deficient thiophene-based comonomers. Calculations showed that the presence of bromine atoms decreases the energy of activation (E a) of the adjacent C–H bonds, allowing undesirable β-defects for some brominated aromatic units. Both calculations and the new ligands should lead to the rational design of monomers and methods for the preparation of defect-free conjugated polymers from DHAP.

We systematically varied the degree of fluorination along the backbone of a series of highly regioregular 3-hexylthiophene-based polymers, P3HT-50F, P3HT-33F, and P3HT-25F, in which 50%, 33%, and 25% of the thiophene units within the polymer chain contain fluorine atoms in the available 4-position, respectively. These materials were homopolymerized using the Kumada catalyst transfer polycondensation method from a set of mono-fluorinated bi-, ter-, and quarterthiophenes to ensure high polymer regioregularity and evenly spaced fluorine atoms along the conjugated thiophene backbone. The monomers were obtained from a synthetic route consisting of iterative Migita–Stille couplings of fluorinated and non-fluorinated 3-hexylthiophenes. The effect of the fluorine atoms on both polymer structure and properties is presented, with supporting quantum mechanical calculations that rationalize the intrinsic conformation preferences of the three P3HT derivatives. P3HT-50F (Mn = 34 kg/mol, 98.5% rr), P3HT-33F (Mn = 46 k...