An ICP-MS study on metal content in biodiesel and bioglycerol produced from heated and unheated canola oils.

This study addresses the challenges of biodiesel production costs and waste oil disposal by investigating the use of low-cost waste oil as a feedstock. The impact of heating temperature on biodiesel yield and trace metal levels is examined using response surface methodology (RSM). Optimal conditions for high biodiesel yields (95-98%) from canola oil are determined with a methanol/oil ratio of 12:1, 1 wt% catalyst, and 60-min reaction time. For crude bioglycerol, the optimal conditions involve a methanol/oil ratio of 4.25:1, 2.93 wt% catalyst, and 119.15-min reaction time. Elemental analysis reveals the presence of high-concentration metals like Cu and Zn and low-concentration ones such as Pb, As, Se, and Zr in both oil feedstocks and their respective biodiesel and bioglycerol products. The study demonstrates that thermal stress on canola oil significantly impacts biodiesel and bioglycerol yields and trace metal levels during the transesterification process. The findings contribute to enhancing cost-effectiveness and environmental sustainability in biodiesel production.

Synthesis of Mesoporous Carbon Adsorbents Using Biowaste Crude Glycerol as a Carbon Source via a Hard Template Method for Efficient CO2 Capture.

Biowaste utilization as a carbon source and its transformation into porous carbons have been of great interest to promote environmental remediation owing to biowaste's cost-effectiveness and useful physicochemical properties. In this work, crude glycerol (CG) residue from waste cooking oil transesterification was employed to fabricate mesoporous crude glycerol-based porous carbons (mCGPCs) using mesoporous silica (KIT-6) as a template. The obtained mCGPCs were characterized and compared to commercial activated carbon (AC) and CMK-8, a carbon material prepared using sucrose. The study aimed to evaluate the potential of mCGPC as a CO2 adsorbent and demonstrated its superior adsorption capacity compared to AC and comparable to CMK-8. The X-ray diffraction (XRD) and Raman results clearly depicted the structure of carbon nature with (002) and (100) planes and defect (D) and graphitic (G) bands, respectively. The specific surface area, pore volume, and pore diameter values confirmed the mesoporosity of mCGPC materials. The transmission electron microscopy (TEM) images also clearly revealed the porous nature with the ordered mesopore structure. The mCGPCs, CMK-8, and AC materials were used as CO2 adsorbents under optimized conditions. The mCGPC adsorption capacity (1.045 mmol/g) is superior to that of AC (0.689 mmol/g) and still comparable to that of CMK-8 (1.8 mmol/g). The thermodynamic analyses of the adsorption phenomena are also carried out. This work demonstrates the successful synthesis of a mesoporous carbon material using a biowaste (CG) and its application as a CO2 adsorbent.

Benzimidazole-Piperazine-Coumarin/Cucurbit[7]uril Supramolecular Photoinduced Electron Transfer Fluorochromes for Detection of Carnosol by Stimuli-Responsive Dye Displacement and pK a Tuning.

A new fluorescent dye (4PBZC) comprising coumarin (C), piperazine (P), and benzimidazole (BZ) was designed, prepared, and complexed to cucurbit[7]uril (CB7) to detect carnosol (CAR), an anti-breast cancer drug, in sub-nanomolar concentrations utilizing the supramolecular indicator displacement assay strategy, the CB7-assisted pK a shift, and the CB7-retarded photoinduced electron transfer process. The host-guest complexation was confirmed by UV-visible absorption, fluorescence, and 1H NMR spectroscopy, which established the binding of 4PBZC to CB7. CB7 preferentially binds the indicator dye (4PBZC) via the protonated BZ residue compared to the neutral BZ one, demonstrated by a higher binding constant of the complex in its di-protonated form, which led to an increase in the pK a of the BZ moiety by ca. 3.0 units after the addition of CB7. In aqueous solution (pH 6), switching the emission signals between 4PBZH+C/CB7 (ON state) and 4PBZC (OFF state) was achieved by displacement of the protonated dye from the cavity of CB7 by the CAR analyte. An efficient sensor was obtained for the sensitive detection of CAR in aqueous solution with a low detection limit of 0.148 ng/mL (0.45 nM) and a linear range from 20 to 627 ng/mL.

Photoinduced Electron Transfer in Encapsulated Heterocycles by Cavitands.

Host-guest complexation of small heterocyclic (guest) and macrocyclic cavitands (hosts) organic molecules is still to date a very popular, inexpensive approach that bypasses the burdens of conventional covalent synthesis. Understanding the selection criteria of these chemicals is crucial to the design and potential applications of their supramolecular assemblies. This review surveys examples within the last 15 years (2005-2020) of supramolecular complexes in which the interacting photoinduced electron transfer (PET)-based chromophore and quencher fragments are commonly used in the market with reported CAS numbers. It appears from this survey that the supramolecular effects can be directed to specifically disrupt PET when the nonemissive macrocycles separately encapsulate the fluorescent acceptor or donor molecules, among other specific factors, such as when inducing conformational changes or pKa shift of the donor. On the contrary, synergetic encapsulation of both donor and acceptor molecules, formation of ternary self-assembly at the rim or encapsulation of one component while grafting the other onto the macrocycle, among other specific factors such as the modulation of the excited-state structure of donor, will lead to the enhancement of PET process. In the event the donor or acceptor molecules have multitopic structures, the PET process can repeatedly be switched on and off. It is generally concluded that understanding the criteria for the combination of these available products for the purpose of manipulating their PET efficiency should pave the way for the facile alternative generation of new noncovalently bonded host-guest supramolecular assemblies with a more specific design tailored for more advanced, diverse and economic applications such as chemical sensing, molecular gates, drug delivery and biolabeling.

Encapsulation of Cinnamic Acid by Cucurbit[7]uril for Enhancing Photoisomerization.

Cis- or Z-configuration is required for the plant growth-promoting activity of cinnamic acid (CA), whereas the E-form is inactive. Herein, we describe the encapsulation of E-CA by cucurbit[7]uril (CB7) and show that photoisomerization reactions can be more efficiently controlled in aqueous solutions by utilizing this supramolecular approach. Measurements of UV-visible absorption and proton NMR spectra at different pH values confirm that E-CA and its methyl ester, methyl-E-cinnamate (MC), form stronger 1:1 host-guest complexes with CB7 compared to cucurbit[8]uril (CB8) or three cyclodextrins (α-, ß-, and γ-CD). Irradiation of (300 nm) UV light to an aqueous solution of the CB7-bound E isomers induces E to Z photoisomerization and the dissociation of the complex. When the same solution is irradiated by (254 nm) UV light, Z to E conformational changes of the unbound Z isomers are observed and are accompanied by restoring the host-guest complex formation.