Computational study on the structural and optoelectronic properties of a carbazole-benzothiadiazole based conjugated oligomer with various alkyl side-chain lengths

The effect of the alkyl side-chain length on the structural and optoelectronic properties of poly[N-9′-heptadecanyl-27-carbazole-alt-55-(4′,7′-di-2-thienyl-2′,1′,3′-benzothiadiazole)] (PCDTBT) conjugated oligomers have been studied by density functional theory (DFT) and time-dependent density functional theory (TD-DFT). The study was carried out by varying the length of alkyl side-chain attached to the nitrogen atom of the carbazole unit of the PCDTBT oligomers. The structural properties of the optimised oligomers were then studied by determining the bond-length alternation and dihedral angles (Φ) for various side-chain lengths. Total energy calculations for the determination of HOMO energy (E_HOMO), LUMO energy (E_LUMO), and fundamental energy gap (E_Gap) were performed using DFT at the B3LYP/6-31G(d), while the first singlet excitation energies (E_Opt) were calculated by TD-DFT also at the same level of theory. It was observed that there are no significant structural changes occurring as the alkyl chain lengths are varied. For the electronic properties, very small differences (i.e. ~0.01 eV) were observed for E_Gap and E_Opt while the exciton binding energies (E_B) were virtually the same. The results suggest that using shorter alkyl side-chains do not significantly affect the structural and optoelectronic properties of the carbazole-benzothiadiazole based polymer. The observations can aid future computational design studies of analogous systems by reducing large structures thus decreasing computational costs.     

Predominance of terrestrial organic matter in sediments from a cyanobacteria- blooming hypereutrophic lake

Although an understanding of the quantity and quality of sedimentary organic matter (SOM) pools is necessary to design sound environmental management strategies for lacustrine systems, the characterization of organic matter sources and the assessment of their relative contributions to eutrophic and inland lake sediments remain insufficient. In this study, the contribution of potential organic matter sources to sediments in shallow and hypereutrophic lake Taihu, China was assessed on the molecular level using source-specific fatty acid biomarkers. The results indicated that SOM was composed mainly of terrestrial plants with a maximal contribution of 45.3 ± 2.4% to the total organic carbon, which accounted for approximately 66% among the determined organic matter sources. Evidence suggests the terrestrial plants remained in a fresh state in surface sediments: the correlation (R² = 0.62, p < 0.05) between bacterial and terrestrial plant carbon was strong. On the other hand, aquatic plant and bacterial carbon contributed 5–15% to the total organic carbon, which was followed by the faint contribution (<5% of total organic carbon) of algae-derived organic carbon including cyanobacteria, diatoms, and dinoflagellates. The results provided details of the contributions of SOM sources, illustrating the usefulness of fatty acid biomarkers in discriminating organic matter sources within lake environments. Although organic matter sources of sediments varied in spatial and temporal patterns, the strong correlation between terrestrial plant and total organic carbon (R² = 0.60, p < 0.05) indicates that terrestrial plants were the dominant source in lake sediments.     

Population dynamics of Macrophomina phaseolina in relation to disease management: A review

Macrophomina phaseolina (Tassi) Goid. causes seedling blight, charcoal rot, leaf blight, stem and pod rot on over 500 plant species in different parts of the world. The pathogen survives as sclerotia formed in host tissues which are released into the soil as tissue decay. Low soil moisture is considered the more important predisposing factor for M. phaseolina-induced diseases than high temperature. The intensity of the disease on a crop is related to the population of viable sclerotia in the soil and abiotic factors. The influence of various management strategies in reducing the number of viable propagules of the pathogen in the soil has been studied in order to minimize the impact of the disease. Any management approach that reduces inoculum density in the soil may reduce disease incidence on the host. However, to reduce inoculum density, quantitative determination of viable propagules from soil is necessary in order to understand the effect of management strategies on the population dynamics of this pathogen. Considerable work has been done on organic amendments, changing crop sequences with tolerant crops, fumigants, herbicides and tillage in managing M. phaseolina populations in the soil and the resulting disease. Solarization has been used in controlling M. phaseolina in different countries where this pathogen is causing disease on economically valuable crops. However, this method of soil disinfestation was effective in eliminating viable populations at the top soil layer although by combining other approaches its effectiveness was improved at lower soil depth. Use of biological control agents with or without organic amendments or after solarization has emerged to be a practical management approach in the control of M. phaseolina. In this paper, an attempt has been made to review those research findings where the influence of various management approaches on survival of M. phaseolina mainly sclerotia have been investigated.     

Zwitterions for Organic/Perovskite Solar Cells,Light‐Emitting Devices,and Lithium Ion Batteries: Recent Progress and Perspectives

Zwitterions, a class of materials that contain covalently bonded cations and anions, have been extensively studied in the past decades owing to their special features, such as excellent solubility in polar solvents, for solution processing and dipole formation for the transfer of carriers and ions. Recently, zwitterions have been developed as electrode modifiers for organic solar cells (OSCs), perovskite solar cells (PVSCs), and organic light‐emitting devices (OLEDs), as well as electrolyte additives for lithium ion batteries (LIBs). With the rapid advances of zwitterionic materials, high‐performance devices have been constructed with enhanced efficiencies by introducing them as interface layers and electrolyte additives. In this review, recent progress in OSCs, PVSCs, OLEDs, and LIBs by using zwitterions is highlighted. The authors also elaborate the role of various zwitterionic materials as interfacial layers and additives for highly efficient OSCs, PVSCs, OLEDs, and LIBs. This article presents an overview of device performance of zwitterionic materials. The structure–property relationship is also discussed. Finally, the prospects of zwitterion materials are also addressed.     

Organic matter mineralization in the pore water of a eutrophic lake (Aydat Lake,Puy de Dôme,France)

The chemical composition of the pore water from the sediment of a eutrophic lake is dominated by high concentrations of total dissolved CO₂ (up to 12 mM), reduced soluble iron (up to 2 mM) and dissolved silica (up to 1 mM). The pH lies within the range of 6.70 ± 0.02; this reflects that the pore water is efficiently buffered by the CO₂ acid/base system. This composition is directly related to the main diagenetic reactions which drive the organic matter mineralization i.e. methanogenesis and ferric oxides reduction. Other geochemical processes are of minor importance. A stoichiometric model based on these main reactions allow us: (i) to define a general formula for the organic matter which is close to Redfield's one for the C:N ratio, while the C:P ratio is much higher owing to a probable adsorption of phosphorus onto reactive surfaces of the solid and due to heterotrophic bacterial uptake; (ii) to calculate a global first order kinetic constant which drives the organo-polymers breakdown. Due to the strong influence on the trophic status of the lake caused by an excess of phosphate, special attention is devoted to this species. We show that the sediment-water interface is a source of dissolved phosphate when the hypolimnion is anoxic between May and November. This contribution represents about 17% of the river input and should be taken into account in any attempt toward lake restoration.     

Weathering of Granite from the Damma Glacier Area: The Contribution of Cyanogenic Bacteria

The dissolution potential of five cyanogenic bacteria was studied at 25°C during 32 days using granite material from the Damma glacier (Central Alps, Switzerland) as the sole source of nutrients. The bacterial species Pseudomonas fluorescens and Pseudomonas sp. CCOS 191 were the most effective to exudate various organic acids and consequently mobilized Fe. The molecular mechanisms include both, proton-promoted and ligand-promoted dissolution, preferentially at pH below 5 and in the pH range between 5.0 and 5.8, respectively. In addition, bacterially produced cyanide plays a minor role through the formation of soluble hexacyanoferrate complexes. To our knowledge, this study is the first that reveals the direct measurement of metal-cyanide complexes formed during biotic granite weathering.     

Corals shed bacteria as a potential mechanism of resilience to organic matter enrichment

Understanding the mechanisms of resilience of coral reefs to anthropogenic stressors is a critical step toward mitigating their current global decline. Coral–bacteria associations are fundamental to reef health and disease, but direct observations of these interactions remain largely unexplored. Here, we use novel technology, high-speed laser scanning confocal microscopy on live coral (Pocillopora damicornis), to test the hypothesis that corals exert control over the abundance of their associated bacterial communities by releasing (‘shedding'') bacteria from their surface, and that this mechanism can counteract bacterial growth stimulated by organic inputs. We also test the hypothesis that the coral pathogen Vibrio coralliilyticus can evade such a defense mechanism. This first report of direct observation with high-speed confocal microscopy of living coral and its associated bacterial community revealed a layer (3.3–146.8 μm thick) on the coral surface where bacteria were concentrated. The results of two independent experiments showed that the bacterial abundance in this layer was not sensitive to enrichment (5 mg l⁻¹ peptone), and that coral fragments exposed to enrichment released significantly more bacteria from their surfaces than control corals (P<0.01; 35.9±1.4 × 10⁵ cells cm⁻² coral versus 1.3±0.5 × 10⁵ cells cm⁻² coral). Our results provide direct support to the hypothesis that shedding bacteria may be an important mechanism by which coral-associated bacterial abundances are regulated under organic matter stress. Additionally, the novel ability to watch this ecological behavior in real-time at the microscale opens an unexplored avenue for mechanistic studies of coral–microbe interactions.     

A Mass Spectrometric Study for Comparative Analysis and Evaluation of Metabolite Recovery from Plasma by Various Solvent Systems

A solvent system that extracts a maximum number of metabolites belonging to diverse chemical classes from complex biofluids, such as plasma, may offer useful inputs to understand the metabolic and physiological state of an individual. The present study compared seven solvent systems for extraction of metabolites from plasma. The extracts were analyzed by mass spectrometry (MS) and MS/MS (MS2) using a quadrupole time-of-flight liquid chromatography/MS system in positive and negative modes of ionization. Metabolites with molecular mass below 400 were identified using Human Metabolome Database MS2 and MS search interfaces. The acetone/isopropanol (2:1) system yielded promising results in positive ionization mode, as the maximum number of MS and MS2 features was detected in the extract. It was found to be superior in extraction of various classes of metabolites, especially organic acids, nucleosides and nucleoside derivatives, and heterocyclic molecules. Glycerophosphocholines in the mass range of 400–700 were found to be efficiently extracted by the methanol/chloroform/water (8:1:1) system. In negative mode as well, the maximum number of MS2 features was detected in methanol/chloroform/water and acetone/isopropanol extracts. The fingerprints of molecular features obtained in the negative and positive modes differed from each other to a significant extent.