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Switchable nonlinear optical (NLO) materials have widespread applications in electronics and optoelectronics. Thermo-switches generate many times higher NLO responses as compared to photo-switches. Herein, we have investigated the geometric, electronic, and nonlinear optical properties of spiropyranes thermochromes via DFT methods. The stabilities of close and open isomers of selected spiropyranes are investigated through relative energies. Electronic properties are studied through frontier molecular orbitals (FMOs) analysis. The lower HOMO-LUMO energy gap and lower excitation energy are observed for open isomers of spiropyranes, which imparts the large first hyperpolarizability value. The delocalization of π-electrons, asymmetric distribution and elongated conjugation system are dominant factors for high hyperpolarizability values of open isomers. For deep understanding, we also analyzed the frequency-dependent hyperpolarizability and refractive index of considered thermochromes. The NLO response increased significantly with increasing frequency. Among all those compounds, the highest refractive index value is observed for the open isomer of the spiropyran 1 (1.99 × 10−17 cm2/W). Molecular absorption analysis confirmed the electronic excitation in the open isomers compared to closed isomers. The results show that reversible thermochromic compounds act as excellent NLO molecular switches and can be used to design advanced electronics. [ABSTRACT FROM AUTHOR]

Biochar was prepared by the hydrothermal carbonization (HTC) of palm leaves, characterized, and utilized as an adsorbent for Malachite Green dye (MG). The Higher Heating Value (HHV) of biochar depends on the carbonization temperature and has a maximum value of 24.81 MJ/kg. Activation using H2O2 oxidation of HTC biochar prepared at 208 °C produced AHTC with improved capacity. The optimum pH was found to be in the range 7–8. Freundlich, Langmuir, Temkin, and Dubinin–Radushkevich adsorption isotherms were used to study MG adsorption data. The Langmuir isotherm provided the best fit for experimental data. Experiments conducted using activated biochar AHTC at 25 °C resulted in an adsorption capacity of 62.80 mg/g, far greater than what was observed for HTC biochar (45.59 mg/g). The maximum adsorption capacity was 88% when the concentration of MG solution was 66 ppm. The free energy change in adsorption DG° indicated that the adsorption process was spontaneous. Adsorption followed pseudo-second-order kinetics. Fixed-column adsorptions models, namely, Thomas, Yan et al. and Yoon–Nelson models, were investigated for AHTC. The column adsorption capacity determined by the Thomas model was 33.57 mg/g. In addition, a computational investigation has been carried out to determine the structural and electronic features, as well as the quantum chemical parameters of HTC and MG. Moreover, the interaction between the HTC and MG is investigated, which is further elaborated by performing non-covalent interaction (NCI) through the reduced density gradient (RDG) analysis. Thus, the easily prepared hydrochar from abundant waste palm leaves can be used as a high-value biocoal and efficient adsorbent of the cationic dye malachite green. [ABSTRACT FROM AUTHOR]

The toxicity of transition metals, including copper(II), manganese(II), iron(II), zinc(II), hexavalent chromium, and cobalt(II), at elevated concentrations presents a significant threat to living organisms. Thus, the development of efficient sensors capable of detecting these metals is of utmost importance. This study explores the utilization of two-dimensional nitrogenated holey graphene (C2N) nanosheet as a sensor for toxic transition metals. The C2N nanosheet's periodic shape and standard pore size render it well suited for adsorbing transition metals. The interaction energies between transition metals and C2N nanosheets were calculated in both gas and solvent phases and were found to primarily result from physisorption, except for manganese and iron which exhibited chemisorption. To assess the interactions, we employed NCI, SAPT0, and QTAIM analyses, as well as FMO and NBO analysis, to examine the electronic properties of the TM@C2N system. Our results indicated that the adsorption of copper and chromium significantly reduced the HOMO–LUMO energy gap of C2N and significantly increased its electrical conductivity, confirming the high sensitivity of C2N towards copper and chromium. The sensitivity test further confirmed the superior sensitivity and selectivity of C2N towards copper. These findings offer valuable insight into the design and development of sensors for the detection of toxic transition metals. [ABSTRACT FROM AUTHOR]

Electronic and nonlinear optical properties of endohedral metallofullerenes are presented. The endohedral metallofullerenes contain transition metal encapsulated in inorganic fullerenes X12Y12 (X = B, Al & Y = N, P). The endohedral metallofullerenes (endo-TM@X12Y12) possess quite interesting geometric and electronic properties, which are the function of the nature of the atom and the size of fullerene. NBO charge and frontier molecular orbital analyses reveal that the transition metal encapsulated Al12N12 fullerenes (endo-TM@Al12N12) are true metalides when the transition metals are Ni, Cu and Zn. Endo-Cr@Al12N12 and endo-Co@Al12N12 are at the borderline between metalides and electrides with predominantly electride characteristics. The other members of the series are excess electron systems, which offer interesting electronic and nonlinear optical properties. The diversity of nature possessed by endo-TM@Al12N12 is not prevalent for other fullerenes. Endo-TM@Al12P12 are true metalides when the transition metals are (Cr-Zn). HOMO-LUMO gaps (EH-L) are reduced significantly for these endohedral metallofullerenes, with a maximum percent decrease in EH-L of up to 70%. Many complexes show odd–even oscillating behavior for EH-L and dipole moments. Odd electron species contain large dipole moments and small EH-L, whereas even electron systems have the opposite behavior. Despite the decrease in EH-L, these systems show high kinetic and thermodynamic stabilities. The encapsulation of transition metals is a highly exergonic process. These endo-TM@X12Y12 possess remarkable nonlinear optical response in which the first hyperpolarizability reaches up to 2.79 × 105 au for endo-V@Al12N12. This study helps in the comparative analysis of the potential nonlinear optical responses of electrides, metalides and other excess electron systems. In general, the potential nonlinear optical response of electrides is higher than metalides but lower than those of simple excess electron compounds. The higher non-linear optical response and interesting electronic characteristics of endo-TM@Al12N12 complexes may be promising contenders for potential NLO applications. [ABSTRACT FROM AUTHOR]

The over-exploitation of groundwater resources is a significant concern due to the potential risks associated with the depletion of this valuable freshwater source. Future planning must consider changes in groundwater availability and urban expansion which are critical for understanding urban growth patterns. This study aims to investigate the impact of land cover change on groundwater depletion. Further, the Land surface temperature (LST) analysis has been performed to find the spatial spread of urbanization and its impact on surface temperature. The Gravity Recovery and Climate Experiment (GRACE) data for groundwater storage monitoring and Landsat data for land cover and LST mapping have been used. The GRACE-based Groundwater Storage (GWS) anomaly has been correlated with Tropical Rainfall Measuring Mission (TRMM)-based precipitation data. The GWS is further cross validated with the groundwater monitoring stations in the study area and the correlation of 0.7 is found. The time series analysis of GWS and the land cover maps with a decadal interval from 1990 to 2020 has been developed to find the impact of groundwater change due to urbanization. The results demonstrate a rapid increase in groundwater depletion and urbanization rates over the past decade. The LST spatial pattern is increasing similarly with the study area's urban expansion, indicating the temperature rise due to urbanization. The study highlights the limitation of effective policies to regulate groundwater extraction in urban areas and the importance of proper planning to ensure the long-term sustainability of freshwater resources. [ABSTRACT FROM AUTHOR]

Zigzag molecular nanobelts have recently captured the interest of scientists because of their appealing aesthetic structures, intriguing chemical reactivities, and tantalizing features. In the current study, first-row transition metals supported on an H6-N3-belt[6]arene nanobelt are investigated for the electrocatalytic properties of these complexes for the hydrogen dissociation reaction (HDR). The interaction of the doped transition metal atom with the nanobelt is evaluated through interaction energy analysis, which reveals the significant thermodynamic stability of TM-doped nanobelt complexes. Electronic properties such as frontier molecular orbitals and natural bond orbitals analyses are also computed, to estimate the electronic perturbation upon doping. The highest reduction in the HOMO–LUMO energy gap compared to the bare nanobelt is seen in the case of the Zn@NB catalyst (4.76 eV). Furthermore, for the HDR reaction, the Sc@NB catalyst displays the best catalytic activity among the studied catalysts, with a hydrogen dissociation barrier of 0.13 eV, whereas the second-best catalytic activity is observed for the Zn@NB catalyst (0.36 eV). It is further found that multiple active sites, i.e., the presence of the metal atom and nitrogen atom moiety, help to facilitate the dissociation of the hydrogen molecule. These key findings of this study enhance the understanding of the relative stability, electronic features, and catalytic bindings of various TM@NB catalysts. [ABSTRACT FROM AUTHOR]

Carbon-based polynuclear clusters are designed and investigated for geometric, electronic, and nonlinear optical (NLO) properties at the CAM-B3LYP/6-311++G(d,p) level of theory. Significant binding energies per atom (ranging from −162.4 to −160.0 kcal mol−1) indicate excellent thermodynamic stabilities of these polynuclear clusters. The frontier molecular orbital (FMOs) analysis indicates excess electron nature of the clusters with low ionization potential, suggesting that they are alkali-like. The decreased energy gaps (EH-L) with increased alkali metals size revael the improved electrical conductivity (σ). The total density of state (TDOS) study reveals the alkali metals' size-dependent electronic and conductive properties. The significant first and second hyperpolarizabilities are observed up to 5.78 × 103 and 5.55 × 106 au, respectively. The βo response shows dependence on the size of alkali metals. Furthermore, the absorption study shows transparency of these clusters in the deep-UV, and absorptions are observed at longer wavelengths (redshifted). The optical gaps from TD-DFT are considerably smaller than those of HOMO-LUMO gaps. The significant scattering hyperpolarizability (βHRS) value (1.62 × 104) is calculated for the C3 cluster, where octupolar contribution to βHRS is 92%. The dynamic first hyperpolarizability β(ω) is more pronounced for the EOPE effect at 532 nm, whereas SHG has notable values for second hyperpolarizability γ(ω). [ABSTRACT FROM AUTHOR]

The building sector is targeting net-zero emissions through the integration of renewable energy technologies, especially for space cooling and heating applications. In this regard, the use of solar thermal concentrating collectors is of vital importance. The performance of these collectors increases by using an efficient fluid such as a nanofluid due to their high thermal conductivity. This research addresses the preparation, stability analysis, and characterisation of metallic and non-metallic oxide nanofluids and their experimental analysis in a compound parabolic collector (CPC) system. Five different combinations of nanofluids are used with different volumetric concentrations (0.025%, 0.05%, and 0.075%) including multi-wall carbon nanotube with water (MWCNT–H2O), multi-wall carbon nanotube with ethylene glycol (MWCNT–EG), aluminium oxide with water (Al2O3–H2O), aluminium oxide with ethylene glycol (Al2O3–EG), and magnesium oxide with ethylene glycol (MgO–EG). The prepared nanofluids are characterised in terms of thermal conductivity and viscosity. Detailed experimentation is performed to investigate the CPC system integrated with the nanofluids. The results obtained from the detailed characterisation of the MWCNT–H2O nanofluid showed that the nanofluids have a 37.17% better thermal conductivity than distilled water as a primary fluid, and the MWCNT–EG nanofluid has demonstrated an increase in viscosity by 8.5% compared to ethylene glycol (EG). The experimental analysis revealed that the thermal efficiency of the collector integrated with the MWCNT–H2O nanofluid is increased by 33% compared to water. Meanwhile, the thermal efficiency of the collector with MWCNT–EG was increased by 24.9% compared to EG. Moreover, a comparative analysis among metallic nanofluids was also performed, i.e., Al2O3–H2O, Al2O3–EG, and MgO–EG. In each case, the thermal efficiency of the collector was recorded, which was greater than the base fluid by percentages of 29.4%, 22.29%, and 23.1%, respectively. The efficiency of non-metallic nanofluids is better than metallic nanofluids by 7.7%. From the obtained results, it can be concluded that the CPC system performed best with MWCNT–H2O compared to any other combination of nanofluids. [ABSTRACT FROM AUTHOR]

V-series nerve agents are very lethal to health and cause the inactivation of acetylcholinesterase which leads to neuromuscular paralysis and, finally, death. Therefore, rapid detection and elimination of V-series nerve agents are very important. Herein, we have carried out a theoretical investigation of carbon nitride quantum dots (C2N) as an electrochemical sensor for the detection of V-series nerve agents, including VX, VS, VE, VG, and VM. Adsorption of V-series nerve agents on C2N quantum dots is explored at M05-2X/6-31++G(d,p) level of theory. The level of theory chosen is quite adequate in systems describing non-bonding interactions. The adsorption behavior of nerve agents is characterized by interaction energy, non-covalent interaction (NCI), Bader's quantum theory of atoms in molecules (QTAIM), frontier molecular orbital (FMO), electron density difference (EDD), and charge transfer analysis. The computed adsorption energies of the studied complexes are in the range of −12.93 to −17.81 kcal/mol, which indicates the nerve agents are physiosorbed onto C2N surface through non-covalent interactions. The non-covalent interactions between V-series and C2N are confirmed through NCI and QTAIM analysis. EDD analysis is carried out to understand electron density shifting, which is further validated by natural bond orbital (NBO) analysis. FMO analysis is used to estimate the changes in energy gap of C2N on complexation through HOMO-LUMO energies. These findings suggest that C2N surface is highly selective toward VX, and it might be a promising candidate for the detection of V-series nerve agents. [ABSTRACT FROM AUTHOR]

A novel approach was carried to prepare trans-CuCl2L2 complex with the ligand L, (E)-(4-chlorophenyl)-N-(3-phenyl-4H-1,2,4-triazol-4-yl)methanimine which was formed in situ during the reaction of CuCl2 with 4-(4-chlorobenzylideneamino)-5-phenyl-2H-1,2,4-triazole-3(4H)-thione. The synthesized compounds were characterized by applying various spectroscopic techniques. The crystal structure of the complex was unambiguously determined using X-ray analysis indicating square planar geometry. Intermolecular H-bonds govern the supramolecular structure of the copper complex. Aromatic rings are stacked in an offset packing due to occurrence of π–π interactions. The structure is further corroborated with a detailed computational investigation. A thione–thiol tautomerism for the triazole compound was also studied. The Schiff base 1,2,4-triazole copper chloride complex is expected to have high anticancer activity. [ABSTRACT FROM AUTHOR]

Currently, hydrogen is recognized as the best alternative for fossil fuels because of its sustainable nature and environmentally friendly processing. In this study, hydrogen dissociation reaction is studied theoretically on the transition metal doped carbon nitride (C2N) surface through single atom catalysis. Each TMs@C2N complex is evaluated to obtain the most stable spin state for catalytic reaction. In addition, electronic properties (natural bond orbital NBO & frontier molecular orbital FMO) of the most stable spin state complex are further explored. During dissociation, hydrogen is primarily adsorbed on metal doped C2N surface and then dissociated heterolytically between metal and nitrogen atom of C2N surface. Results revealed that theFe@C2N surface is the most suitable catalyst for H2 dissociation reaction with activation barrier of 0.36 eV compared with Ni@C2N (0.40 eV) and Co@C2N (0.45 eV) complexes. The activation barrier for H2 dissociation reaction is quite low in case of Fe@C2N surface, which is comparatively better than already reported noble metal catalysts. [ABSTRACT FROM AUTHOR]

The corrosion inhibition effect of the three extracts from Harmal roots (HRE), leaves (HLE), and flowers (HFE) were studied for carbon steel corrosion inhibition in 0.25 M H2SO4 solution. The electrochemical impedance study indicated that the three types of extracts decreased corrosion effectively through a charge transfer mechanism. Harmal roots and leaf extracts showed inhibition values of 94.1% and 94.2%, while it was 88.7% for Harmal flower extract at the inhibitor concentration of 82.6 ppm. Potentiodynamic polarization data revealed that Harmal extracts acted through predominant cathodic type inhibition. Both the corrosion current density and corrosion rate decreased significantly in the presence of Harmal extracts compared to blank solution. The corrosion rate (mpy) value was 63.3, 86.1, and 180.7 for HRE, HLE, and HFE, respectively. The adsorption-free energy change ΔGads (kJ·mol−1) values calculated from the Langmuir adsorption isotherm plots were for HRE (−35.08), HLE (−33.17), and HFE (−33.12). Thus, corrosion inhibition occurred due to the adsorption of Harmal extract on the carbon steel surface via the chemisorption mechanism. Moreover, a computational investigation using B3LYP/6-311G++(d,p) basis set in both gaseous and aqueous phases was performed for the major alkaloids (1–8) present in the Harmal extract. [ABSTRACT FROM AUTHOR]

Continuous studies are being carried out to explore new methods and carrier surfaces for target drug delivery. Herein, we report the covalent triazine framework C6N6 as a drug delivery carrier for fluorouracil (FU) and nitrosourea (NU) anti-cancer drugs. FU and NU are physiosorbed on C6N6 with adsorption energies of −28.14 kcal/mol and −27.54 kcal/mol, respectively. The outcomes of the non-covalent index (NCI) and quantum theory of atoms in molecules (QTAIM) analyses reveal that the FU@C6N6 and NU@C6N6 complexes were stabilized through van der Waals interactions. Natural bond order (NBO) and electron density difference (EDD) analyses show an appreciable charge transfer from the drug and carrier. The FU@C6N6 complex had a higher charge transfer (−0.16 e−) compared to the NU@C6N6 complex (−0.02 e−). Frontier molecular orbital (FMO) analysis reveals that the adsorption of FU on C6N6 caused a more pronounced decrease in the HOMO-LUMO gap (EH-L) compared to that of NU. The results of the FMO analysis are consistent with the NBO and EDD analyses. The drug release mechanism was studied through dipole moments and pH effects. The highest decrease in adsorption energy was observed for the FU@C6N6 complex in an acidic medium, which indicates that FU can easily be off-loaded from the carrier (C6N6) to a target site because the cancerous cells have a low pH compared to a normal cell. Thus, it may be concluded that C6N6 possesses the therapeutic potential to act as a nanocarrier for FU to treat cancer. Furthermore, the current study will also provide motivation to the scientific community to explore new surfaces for drug delivery applications. [ABSTRACT FROM AUTHOR]

In this work it is demonstrated that enantiomerically enriched N-alkyl 2-oxazolinylazetidines undergo exclusive α-lithiation, and that the resulting lithiated intermediate is chemically stable but configurationally labile under the given experimental conditions that afford enantioenriched N-alkyl-2,2-disubstituted azetidines. Although this study reveals the configurational instability of the diastereomeric lithiated azetidines, it points out an interesting stereoconvergence of such lithiated intermediates towards the thermodynamically stable species, making the overall process highly stereoselective (er > 95:5, dr > 85:15) after trapping with electrophiles. This peculiar behavior has been rationalized by considering the dynamics at the azetidine nitrogen atom, the inversion at the C-Li center supported by in situ FT-IR experiments, and DFT calculations that suggested the presence of η3-coordinated species for diastereomeric lithiated azetidines. The described situation contrasted with the demonstrated stability of the smaller lithiated aziridine analogue. The capability of oxazolinylazetidines to undergo different reaction patterns with organolithium bases supports the model termed "dynamic control of reactivity" of relevance in organolithium chemistry. It has been demonstrated that only 2,2-substituted oxazolinylazetidines with suitable stereochemical requirements could undergo C=N addition of organolithiums in non-coordinating solvents, leading to useful precursors of chiral (er > 95:5) ketoazetidines. [ABSTRACT FROM AUTHOR]

Energy-environmental planning for road transportation involves a vast investigation of vehicles' technologies and electricity production. However, in developing countries where the public transportation sector is growing quickly, energy-environmental planning is urgently needed. This paper evaluates the future electricity demand, as well as fuel consumption and CO2 emissions reduction, due to the operation of an expected increasing number of electric vehicles (EVs) in Pakistan. The planning of EVs up to 2040 is performed with the ePop simulator that calculates the future EVs' electricity demand, while EnergyPLAN® assesses the expected new power capacities. Two scenarios are investigated by penetrating 30% and 90% of 2/3 electric wheelers and cars by 2030 and 2040 compared to 2020, respectively. To fulfill the expected energy demand, PV in the daytime and the national electric grid at nighttime are here considered. Finally, a 9 GW of PV capacity is needed to satisfy the EVs' electricity demand of 14.7 TWh/year, and a 0.7 GW power plants capacity is needed to fulfill 4.7 TWh/year by 2040. Consequently, EVs' charging scenarios at daytime and nighttime are assessed. Results indicated a total reduction of 10.4 Mtonnes of CO2 emissions and 9.1 Mtoe of fuel consumption by 2040 in the transportation sector. [ABSTRACT FROM AUTHOR]

Water-in-oil droplets have huge importance in chemical and biotechnology applications, despite their difficulty being produced in microfluidics. Moreover, existing studies focus more on the different shape of microchannels instead of their size, which is one of the critical factors that can influence flow characteristics of the droplets. Therefore, the present work aims to study the behaviours of water-in-oil droplets at the interfacial surface in an offset T-junction microchannel, having different radiuses, using micro-PIV software. Food-grade palm olein and distilled water seeded with polystyrene microspheres particles were used as working fluids, and their captured images showing their generated droplets' behaviours focused on the junction of the respective microfluidic channel, i.e., radiuses of 400 µm, 500 µm, 750 µm and 1000 µm, were analysed via PIVlab. The increasing in the radius of the offset T-junction microchannel leads to the increase in the cross-sectional area and the decrease in the distilled water phase's velocity. The experimental velocity of the water droplet is in agreement with theoretical values, having a minimal difference as low as 0.004 mm/s for the case of the microchannel with a radius of 750 µm. In summary, a small increase in the channel's size yields a significant increase in the overall flow of a liquid. [ABSTRACT FROM AUTHOR]

This study discloses a method for painting artwork using a CO2 laser. The continuous-wave laser beam, at a predetermined heat flux and a predetermined number of laser beam passes, mixes and displaces the plurality of colored polymer-based compositions, respectively, by way of melting and vaporizing them. Experiments showed a great accuracy of colors and designed patterns between the computer aided design (CAD) drawing and what was achieved after laser discoloration. It was found that lower values of power and speed provide sufficient energy and time to make a melt pool of colors and cause their vaporization from the surface. A detailed numerical simulation was performed to obtain a detailed understanding of the physics of laser interaction with paint using ABAQUS software. The comparative analysis indicated that the top layer of paint (including yellow and green colors) melted upon increasing cutting speed and employing one laser pass. For blue and red paints, two passes of lasers are required; in the case of red color, lower laser speed is also necessary to intensify the heat. This method can be applied for making art designs on each surface color because it is based on melting and vaporization using a laser. [ABSTRACT FROM AUTHOR]

Laser-assisted high speed milling is a subtractive machining method that employs a laser to thermally soften a difficult-to-cut material's surface in order to enhance machinability at a high material removal rate with improved surface finish and tool life. However, this machining with high speed leads to high friction between workpiece and tool, and can result in high temperatures, impairing the surface quality. Use of conventional cutting fluid may not effectively control the heat generation. Besides, vegetable-based cutting fluids are invariably a major source of food insecurity of edible oils which is traditionally used as a staple food in many countries. Thus, the primary objective of this study is to experimentally investigate the effects of water-soluble sago starch-based cutting fluid on surface roughness and tool's flank wear using response surface methodology (RSM) while machining of 316 stainless steel. In order to observe the comparison, the experiments with same machining parameters are conducted with conventional cutting fluid. The prepared water-soluble sago starch based cutting fluid showed excellent cooling and lubricating performance. Therefore, in comparison to the machining using conventional cutting fluid, a decrease of 48.23% in surface roughness and 38.41% in flank wear were noted using presented approach. Furthermore, using the extreme learning machine (ELM), the obtained data is modeled to predict surface roughness and flank wear and showed good agreement between observations and predictions. [ABSTRACT FROM AUTHOR]

Water desalination presents a need to address the growing water-energy nexus. In this work, a literature survey is carried out, along an application of a mathematical model is presented to enhance the freshwater productivity rate of a solar-assisted humidification-dehumidification (HDH) type of desalination system. The prime novelty of this work is to recover the waste heat by reusing the feedwater at the exit of the condenser in the brackish water storage tank and to carry out the analysis of its effectiveness in terms of the system's yearly thermoeconomics. The developed mathematical model for each of the components of the plant is solved through an iterative procedure. In a parametric study, the influence of mass flow rates (MFRs) of inlet air, saline water, feedwater, and air temperature on the freshwater productivity is shown with and without the waste heat recovery from the condensing coil. It is reported that the production rate of water is increased to a maximum of 15% by recovering the waste heat. Furthermore, yearly analysis has shown that the production rate of water is increased to a maximum of 16% for June in the location of Taxila, Pakistan. An analysis is also carried out on the economics of the proposed modification, which shows that the cost per litre of the desalinated water is reduced by ~13%. It is concluded that the water productivity of an HDH solar desalination plant can be significantly increased by recovering the waste heat from the condensing coil. [ABSTRACT FROM AUTHOR]

An accumulating body of evidence reports the synthesis and biomedical applications of silver nanoparticles. However, the studies regarding the use of maleic acid and citric acid in the synthesis of nano-sized silver particles (AgNPs) and micro-sized silver particles (AgMPs) as well as their antibacterial, antifungal, and anticancer activities have not been reported. In the current study, we synthesized AgNPs and AgMPs using maleic acid and citric acid as capping agents and have characterized them by UV-Vis, energy-dispersive X-Ray spectroscopy (EDS), X-Ray diffraction (XRD), and scanning electron microscope (SEM) analysis. The capped silver particles were examined for their antimicrobial activity and cytotoxicity against bacteria, fungi, and brine shrimp. Additionally, the anticancer activity of these particles was tested against human breast and liver cancer cell lines. The free radical scavenging activity of capped silver particles was evaluated by 2,2-diphenyl-1-picrylhydrazyl (DPPH) assay. SEM analysis revealed a round plate-like morphology of maleic acid capped particles with an average size of 39 ± 4 nm, whereas citric acid capped particles display flower-shaped morphology with rough surfaces and an average size of 250 ± 5 nm. The uncapped AgMPs were hexagonal with 500 ± 4 nm size. EDS and XRD analysis confirmed the presence of Ag and face-centered cubic crystalline nature, respectively. Functionally, capped silver particles exhibited antibacterial activity against Gram-positive (Staphylococcus aureus, Bacillus subtilis, and Micrococcus luteus) and Gram-negative bacteria (Salmonella setubal, Enterobacter aerogenes, and Agrobacterium tumefaciens). The bactericidal activity was more active against Gram-negative bacteria with minimum inhibitory concentration (MIC) as low as 5 ppm as compared to 25 ppm for Gram-positive. Similarly, the silver particles demonstrated antifungal activity by inhibiting the growth of five fungal strains (Mucor species, Aspergillus niger, Aspergillus flavus, Aspergillus fumigatus, and Fusarium solani) up to 50% at the concentration of 500 ppm. Additionally, these particles showed substantial toxicity against brine shrimp and also significantly inhibited the proliferation of breast cancer (MCF7) and liver cancer (HePG2) cell lines (IC50 8.9–18.56 µM). Uncapped AgMPs were less effective, inhibiting only the proliferation of MCF7 cells with IC50 46.54 µM. Besides cytotoxicity, these particles acted as potential antioxidants, showing free radical scavenging up to 74.4% in a concentration-dependent manner. Taken together, our results showed that the modifiers affect the shape and size of silver particles and may, in part, contribute to the antimicrobial and antioxidant activity of silver particles. However, the contribution of maleic acid and citric acid in enhancing the antimicrobial, anticancer, and antioxidant potential independent of silver nano and microparticles needs to be studied further. In vivo experiments may determine the therapeutic effectiveness of silver particles capped with these modifiers. [ABSTRACT FROM AUTHOR]

This study focused on investigating the bottoming power cycles operating with CO2-based binary mixture, taking into account exergetic, economic and exergo-environmental impact indices. The main intent is to assess the benefits of employing a CO2-based mixture working fluid in closed Brayton bottoming power cycles in comparison with pure CO2 working fluid. Firstly, selection criteria for the choice of suitable additive compound for CO2-based binary mixture is delineated and the composition of the binary mixture is decided based on required cycle minimum temperature. The decided CO2-C7H8 binary mixture with a 0.9 mole fraction of CO2 is analyzed in two cycle configurations: Simple regenerative cycle (SRC) and Partial heating cycle (PHC). Comparative analysis among two configurations with selected working fluid are carried out. Thermodynamic analyses at varying cycle pressure ratio shows that cycle with CO2-C7H8 mixture shows maximum power output and exergy efficiency at rather higher cycle pressure ratio compared to pure CO2 power cycles. PHC with CO2-C7H8 mixture shows 28.68% increment in exergy efficiency with the levelized cost of electricity (LCOE) 21.62% higher than pure CO2 PHC. Whereas, SRC with CO2-C7H8 mixture shows 25.17% increment in exergy efficiency with LCOE 57.14% higher than pure CO2 SRC. Besides showing lower economic value, cycles with a CO2-C7H8 mixture saves larger CO2 emissions and also shows greater exergo-environmental impact improvement and plant sustainability index. [ABSTRACT FROM AUTHOR]

A plate fin heat exchanger (PFHE) is a critical part of the cryogenic industry. A plate fin heat exchanger has many applications, but it is commonly used in the liquefied natural gas (LNG) industry for the gasification/liquefaction process. During this gasification to the liquefaction process, there is a large temperature gradient. Due to this large temperature gradient, stresses are produced that directly influence the braze joint of PFHE. Significant work has been carried out on heat transfer and the flow enhancement of PFHE; however, little attention has been paid to structural stability and stresses produced in these brazed joints. Due to these stresses, leakages in PFHE are observed, mostly in braze joints. In the current study, standard fin design is analyzed. In addition, the structural stability of brazed joints under standard conditions is also tested. Two techniques are used here to analyze fins, using the finite element method (FEM), first by examining the whole fin brazed joint on the basis of experimentally calculated yield strength and second by dividing the braze seam into three sections and defining individual strength for each section of the seam to find stress magnitude on the basis of heat-affected zones. Moreover, by using two different techniques to analyze brazed joints, the stresses in the lower face of the brazed joint were increased by 13% and decreased by 18% in the upper face using different zone techniques as compared to standard full braze seam analysis. It can be concluded that different zone techniques are better in predicting stresses as compared to simple full braze seam analysis using the finite element method since stresses along the lower face are more critical. [ABSTRACT FROM AUTHOR]

Concrete is a non-Newtonian fluid which is a counterexample of Jeffrey fluid. The flow of Jeffrey fluid is considered containing nanostructures of zinc oxide in this study. The flow of the nanofluid is modeled in terms of partial fractional differential equations via Atangana–Baleanu (AB) fractional derivative approach and then solved using the integral transformation. Specifically, the applications are discussed in the field of concrete and cement industry. The variations in heat transfer rate and skin friction have been observed for different values of volume fractions of nanoparticles. The results show that by adding 4% Z n O nanoparticles increase skin friction up to 15%, ultimately enhancing the adhesion capacity of concrete. Moreover, Z n O increase the density of concrete, minimizing the pores in the concrete and consequently increasing the strength of concrete. The solutions are simplified to the corresponding solutions of the integer ordered model of Jeffrey-nanofluid. Applications of this work can be found in construction engineering and management such as buildings, roads, tunnels, bridges, airports, railroads, dams, and utilities. [ABSTRACT FROM AUTHOR]

In the present era, nanofluids are one of the most important and hot issue for scientists, physicists, and mathematicians. Nanofluids have many important and updated characteristics compared to conventional fluids. The thermal conductivity, thermal expansion, and the heat transfer rate of conventional fluids are not up to the mark for industrial and experimental uses. To overcome these deficiencies, nanoparticles have been dispersed into base fluids to make them more efficient. The heat transfer characteristics through symmetry trapezoidal-corrugated channels can be enhanced using nanofluids. In the present article, a literature survey has been presented for different models of nanofluids and their solutions—particularly, exact solutions. The models for hybrid nanofluids were also mentioned in the present study. Furthermore, some important and most used models for the viscosity, density, coefficient of thermal expansion, coefficient of mass expansion, heat capacitance, electrical conductivity, and thermal conductivity are also presented in tabular form. Moreover, some future suggestions are also provided in this article. [ABSTRACT FROM AUTHOR]

Liquefied natural gas (LNG) is one of the hydrocarbon fuels with the least carbon footprint having a rapidly rising global share in the prime energy market. LNG processing for transportation at longer distances works under cryogenic conditions, especially when used for liquefaction and gasification applications. The supply chain of the eco-environmental friendly hydrocarbon is heavily dependent on the processing plant used for liquefaction and subsequent re-gasification of the natural gas. Plate-fin heat exchangers are extensively used in the LNG industry for both re-gasification as well as liquefaction processes. The exchange of heat during the process of natural gas phase change involves plate-fin heat exchangers working under cryogenic low-temperature conditions. The heat exchangers are designed to have brazed joints that are most vulnerable to failure under these temperature conditions. One failure of such a joint can not only hinder the supply chain but also may result in fire and life hazards. In almost all earlier studies, analytical and numerical methods were used to analyze these braze joints using finite element method methods and examining the stresses while keeping them at or near to ambient conditions. In this research, the plate-fin heat exchanger is investigated for its structural stability of brazed fins for three different fin configurations: plain, wavy and compound having different joint geometries. In addition, the analyses are carried out using experimentally measured brazed joint strength which is measured to be on average 22% lower than the base material strength owing to brazing process and resultant heat-affected zone (HAZ). Therefore, the reliability is assessed for these joints in terms of factor of safety (FOS) while keeping in view the actual yield criteria. It was found that the structural stability of compound fins configuration is weakest amongst all considered fin configurations. The failure of the compound fin brazed joint is expected to be along the horizontal path of the joint due to yielding. The study also predicts the life of the fin brazed joints in different joining directions with different topologies of fins commonly recommended in the literature. It is observed that the commonly recommended safe fin geometries are predicted to be susceptible to failure if a reduction in the brazed joint is considered. The analysis and recommendation in this paper shall provide a reliable and safe design approach for plate-fin exchangers for different operating conditions especially in low to cryogenic temperature applications. [ABSTRACT FROM AUTHOR]

Processing of fossil fuels is the major environmental issue today. Biomass utilization for the production of chemicals presents an alternative to simple energy generation by burning. Lignocellulosic biomass (cellulose, hemicellulose and lignin) is abundant and has been used for variety of purposes. Among them, lignin polymer having phenyl-propanoid subunits linked together either through C-C bonds or ether linkages can produce chemicals. It can be depolymerized by fungi using their enzyme machinery (laccases and peroxidases). Both acetic acid and formic acid production by certain fungi contribute significantly to lignin depolymerization. Fungal natural organic acids production is thought to have many key roles in nature depending upon the type of fungi producing them. Biological conversion of lignocellulosic biomass is beneficial over physiochemical processes. Laccases, copper containing proteins oxidize a broad spectrum of inorganic as well as organic compounds but most specifically phenolic compounds by radical catalyzed mechanism. Similarly, lignin peroxidases (LiP), heme containing proteins perform a vital part in oxidizing a wide variety of aromatic compounds with H2O2. Lignin depolymerization yields value-added compounds, the important ones are aromatics and phenols as well as certain polymers like polyurethane and carbon fibers. Thus, this review will provide a concept that biological modifications of lignin using acidophilic fungi can generate certain value added and environmentally friendly chemicals. [ABSTRACT FROM AUTHOR]

The incorporation of a Maisotsenko (M) Cycle into an indirect evaporative cooler has led to the achievement of sub-wet bulb temperature without any humidification, thus making it a possible green and sustainable alternative for handling the cooling load of a building. In this work, the thermal performance of a cross-flow heat and mass exchanger (HMX) is enhanced by the addition of nanoparticles in the wet channel because they significantly influence the heat and mass transfer characteristics of the base fluid. A governing model for the temperature and humidity variations of the HMX is numerically simulated. Initial benchmarking is achieved using water properties. Afterward, a comparative study is conducted using aluminum-oxide-, copper-oxide-, and titanium-oxide-based nanofluids. Enhancements of 24.2% in heat flux, 19.24% in wet bulb effectiveness, 7.04% in dew point effectiveness, 29.66% in cooling capacity, and 28.43% in energy efficiency ratio are observed by using alumina-based nanofluid as compared to water in the wet channel of the cross-flow HMX. Furthermore, a particle volume concentration of 1% and a particle diameter of 20nm are recommended for maximum performance. [ABSTRACT FROM AUTHOR]

Small-CHP (Combined Heat and Power) systems are generally considered a valuable technological option to the conventional boilers, in a technology developed context. If small-CHP systems are associated with the use of renewable energies (biomass, for example) they could play an important role in distributed generation even in developing countries or, in any case, where there are no extensive electricity networks. Traditionally the considered heat engines for micro- or mini-CHP are: the gas engine, the gas turbine (with internal combustion), the steam engine, engine working according to the Stirling and to the Rankine cycles, the last with organic fluids. In principle, also fuel cells could be used. In this paper, we focus on small size Rankine cycles (10–15 k W ) with organic working fluids. The assumed heat source is hot combustion gases at high temperature (900–950 ∘ C ) and we assume to use only single stages axial turbines. The need to work at high temperatures, limits the choice of the right organic working fluids. The calculation results show the limitation in the performances of simple cycles and suggest the opportunity to resort to complex (binary) cycle configurations to achieve high net conversion efficiencies (15–16%). [ABSTRACT FROM AUTHOR]