Methyl Research Articles

Meso-Hydroxylmethyl-1,3,5,7-tetramethylBODIPY: A Visible-Light Photoremovable Protective Group for Carboxyl Groups

AbstractA meso-BODIPY-type photoremovable protecting group for carboxyl group is developed. BODIPYs are well-known for brilliant color, favorable to reaction monitoring and purification. meso-BODIPY esters are achieved via esterification in 44–89% yields, while deprotection is fulfilled under irradiation of blue LED bulb in the presence of photocatalyst and organic hydrogen donor in 43–95% yields. This method is applicable to a variety of acids, such as aromatic, heteroaromatic, alkyl, α,β-unsaturated carboxylic acids, etc. Our BODIPY-deprotective condition is almost neutral that both methyl and tert-butyl esters are compatible.

Aspects of Reaction Engineering for Biodiesel Production

Biodiesel is a non-toxic, drop-in liquid transportation fuel that is amenable to continuous production from sustainable biomass resources using catalytic technologies. A diverse range of catalysts and reactor technologies have been experimentally investigated and computationally modelled, for producing biodiesel (fatty acid methyl esters) from oil feedstocks by their esterification or transesterification with short-chain alcohols. Solid-acid and base catalysts are attractive for biodiesel production from renewable oil feedstocks due to their ease of separation from the desired biodiesel and glycerol by-product, use of Earth’s abundant elements, and suitability in continuous processes. Here, we review the technical challenges and opportunities in designing catalytic reactor systems for biodiesel production.

Fungal Biostarter and Bacterial Occurrence of Dry-Aged Beef: The Sensory Quality and Volatile Aroma Compounds after 21 Days of Aging

In this study, we decided to test the hypothesis that the fungal biostarter M. flavus used during a 21-day beef dry-aging process significantly impacts the composition of other microorganisms, the profile of volatile compounds, meat hardness characteristics, and, consequently, the sensory quality. The experiments were performed on samples derived from animals crossbred between Holstein–Fresian cows and meat breed bulls. Two groups of samples were studied, including the control group, without biostarter, and a group inoculated with the M. flavus biostarter. Both sample groups were seasoned for 21 days in the dry-aging fridge. The physicochemical parameters (pH, color parameters), the chemical composition of muscle, the determination of the shear force, the profile of volatile compounds (VOCs), and the sensory quality were evaluated after aging. During this study, classical microbiological methods were used to investigate the influence of fungal biostarters on the growth and survival of bacteria and other fungi (e.g., yeasts) during the dry-aging process of beef (DAB). The M. flavus biostarter improved the sensory quality of DAB, allowing high sensory quality to be achieved after just 21 days. This is likely due to the diverse VOCs produced by the fungus, including 1-tetradecanol, 2-nonenal, trans-2-undecenoic acid, and the following esters: formic acid hexyl ester, 10-undecenoic acid methyl ester, and 4-methylpentanoic acid methyl ester. The presence of the biostarter had no significant effect on the number of the bacteria or the survivability of the L. monocytogenes on the meat’s surface in laboratory conditions.

Experimental Investigation on Performance Characteristics o f Diesel Engine Using Various Blended Biodiesels

Objectives: To evaluate the performance characteristics of diesel engines through experimental research with various biodiesel blends. Method: Three types of oils were chosen for this study: waste cooking oil, waste chicken oil, and palm oil. The methyl esters were produced from waste chicken oil (COME), waste cooking oil (WCOME), and palm oil (POME). The test runs were done on a 4.5 kW direct injection, air-cooled, four-stroke, single-cylinder, and constant-speed diesel engine using varied fuel at maximum load. Findings: This study finds performance analysis for a variety of methyl esters and diesel. The Brake Thermal Efficiency (BTE) was found to be: for Diesel (33.36%), POME (30.53%), WCOME (27.5%), COME (25.0%) at rated power (4.5) K.W. The brake thermal efficiency for palm oil methyl esters is similar to the diesel compared to the other methyl esters. Novelty: This research study provides a comparison between the diesel and methyl esters of break thermal efficiency for diesel engines. Keywords: Diesel Engine, Trans esterification, Biodiesels, Performance characteristics

Unveiling Nanoscale Ordering in Amorphous Semiconducting Polymers Using Four-Dimensional Scanning Transmission Electron Microscopy.

We present four-dimensional (4D) scanning transmission electron microscopy (STEM) analysis to obtain a high level of detail regarding the nanoscale ordering within largely disordered organic semiconducting polymers. Understanding nanoscale molecular ordering in semiconducting polymers is crucial due to its connection to the materials' important properties. However, acquiring such information in a spatially localized manner has been limited by the lack of a nanoscale experimental probe, weak signal from ordering, and radiation damage to the sample. By collecting nanodiffraction patterns with a high dynamic range pixelated detector, we acquired statistically robust, high signal-to-noise ratio diffraction patterns from semiconducting organic materials, including poly(3-hexylthiophene-2,5-diyl) (P3HT), P3HT/[6,6]-phenyl C61 butyric acid methyl ester, and indacenodithiophene-co-benzothiadiazole (IDTBT), which largely have disordered structures. Real-space images of the ordered domains were reconstructed from the 4D-STEM data set for a variety of scattering vectors and in-plane angles to capture the different molecular stacking distances and their in-plane orientation. These were then analyzed to obtain the average size of the ordered domains within the sample. Such measurements were arranged in a two-dimensional (2D) histogram, which showed a direct relationship between the type and size of molecular ordering. Complementary analyses, such as intensity variance and angular correlation, were applied to obtain ordering and symmetry information. These analyses enabled us to directly characterize the alkyl and π-π stacking of P3HT, as well as the fullerene domains caused by donor segregation in the P3HT sample. Furthermore, the analysis also captured changes in the P3HT domains when the fullerenes are incorporated. Lastly, IDTBT showed a much lesser degree of ordering without much disinclination between the domains within the 2D histogram. The 4D-STEM analysis that we report here unveils new details of molecular ordering that can be used to optimize the properties of this important class of materials.

Integrating environmental remediation with biodiesel production from toxic non-edible oil seeds (Croton bonplandianus) using a sustainable phyto-nano catalyst

In the current situation of the environmental uprising toxicology, rising global temperature, and energy-depleting urges to explore and discover more renewable and greener ecological-benefiting energy resources. Biobased renewable fuels generated by using waste products can help in waste management, climate change mitigation, and a low-carbon future. The main objective of this research is to produce environment-friendly and cost-effective biofuel. The potentiality of the novel, toxic, waste, and inedible feedstock Croton bonplandianus was evaluated for biodiesel synthesis through transesterification utilizing a Phyto-nano catalyst of potassium oxide prepared by Croton bonplandianus floral stalk's aqueous extract focusing on waste management. Phyto-nano catalyst characterization was done through innovative tools such as Scanning Electron Microscopy (SEM), Energy Dispersive Spectroscopy (EDS), Zeta Potential (ZP), X-Ray Diffraction (XRD), Fourier Transformed Infrared spectroscopy (FTIR), and Diffuse Reflectance Spectroscopy (DRS). The characterization results revealed that the potassium oxide phyto-nanocatalyst possesses an average nanoparticle size of 44.5 nm. This size is optimal for enhanced catalytic activity, indicating significant potential for efficient catalysis. The highest yield (94 %) of biodiesel was secured at optimized reaction conditions of catalyst quantity (0.50 wt%), reaction time (180 min), methanol: oil ratio (9:1), and reaction thermal point (70 °C). Transformation of triglycerides to methyl esters was confirmed by GC/MS, NMR, and FTIR techniques. A total of 21 methyl esters were observed in Croton bonplandianus biodiesel confirmed via GC/MS results. Evaluation of fuel properties was done and matched with international fuel standards. The conclusive remarks for the conducted research are that Croton bonplandianus has a high potential for biodiesel production by applying Phyto-nanocatalysts of potassium oxide while dealing with hazardous environmental conditions and waste management. Phyto nanocatalyst of potassium oxide can be reused and gives the same yield after several cycles of reusability, this reusability of heterogenous Phyto nanocatalyst can reduce to total cost of biodiesel production and can contribute towards circular economy.

Biodiesel from Higher Alcohols for Removal of Crude Oil Spills from Coastal Sediments

Throughout the decades, the production, transport, and use of fossil fuels have led to numerous environmental concerns. Crude oil has caused catastrophic accidents after its spillage into the aqueous environment and accumulation on coastal sediments. To tackle this problem in a sustainable manner, researchers have used alternative remediation agents to extract these crude oil spills from the sediments. In this study, the biodiesels fatty acid methyl, ethyl, and butyl esters (FAME, FAEE, and FABE, respectively) were synthesized via transesterification reaction from waste cooking oil and corresponding alcohol in the presence of a catalyst, potassium hydroxide, and used as remediation agents for crude oil extraction. The influence of different experimental conditions on the crude-oil removal efficiency was studied (time of 1, 2, or 4 h; mass ratio of biodiesel to crude oil of 0.5:1, 1:1, or 2:1), with a simulation of coastal effects using a shaker. UV/Vis spectrophotometry was used to determine crude-oil separation efficiency based on the correlation of the residual crude-oil mass fraction and corresponding absorbance. The results show that FAME and FAEE were most effective in the removal of crude oil from sand (removing 88–89%), while FAEE and FABE extracted the most crude oil from gravel (removing 74–77%).

Online characterization of primary and secondary emissions of particulate matter and acidic molecules from a modern fleet of city buses

Abstract. The potential impact of transitioning from conventional fossil fuel to a non-fossil-fuel vehicle fleet was investigated by measuring primary emissions via extractive sampling of bus plumes and assessing secondary mass formation using the Gothenburg Potential Aerosol Mass (Go:PAM) reactor from 76 in-use transit buses. Online chemical characterization of gaseous and particulate emissions from these buses was conducted using chemical ionization mass spectrometry (CIMS) with acetate as the reagent ion, coupled with the Filter Inlet for Gases and AEROsols (FIGAERO). Acetate reagent ion chemistry selectively ionizes acidic compounds, including organic and inorganic acids, as well as nitrated and sulfated organics. A significant reduction (48 %–98 %) in fresh particle emissions was observed in buses utilizing compressed natural gas (CNG), biodiesels like rapeseed methyl ester (RME) and hydrotreated vegetable oil (HVO), and hybrid-electric HVO (HVOHEV) compared to diesel (DSL). However, secondary particle formation from photooxidation of emissions was substantial across all the fuel types. The median ratio of particle mass emission factors of aged to fresh emissions increased in the following order: DSL buses at 4.0, HVO buses at 6.7, HVOHEV buses at 10.5, RME buses at 10.8, and CNG buses at 84. Of the compounds that can be identified by CIMS, fresh gaseous emissions from all Euro V/EEV (Enhanced Environmentally friendly Vehicle) buses, regardless of fuel type, were dominated by nitrogen-containing compounds such as nitrous acid (HONO), nitric acid (HNO3), and isocyanic acid (HNCO), alongside small monoacids (C1−C3). Notably, the emission of nitrogen-containing compounds was lower in Euro VI buses equipped with more advanced emission control technologies. Secondary gaseous organic acids correlated strongly with gaseous HNO3 signals (R2=0.85–0.99) in Go:PAM, but their moderate to weak correlations with post-photooxidation secondary particle mass suggest that they are not reliable tracers of secondary organic aerosol formation from bus exhaust. Our study highlights that non-regulated compounds and secondary pollutant formation, not currently addressed in legislation, are crucial considerations in the evaluation of environmental impacts of future fuel and engine technology shifts.

Quercus ballot as an innovative feedstock for biodiesel production using ZnO nanocatalyst

Selecting non-edible plant seed oil remains the best choice for biodiesel production using an effective nanocatalyst. In this study, the ZnO was prepared as a nanocatalyst using an aqueous extract from the Alhaji marorum plant. Nano ZnO has shown high catalytic activity, is cost-effective, environmentally friendly and converts triglycerides into fatty acid methyl esters. The results indicate that ZnO nanocatalyst exhibit a high specific surface area (146.82 m2 g-1), large pore volume (0.35 cm3 g-1), and an average crystallite size of 42.3 nm. The FESEM analysis shows that the particle size of ZnO lies in the range of 30–50 nm with a rod shape and densely packed morphology. The biodiesel is produced using a transesterification process from novel non-edible Quercus ballot plant seeds. The resulting biodiesel has a 98.06 % yield under a methanol/oil ratio of 6:1 with 0.5 wt% ZnO nanocatalyst at 65 °C for 80 min. It is established that the methanol-to-oil ratio and the catalyst concentration significantly affect the transesterification reaction. The biodiesel produced is characterized by GC–MS to determine its exact composition and FTIR is used to confirm functional groups and is evaluated according to ASTM D6751.

Synthesis of Azabicyclic Isosteres of Piperazine 2S-Carboxylic Acid.

Methods have been developed for the stereocontrolled synthesis of bicyclic diaza [3.3.0] octane carboxylic acids as possible isosteres of piperazine 2S-carboxylic acid. In the first approach, l-pyroglutamic acid was functionalized adopting new as well as documented reaction sequences via Michael and aza-Michael reactions, leading to two of the four intended isosteres. An alternative shorter route relying on enolate chemistry starting with N-Pf 4-keto l-proline methyl ester led to two other isosteres. Calculated pKa values and density functional theory (DFT) calculations have provided some insights into the relative basicities of the nitrogen atoms in these diaza [3.3.0] octane carboxylic acids in relation to piperazine 2S-carboxylic acid.

Evaluation of Microbial Phospholipase and Lipase Activity Through the Chromatographic Analysis of Crude, Degummed, and Transesterified Soybean Oil for Biodiesel Production.

The present study aimed at synthesizing fatty acid methyl esters in a combined enzymatic method by applying degumming and transesterification of soybean oil. A soluble lipase from Serratia sp. W3 and a recombinant phosphatidylcholine-preferring phospholipase C (PC-PLC) from Bacillus thuringiensis were used in a consecutive manner for phosphorus removal and conversion into methyl esters. By applying 1% of recombinant PC-PLC almost 83% of phosphorus was removed (final content of 21.01mg/kg). Moreover, a sensitive and selective high-performance liquid chromatography method coupled to tandem mass spectrometry was applied to obtain a comprehensive lipid profile for the simultaneous evaluation of phospholipids removal and diacylglycerol (DAG) increase. A significant increase for all the monitored DAG species, up to 138.42%, was observed by using the enzymatic degumming, in comparison to the crude sample, resulting in an increased oil yield. Serratia sp. W3 lipase was identified as a suitable biocatalyst for biodiesel production, converting efficiently the acylglycerols. The results regarding the physical-chemical characteristics show that the cetane level, density and pour point of the obtained biodiesel are close to current regulation requirements. These findings highlight the potential of a two-step process implementation, based on the combination of lipase and phospholipase, as a suitable alternative for biodiesel production.

Impaired microvascular insulin-dependent dilation in women with a history of gestational diabetes.

Women with a history of gestational diabetes mellitus (GDM) have a significantly greater lifetime risk of developing cardiovascular disease and type 2 diabetes compared with women who had an uncomplicated pregnancy (HC). Microvascular endothelial dysfunction, mediated via reduced nitric oxide (NO)-dependent dilation secondary to increases in oxidative stress, persists after pregnancy complicated by GDM. We examined whether this microvascular dysfunction reduces insulin-mediated vascular responses in women with a history of GDM. We assessed in vivo microvascular endothelium-dependent vasodilator function by measuring cutaneous vascular conductance responses to graded infusions of acetylcholine (10-10-10-1 M) and insulin (10-8-10-4 M) in control sites and sites treated with 15 mM l-NAME [NG-nitro-l-arginine methyl ester; NO-synthase (NOS) inhibitor] or 5 mM l-ascorbate. We also measured protein expression of total endothelial NOS (eNOS), insulin-mediated eNOS phosphorylation, and endothelial nitrotyrosine in isolated endothelial cells from GDM and HC. Women with a history of GDM had reduced acetylcholine (P < 0.001)- and insulin (P < 0.001)-mediated dilation, and the NO-dependent responses to both acetylcholine (P = 0.006) and insulin (P = 0.006) were reduced in GDM compared with HC. Insulin stimulation increased phosphorylated eNOS content in HC (P = 0.009) but had no effect in GDM (P = 0.306). Ascorbate treatment increased acetylcholine (P < 0.001)- and insulin (P < 0.001)-mediated dilation in GDM, and endothelial cell nitrotyrosine expression was higher in GDM compared with HC (P = 0.014). Women with a history of GDM have attenuated microvascular vasodilation responses to insulin, and this attenuation is mediated, in part, by reduced NO-dependent mechanisms. Our findings further implicate increased endothelial oxidative stress in this microvascular insulin resistance.NEW & NOTEWORTHY Women who have gestational diabetes during pregnancy are at a greater risk for cardiovascular disease and type 2 diabetes in the decade following pregnancy. The mechanisms mediating this increased risk are unclear. Herein, we demonstrate that insulin-dependent microvascular responses are reduced in women who had gestational diabetes, despite the remission of glucose intolerance. This reduced microvascular sensitivity to insulin may contribute to increased cardiovascular disease and type 2 diabetes risk in these women.

Time of day affects MrgD-dependent modulation of cardiomyocyte contractility.

The renin-angiotensin system (RAS) is composed of a series of peptides, receptors, and enzymes that play a pivotal role in maintaining cardiovascular homeostasis. Among the most important players in this system are the angiotensin-II and angiotensin-(1-7) peptides. Our group has recently demonstrated that alamandine (ALA), a peptide with structural and functional similarities to angiotensin-(1-7), interacts with cardiomyocytes, enhancing contractility via the Mas-related G protein-coupled receptor member D (MrgD). It is currently unknown whether this modulation varies along the distinct phases of the day. To address this issue, we assessed the ALA-induced contractility response of cardiomyocytes from mice at four Zeitgeber times (ZTs). At ZT2 (light phase), ALA enhanced cardiomyocyte shortening in an MrgD receptor-dependent manner, which was associated with nitric oxide (NO) production. At ZT14 (dark phase), ALA induced a negative modulation on the cardiomyocyte contraction. β-Alanine, an MrgD agonist, reproduced the time-of-day effects of ALA on myocyte shortening. NG-nitro-l-arginine methyl ester, an NO synthase inhibitor, blocked the increase in fractional shortening induced by ALA at ZT2. No effect of ALA on myocyte shortening was observed at ZT8 and ZT20. Our results show that ALA/MrgD signaling in cardiomyocytes is subject to temporal modulation. This finding has significant implications for pharmacological approaches that combine chronotherapy for cardiac conditions triggered by disruption of circadian rhythms and hormonal signaling.NEW & NOTEWORTHY Alamandine, a member of the renin-angiotensin system, serves critical roles in cardioprotection, including the modulation of cardiomyocyte contractility. Whether this effect varies along the day is unknown. Our results provide evidence that alamandine via receptor MrgD exerts opposing actions on cardiomyocyte shortening, enhancing, or reducing contraction depending on the time of day. These findings may have significant implications for the development and effectiveness of future cardiac therapies.

Molecular Architecture of A Novel Indoline-Fused Chromenylium-Cyanine Probe Carrying Methionine Biomolecule for Ultrasensitive Analyzing Hg2+ Ion in Real Samples

In this study, by decorating the chromenylium-cyanine structure with an indoline ring, a new sensor platform CSI with a highly rigid structure and improved photophysical properties was developed for the first time. The CSI platform was modified with glyoxal and L-methionine methyl ester to produce a new NIR, ratiometric, and switch-on probe (CIME). This probe is biocompatible, water soluble, and has a specific binding mode for Hg2+ ion selectivity. The crystal structure of CSI was determined by x-ray crystallography, and its electronic characteristics, including HOMO-LUMO energy levels were determined by quantum mechanical calculations. CIME is the first instance of an indoline-fused chromenylium-cyanine used for quantification of trace level of Hg2+ in both the living cells and the environment. The new probe has a high level of selectivity and sensitivity for Hg2+ in aqueous media, with broad linear ranges (0-300μM for UV-Vis and 0-225μM for fluorescence). It has a rapid response time of 30seconds, and UV-Vis and fluorescence detection limits of 7.4ng/mL and 0.13ng/mL, respectively. Probe quantitatively detected Hg2+ in real samples using UV-Vis, fluorescence spectrophotometry and a smartphone. The interaction between CIME and Hg2+ was verified by FTIR, HRMS and DFT calculations. Furthermore, the ability of CIME to sense Hg2+ in living cells was confirmed in both MCF-7 cells and 3T3 cells.

Synthesis and characterisation of waste-derived biodiesel and enhancement of its energy and environmental metrics using cetane improver: an experimental study

The primary objective of this study is to produce Bauhinia monandra biodiesel (BMB) using seed waste and improve its energy and environmental properties by integrating a cetane enhancer. The methyl ester of biooil was obtained using the transesterification method, and the properties were analyzed. Different quantities of BMB were combined with diesel fuel, and 2-ethyl hexyl nitrate (EHN) was introduced to the blend of 30% BMB-diesel fuel to improve both energy and environmental performance measurements. The research findings indicate that the FAME and physicochemical properties of BMB are comparable to those of diesel fuel. The brake thermal efficiency (BTE) of the engine decreases by 4.2% for 30% BMB blended fuel, whereas hydrocarbon (HC), carbon monoxide (CO), and smoke emissions decrease by 11.6%, 6.7%, and 10.5%, respectively. As the concentration of BMB increases, there is a reduction in both the maximum value of in-cylinder pressure and the net heat release rate. Conversely, brake-specific fuel consumption (BSFC) and NOx emissions increase by 5.7% and 4.7%, respectively. The incorporation of EHN in the test fuel enhances BSFC and BTE by 4.2% and 4.3%, respectively, whereas NOx, HC, and CO emissions are reduced by 5.2%, 9.2%, and 9.9%, respectively.

Plant growth-promoting Bacillus cereus MCC3402 facilitates rice seedling growth under arsenic-spiked soil

Microorganisms can solve the global problem of arsenic (As) contamination in soil and water, by eliminating the hazardous metalloid from contaminated habitats. A native As- resistant PMM6 strain was isolated from the tainted agricultural field in Durgapur, India. Following phenotypic investigations, fatty acid methyl ester analysis, and 16S rDNA sequence-based homology, it was identified as Bacillus cereus. Various analytical techniques such as Atomic absorption spectroscopy, Fourier transform infrared spectroscopy, X-ray diffraction, X-ray fluorescence, Scanning electron microscopy, Transmission electron microscopy, and energy dispersive X-ray spectroscopy studies revealed a positive correlation between the strain's resistance properties against arsenate (75 mM) and arsenite (25 mM)) and the biosorption and bioaccumulation of arsenic. The strain exhibited several important plant growth-promoting traits, including indole-3-acetic acid production (110.0 ± 0.33 μg/mL), 1-aminocyclopropane-1-carboxylate deaminase activity (2334.2 ± 1.90 nm α-ketobutyrate/mg protein/h), phosphate solubilization, and siderophore production (68.0 ± 2%). These traits facilitated the growth augmentation of rice seedlings under As stress, both in terms of physiological and biochemical parameters. Compared to un-inoculated soil, the use of strain PMM6 helped reduce As mobilization and oxidative stress in rice seedlings growing in As-spiked soil. Therefore, strain PMM6 holds the potential as bioremediator to restore As-contaminated agricultural lands while also promoting the growth of rice seedlings. It could thus be utilized in the bioremediation of As-contaminated agricultural lands in the near future.

Thermal Conversion of Coral Waste and its Utilization as Low-Cost Catalyst for Biodiesel Production

This study investigates the thermal conversion of waste coral and its utilization as a heterogeneous catalyst for biodiesel production from soybean oil. In this work, waste coral is calcined at varied temperatures of 800, 900, and 1000°C, and the effect of the calcination temperature on the physicochemical character of the solid is evaluated through Fourier-transform infrared spectroscopy, X-ray diffraction, scanning electron microscopy, and basicity measurement. The results show that the higher temperature facilitates the conversion of CaCO3 of the aragonite and calcite phases in raw waste coral into CaO, achieving a complete conversion at the temperature of 1000°C. Thermal conversion influences the increased surface basicity of the solid, which is associated with the higher activity for biodiesel production. Further studies on the obtained CaO as a catalyst demonstrate the catalyst dosage and the methanol-to-oil ratio as significant factors for fatty acid methyl ester production. The highest yield of 98.7% is achieved after a 3 hours reaction with 8 wt.% catalyst dosage and 9:1 methanol-to-oil ratio. The catalyst exhibits stability with an insignificantly decreased yield until the fifth usage cycle. The optimum conditions and reusability features of the calcined waste coral suggest that waste coral is a favorable CaO catalyst source for biodiesel production.

Self-powered Schottky barrier photodetectors based on P3HT:PC61BM bulk heterojunction films

By employing the classic system poly(3-hexylthiophene-2,5-diyl): [6,6]-phenyl-C61-butyric acid methyl ester (P3HT:PC61BM), organic bulk heterojunction films were applied on an indium tin oxide substrate using a one-step spin-coating method, without requiring any complex manufacturing processes, to obtain self-powered photodetectors (PDs) with a simple preparation process. The fullerene material was introduced to create a bulk heterojunction film with proper phase separation and greatly enrich the donor/acceptor dissociation interface, thus improving the high exciton binding energy and short exciton diffusion distance. The built-in electric field formed by the Schottky junction at the interface between the active layer and electrode can enhance the separation of excitons and the transport of charge carriers, realizing optical detection without external energy sources. Moreover, femtosecond transient absorption was employed to investigate the exciton dynamics in organic films and analyze the working mechanism of self-powered detection performance. The long-lived behavior of carriers and the formation of charge transfer states were further verified, which contributed to the enhanced performance of the device. As a result, the self-powered PD-based Schottky bulk heterojunction presents a high light on/off ratio of over 104 (0 V) and fast response speed with rise and decay times of 33 and 36 µs, respectively, under a 532 nm light illumination. These results provide theoretical and experimental verification of this technique for the development of self-powered PDs in the field of organic materials.

Effect of 4,4′-dialkyl-2,2′-bipyridine ligands on the hydrolysis of dichlorodioxomolybdenum(VI) catalyst precursors and the switch from homogeneous epoxidation to heterogeneous systems

Molybdenum catalysts have been industrially recognized, for decades for liquid phase epoxidation, which is an important chemical reaction process, since epoxides are used for many industrial applications. In this work, molybdenum oxide hybrid catalysts, prepared by a reflux hydrolysis methodology, performed effectively as heterogeneous catalysts or reaction-induced self-separating catalysts under mild reaction conditions; in the two cases, the catalyst separation and reuse are facilitated. Specifically, catalysts with the general formula [MoO3(L)], possessing polymeric chain-like (L = 4,4′-dimethyl-2,2′-bipyridine (1)) or oligomeric (L = 4,4′-dinonyl-2,2′-bipyridine (2)) structures comprising corner-sharing {MoO4N2} units, were synthesized and characterized by various complementary techniques (ATR FT-IR, Raman, 13C{1H} CP MAS NMR spectroscopy, PXRD, SEM, TGA, elemental analysis, ICP-OES and N2 sorption isotherms). Small chemical differences in the organic synthesis precursor had important structure directing effects on the type of hybrid material formed. The hybrids promoted olefin epoxidation with H2O2 or tert-butylhydroperoxide (TBHP) as oxidant. For example, 1 catalyzed the conversion of biobased olefins (70 °C) and lignin-based isoeugenol (50 °C) with TBHP to useful bioproducts, in heterogeneous phase, leading to an epoxide yield of 100 % for DL-limonene (3:1 M ratio of 1,2-epoxy-p-menth-8-ene to 1,2:8,9-diepoxy-p-menthane), 81 % epoxide yield for fatty acid methyl esters, and 80 % Licarin A selectivity at 40 % isoeugenol conversion. For dienes (DL-limonene, methyl linoleate), kinetic modelling studies suggested that the formation of the monoepoxides was faster than that of diepoxides, accounting for enhanced monoepoxide selectivity.

Determination of the effect of low concentration titanium dioxide nano fuel additive in biodiesel on performance and emissions

In this study, the effect of nanoparticle addition into rapeseed methyl ester (R0) produced by the transesterification method on engine performance and emissions was experimentally investigated. Titanium dioxide was used as a nano fuel additive and was added to the test fuels at rates of 50 ppm (RTi50) and 75 ppm (RTi75) using an ultrasonic mixer. The effect of titanium dioxide on engine performance and exhaust emissions was experimentally determined by taking advantage of its photocatalysis effect and chemical reaction accelerator properties. Additionally, titanium dioxide additive reduced the viscosity and density of biodiesel fuel, resulting in higher micro explosion. According to the test results carried out at 4 different engine loads, brake specific fuel consumption decreased by 7.51% and 8.62% in RTi50 and RTi75 fuels compared to R0 fuel. Brake thermal efficiency increased by 2.47% and 6.21%, respectively. The improvement in combustion achieved by the nano additive increased the conversion of CO emissions into CO2, increased NOX emissions, reduced smoke emissions and caused more complete combustion products to come out of the exhaust.