Dimethylformamide dimethyl acetal in heterocyclic synthesis: Synthesis of polyfunctionally substituted pyridine derivatives as precursors to bicycles and polycycles

Polysubstituted pyridines 11a,c and 12 were prepared by the reaction of benzoylacetone with dimethylformamide dimethyl acetal followed by treatment with cyanothioacetamide 9a , cyanoacetamide 9b and the anion of malononitrile dimmer 9c in dry DMF. When the reaction was carried out in ethanol as a solvent and piperidine as a base afforded 14a,b . Thienopyridines 16a,b were prepared by the reaction of pyridinethiones 11a and 14a with 2‐chloro‐N‐p‐tolyl‐acetamide ( 15 ). Further reaction of thienopyridines 16a,b with either DMFDMA or nitrous acid to gave 17a,b and 18a,b respectively. The reaction of pyridine derivative 11c with hydrazine and phenylhydrazine afforded the tricyclic compounds 19a,b .     

Inhibition of UVB-mediated oxidative stress and markers of photoaging in immortalized HaCaT keratinocytes by pomegranate polyphenol extract POMx

In recent years there has been an increase in use of botanicals with antioxidant properties as skin photoprotective agents. Pomegranate (Punica granatum L.) fruit possesses strong antioxidant and antiinflammatory properties. Recently, we have shown that pomegranate-derived products rich in anthocyanidins and ellagitannins inhibit UVB-mediated activation of nuclear factor kappa B and modulate UVA-mediated cell proliferation pathways in normal human epidermal keratinocytes. In this study, we evaluated the effect of polyphenol-rich pomegranate fruit extract (POMx) on UVB-induced oxidative stress and photoaging in human immortalized HaCaT keratinocytes. Our data show that pretreatment of HaCaT cells with POMx (10-40 microg mL(-1)) inhibited UVB (15-30 mJ cm(-2))-mediated (1) decrease in cell viability, (2) decrease in intracellular glutathione content and (3) increase in lipid peroxidation. Employing immunoblot analysis we found that pretreatment of HaCaT cells with POMx inhibited UVB-induced (1) upregulation of MMP-1, -2, -7 and -9, (2) decrease in TIMP-1, (3) phosphorylation of MAPKs and (iv) phosphorylation of c-jun, whereas no effect was observed on UVB-induced c-fos protein levels. These results suggest that POMx protects HaCaT cells against UVB-induced oxidative stress and markers of photoaging and could be a useful supplement in skin care products.     

Development of Antibacterial,Degradable and pH-Responsive Chitosan/Guar Gum/Polyvinyl Alcohol Blended Hydrogels for Wound Dressing

The present research is based on the fabrication preparation of CS/PVA/GG blended hydrogel with nontoxic tetra orthosilicate (TEOS) for sustained paracetamol release. Different TEOS percentages were used because of their nontoxic behavior to study newly designed hydrogels’ crosslinking and physicochemical properties. These hydrogels were characterized using Fourier-transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), and wetting to determine the functional, surface morphology, hydrophilic, or hydrophobic properties. The swelling analysis in different media, degradation in PBS, and drug release kinetics were conducted to observe their response against corresponding media. The FTIR analysis confirmed the components added and crosslinking between them, and surface morphology confirmed different surface and wetting behavior due to different crosslinking. In various solvents, including water, buffer, and electrolyte solutions, the swelling behaviour of hydrogel was investigated and observed that TEOS amount caused less hydrogel swelling. In acidic pH, hydrogels swell the most, while they swell the least at pH 7 or higher. These hydrogels are pH-sensitive and appropriate for controlled drug release. These hydrogels demonstrated that, as the ionic concentration was increased, swelling decreased due to decreased osmotic pressure in various electrolyte solutions. The antimicrobial analysis revealed that these hydrogels are highly antibacterial against Gram-positive (Staphylococcus aureus and Bacillus cereus) and Gram negative (Pseudomonas aeruginosa and Escherichia coli) bacterial strains. The drug release mechanism was 98% in phosphate buffer saline (PBS) media at pH 7.4 in 140 min. To analyze drug release behaviour, the drug release kinetics was assessed against different mathematical models (such as zero and first order, Higuchi, Baker–Lonsdale, Hixson, and Peppas). It was found that hydrogel (CPG2) follows the Peppas model with the highest value of regression (R² = 0.98509). Hence, from the results, these hydrogels could be a potential biomaterial for wound dressing in biomedical applications.     

Influence of gamma radiation on the absorption spectra and optical energy gap of Li‐ doped ZnO thin films

We have studied the effect of subsequent gamma (γ) irradiation on the absorption spectra and the optical energy gap of ZnO thin films doped with Li (ZnO:Li). The optical transmission (T) and optical reflection (R) in the wavelength range 190∼800 nm of films deposited at 300 °C on sapphire, MgO or quartz substrates were measured. The dependence of the absorption coefficient α on photon energy hν was determined as a function of γ‐doses. The films show direct allowed interband transition that influenced by the gamma doses. Both the optical energy gap E^opt_g and the absorption coefficient (α) were found to be γ‐dose dependent. The results can be discussed on the basis of γ‐irradiation‐induced defects in the film and on the film structure. The absorption coefficient exhibits exponential dependence on photon energy obeying Urbach's rule in the absorption edge. (© 2004 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Fabrication and Mechanical Performance of Non-Crimp Unidirectional Jute-Yarn Preform-Based Composites

This work developed novel jute-yarn, non-crimp, unidirectional (UD) preforms and their composites, with three different types of warp jute yarns of varying linear densities and twists in the dry UD preforms, in order to present a possible solution to the detrimental effects of higher yarn twists and crimp at the warp–weft yarn interlacements of traditional, woven, preform-based composites on their mechanical properties. In the developed UD preforms, warp jute yarns were placed in parallel by using a wooden picture-frame pin board, with the minimal number of glass weft yarns to avoid crimp at the warp–weft yarns interlacements, which can significantly enhance the load-bearing ability of UD composites compared to traditional, woven, preform composites. It was found that an optimal combination of jute warp yarn linear densities and twists in the UD preforms is important to achieve the best possible mechanical properties of newly developed UD composites, because it encourages a proper polymer-matrix impregnation on jute fibres, leading to excellent fibre–matrix interface bonding. Composites made from the 25 lb/spindle jute warp yarn linear density (UD25) exhibited higher tensile and flexural properties than other UD composites (UD20, UD30). All the UD composites showed a much better performance compared to the traditional woven preform composites (W20), which were obviously related to the higher crimp and yarn interlacements, less load-carrying capacity, and poor fiber–matrix interfaces of W20 composites. UD25 composites exhibited a significant enhancement in tensile modulus by ~232% and strength by ~146%; flexural modulus by 138.5% and strength by 145% compared to W20 composites. This reveals that newly developed, non-crimp, UD preform composites can effectively replace the traditional woven composites in lightweight, load-bearing, complex-shaped composite applications, and hence, this warrants further investigations of the developed composites, especially on long-term and dynamic-loading mechanical characterizations.     

Study of Antibacterial and Anticancer Properties of bioAgNPs Synthesized Using Streptomyces sp. PBD-311B and the Application of bioAgNP-CNC/Alg as an Antibacterial Hydrogel Film against P. aeruginosa USM-AR2 and MRSA

Here, we report the extracellular biosynthesis of silver nanoparticles (AgNPs) and determination of their antibacterial and anticancer properties. We also explore the efficacy of bioAgNPs incorporated in cellulose nanocrystals (CNCs) and alginate (Alg) for the formation of an antibacterial hydrogel film. Streptomyces sp. PBD-311B was used for the biosynthesis of AgNPs. The synthesized bioAgNPs were characterized using UV-Vis spectroscopy, TEM, XRD, and FTIR analysis. Then, the bioAgNPs’ antibacterial and anticancer properties were determined using TEMA and cytotoxicity analysis. To form the antibacterial hydrogel film, bioAgNPs were mixed with a CNC and Alg solution and further characterized using FTIR analysis and a disc diffusion test. The average size of the synthesized bioAgNPs is around 69 ± 2 nm with a spherical shape. XRD analysis confirmed the formation of silver nanocrystals. FTIR analysis showed the presence of protein capping at the bioAgNP surface and could be attributed to the extracellular protein binding to bioAgNPs. The MIC value of bioAgNPs against P. aeruginosa USM-AR2 and MRSA was 6.25 mg/mL and 3.13 mg/mL, respectively. In addition, the bioAgNPs displayed cytotoxicity effects against cancer cells (DBTRG-0.5MG and MCF-7) and showed minimal effects against normal cells (SVG-p12 and MCF-10A), conferring selective toxicity. Interestingly, the bioAgNPs still exhibited inhibition activity when incorporated into CNC/Alg, which implies that the hydrogel film has antibacterial properties. It was also found that bioAgNP-CNC/Alg displayed a minimal or slow release of bioAgNPs owing to the intermolecular interaction and the hydrogel’s properties. Overall, bioAgNP-CNC/Alg is a promising antibacterial hydrogel film that showed inhibition against the pathogenic bacteria P. aeruginosa and MRSA and its application can be further evaluated for the inhibition of cancer cells. It showed benefits for surgical resection of a tumor to avoid post-operative wound infection and tumor recurrence at the surgical site.     

Electronic absorption spectra of some nicotinamides and nicotinic acids. Molecular orbital treatment

The electronic absorption spectra of the position isomers nicotinamide and isonicotinamide, nicotinic acid, and isonicotinic acid were investigated, together with the spectra of thionicotinamide, N-methyl nicotinamide and nicotinic acid N oxide. Apparent differences in the spectra of the position isomers were interpreted in terms of the torsion angle between the planes of the molecule, the height of the barrier to internal rotation, and the results of molecular orbital (MO) calculations. The largest perturbation effect was observed in the case of thionicotinamide whereas the smallest effect was observed in the case of nicotinic acid N oxide. MO calculations have indicated the existence of overlapping transitions. The observed transitions proved to be π-π* transitions, none of the n-π* was observed. © 1997 John Wiley & Sons, Inc. Int J Quant Chem 64 : 689–701, 1997     

MHD Stagnation Point on Nanofluid Flow and Heat Transfer of Carbon Nanotube over a Shrinking Surface with Heat Sink Effect

This study is to investigate the magnetohydrodynamic (MHD) stagnation point flow and heat transfer characteristic nanofluid of carbon nanotube (CNTs) over the shrinking surface with heat sink effects. Similarity equations deduced from momentum and energy equation of partial differential equations are solved numerically. This study looks at the different parameters of the flow and heat transfer using first phase model which is Tiwari-Das. The parameter discussed were volume fraction nanoparticle, magnetic parameter, heat sink/source parameters, and a different type of nanofluid and based fluids. Present results revealed that the rate of nanofluid (SWCNT/kerosene) in terms of flow and heat transfer is better than (MWCNT/kerosene) and (CNT/water) and regular fluid (water). Graphically, the variation results of dual solution exist for shrinking parameter in range λc<λ≤−1 for different values of volume fraction nanoparticle, magnetic, heat sink parameters, and a different type of nanofluid. However, a unique solution exists at −1<λ<1, and no solutions exist at λ<λc which is a critical value. In addition, the local Nusselt number decreases with increasing volume fraction nanoparticle when there exists a heat sink effect. The values of the skin friction coefficient and local Nusselt number increase for both solutions with the increase in magnetic parameter. In this study, the investigation on the flow and heat transfer of MHD stagnation point nanofluid through a shrinking surface with heat sink effect shows how important the application to industrial applications.     

The Effect of Wall Material Type on the Encapsulation Efficiency and Oxidative Stability of Fish Oils

Fish oil is the primary source of long-chain omega-3 fatty acids, which are important nutrients that assist in the prevention and treatment of heart disease and have many health benefits. It also contains vitamins that are lipid-soluble, such as vitamins A and D. This work aimed to determine how the wall material composition influenced the encapsulation efficiency and oxidative stability of omega fish oils in spray-dried microcapsules. In this study, mackerel, sardine waste oil, and sand smelt fish oil were encapsulated in three different wall materials (whey protein, gum Arabic (AG), and maltodextrin) by conventional spray-drying. The effect of the different wall materials on the encapsulation efficiency (EE), flowability, and oxidative stability of encapsulated oils during storage at 4 °C was investigated. All three encapsulating agents provided a highly protective effect against the oxidative deterioration of the encapsulated oils. Whey protein was found to be the most effective encapsulated agent comparing to gum Arabic and maltodextrin. The results indicated that whey protein recorded the highest encapsulation efficiency compared to the gum Arabic and maltodextrin in all encapsulated samples with EE of 71.71%, 68.61%, and 64.71% for sand smelt, mackerel, and sardine oil, respectively. Unencapsulated fish oil samples (control) recorded peroxide values (PV) of 33.19, 40.64, and 47.76 meq/kg oil for sand smelt, mackerel, and sardine oils after 35 days of storage, while all the encapsulated samples showed PV less than 10 in the same storage period. It could be concluded that all the encapsulating agents provided a protective effect to the encapsulated fish oil and elongated the shelf life of it comparing to the untreated oil sample (control). The results suggest that encapsulation of fish oil is beneficial for its oxidative stability and its uses in the production of functional foods.     

Scale-up and Sustainability Evaluation of Biopolymer Production from Citrus Waste Offering Carbon Capture and Utilisation Pathway

Poly(limonene carbonate) (PLC) has been highlighted as an attractive substitute to petroleum derived plastics, due to its utilisation of CO₂ and bio-based limonene as feedstocks, offering an effective carbon capture and utilisation pathway. Our study investigates the techno-economic viability and environmental sustainability of a novel process to produce PLC from citrus waste derived limonene, coupled with an anaerobic digestion process to enable energy cogeneration and waste recovery maximisation. Computational process design was integrated with a life cycle assessment to identify the sustainability improvement opportunities. PLC production was found to be economically viable, assuming sufficient citrus waste is supplied to the process, and environmentally preferable to polystyrene (PS) in various impact categories including climate change. However, it exhibited greater environmental burdens than PS across other impact categories, although the environmental performance could be improved with a waste recovery system, at the cost of a process design shift towards energy generation. Finally, our study quantified the potential contribution of PLC to mitigating the escape of atmospheric CO₂ concentration from the planetary boundary. We emphasise the importance of a holistic approach to process design and highlight the potential impacts of biopolymers, which is instrumental in solving environmental problems facing the plastic industry and building a sustainable circular economy.