Oral delivery of the sparingly soluble drug methotrexate (MTX) is challenging owing to its poor bioavailability and low solubility. To address this challenge, the present study reports the conversion of MTX into a series of five ionic liquids (ILs) comprising a cationic component-i.e., cholinium (Cho), tetramethylammonium (TMA), tetrabutylphosphonium (TBP), or an amino acid ester-and an anionic component-i.e., MTX. The biocompatibility, pharmacokinetics, tissue distribution, and antitumor efficacy of each MTX-based IL were investigated to determine its usefulness as a pharmaceutical. Oral administration to mice revealed that proline ethyl ester MTX (IL[ProEt][MTX]) had 4.6-fold higher oral bioavailability than MTX sodium, followed by aspartic diethyl ester MTX, IL[TBP][MTX], IL[Cho][MTX], and IL[TMA][MTX]. The peak plasma concentration, elimination half-life, area under the plasma concentration, mean absorption time, and body clearance of IL[ProEt][MTX] were significantly (p
The suitability of the dispersive liquid-liquid microextraction (DLLME) technique for gas chromatography (GC) characterization of minor organic compounds in honey samples is evaluated. Under optimized conditions, samples were pre-treated by liquid-liquid extraction with acetonitrile followed by DLLME using carbon tetrachloride (CCl4, 0.075 mL) as extractant. The yielded settled phase was analyzed by GC using high resolution time-of-flight (TOF) mass spectrometry (MS). The whole sample preparation process is completed in approximately 10 min, with a total consumption of organic solvents below 4 mL, relative standard deviations lower than 12% and with more than 70 organic compounds, displaying linear retention index in the range from 990 to 2900, identified in the obtained extracts. In comparison with HS SPME extraction, higher peak intensities were attained for most volatile and semi-volatile compounds amenable to both extraction techniques. Furthermore, other species such as highly polar and water soluble benzene acids, long chain fatty acids, esters and flavonoids, which are difficult to concentrate by HS SPME, could be identified in DLLME extracts. Some of the compounds identified in DLLME extracts have been proposed as useful for samples classification and/or they are recognized as markers of honeys from certain geographic areas.
The aim of the present study was to characterize the phenolic acids, flavonoids, and antioxidant properties of monofloral honey collected from five different districts in Bangladesh. A new high performance liquid chromatography (HPLC) equipped with a UV detector method was developed for the identification of the phenolic acids and flavonoids. A total of five different phenolic acids were identified, with the most abundant being caffeic acid, benzoic acid, gallic acid, followed by chlorogenic acid and trans-cinnamic acid. The flavonoids, kaempferol, and catechin were most abundant, followed by myricetin and naringenin. The mean moisture content, total sugar content, and color characteristics of the honey samples were 18.36 ± 0.95%, 67.40 ± 5.63 g/100 g, and 129.27 ± 34.66 mm Pfund, respectively. The mean total phenolic acids, total flavonoid content, and proline content were 199.20 ± 135.23, 46.73 ± 34.16, and 556.40 ± 376.86 mg/kg, respectively, while the mean FRAP values and DPPH radical scavenging activity were 327.30 ± 231.87 μM Fe (II)/100 g and 36.95 ± 20.53%, respectively. Among the different types of honey, kalijira exhibited the highest phenolics and antioxidant properties. Overall, our study confirms that all the investigated honey samples are good sources of phenolic acids and flavonoids with good antioxidant properties.
The present study was undertaken to determine the content of six minerals, five trace elements, and ten pesticide residues in honeys originating from different regions of Malaysia. Calcium (Ca), magnesium (Mg), iron (Fe), and zinc (Zn) were analyzed by flame atomic absorption spectrometry (FAAS), while sodium (Na) and potassium (K) were analyzed by flame emission spectrometry (FAES). Trace elements such as arsenic (As), lead (Pb), cadmium (Cd), copper (Cu), and cobalt (Co) were analyzed by graphite furnace atomic absorption spectrometry (GFAAS) following the microwave digestion of honey. High mineral contents were observed in the investigated honeys with K, Na, Ca, and Fe being the most abundant elements (mean concentrations of 1349.34, 236.80, 183.67, and 162.31 mg/kg, resp.). The concentrations of the trace elements were within the recommended limits, indicating that the honeys were of good quality. Principal component analysis reveals good discrimination between the different honey samples. The pesticide analysis for the presence of organophosphorus and carbamates was performed by high performance liquid chromatography (HPLC). No pesticide residues were detected in any of the investigated honey samples, indicating that the honeys were pure. Our study reveals that Malaysian honeys are rich sources of minerals with trace elements present within permissible limits and that they are free from pesticide contamination.
The performance of gas chromatography (GC) combined with a hybrid quadrupole time-of-flight (QTOF) mass spectrometry (MS) system for the determination of volatile and semi-volatile compounds in honey samples is evaluated. After headspace (HS) solid-phase microextraction (SPME) of samples, the accurate mass capabilities of the above system were evaluated for compounds identification. Accurate scan electron impact (EI) MS spectra allowed discriminating compounds displaying the same nominal masses, but having different empirical formulae. Moreover, the use of a mass window with a width of 0.005 Da provided highly specific chromatograms for selected ions, avoiding the contribution of interferences to their peak areas. Additional information derived from positive chemical ionization (PCI) MS spectra and ion product scan MS/MS spectra permitted confirming the identity of novel compounds. The above possibilities are illustrated with examples of honey aroma compounds, belonging to different chemical classes and containing different elements in their molecules. Examples of compounds whose structures could not be described are also provided. Overall, 84 compounds, from a total of 89 species, could be identified in 19 honey samples from 3 different geographic areas in the world. The suitability of responses measured for selected ions, corresponding to above species, for authentication purposes is assessed through principal components analysis.
Honey is a good source of several important chemical compounds and antioxidants and is harvested throughout the year. However, no study has determined how their contents change over the years. The aim of the present research was to investigate the changes in the phenolics, flavonoids and antioxidant properties, as well as other physicochemical properties, of Malaysian acacia honey collected during different months during a two year period. The DPPH (1,1-diphenyl-2-picrylhydrazyl) and FRAP (ferric reducing antioxidant power) methods were used to determine the total antioxidant activity of the honey samples. Generally, honey samples collected in the beginning and the middle of the year tended to have higher sugar content, which may be attributed to its high acidic nature and low moisture content. There was a gradual increase in the phenolic content of the acacia honey samples collected between September 2010 and December 2010. The honey sample collected at the beginning of the year (January) showed the highest color intensity and was dark amber in color. It also contained the highest concentration of phenolic compounds (341.67 ± 2.94 mg(gallic acid)/kg), the highest flavonoid content (113.06 ± 6.18 mg(catechin)/kg) and the highest percentage of DPPH inhibition and the highest FRAP value, confirming its high antioxidant potential. There was a positive correlation between DPPH and total phenolic content, suggesting that phenolic compounds are the strongest contributing factor to the radical scavenging activity of Malaysian acacia honeys. Overall, our results indicated that there were significant seasonal variations in the antioxidant potentials of honey over the two year period and the time of honey collection affects its physicochemical properties. Therefore, acacia honey from Malaysia should ideally be collected during the dry season, particularly in the months of January, May and June.
The aim of the present study was to evaluate the physical, biochemical and antioxidant properties of four Malaysian monofloral types of honey (gelam, longan, rubber tree and sourwood honeys) compared to manuka honey. Several physical parameters of honey, such as pH, moisture content, electrical conductivity (EC), total dissolved solids (TDS), color intensity, total sugar and sucrose content, were measured. A number of biochemical and antioxidant tests were performed to determine the antioxidant properties of the honey samples. Hydroxymethylfurfural (HMF) levels were determined using high performance liquid chromatography.
Free radicals and reactive oxygen species (ROS) have been implicated in contributing to the processes of aging and disease. In an effort to combat free radical activity, scientists are studying the effects of increasing individuals' antioxidant levels through diet and dietary supplements. Honey appears to act as an antioxidant in more ways than one. In the body, honey can mop up free radicals and contribute to better health. Various antioxidant activity methods have been used to measure and compare the antioxidant activity of honey. In recent years, DPPH (Diphenyl-1-picrylhydrazyl), FRAP (Ferric Reducing Antioxidant Power), ORAC (The Oxygen Radical Absorbance Capacity), ABTS [2, 2-azinobis (3ehtylbenzothiazoline-6-sulfonic acid) diamonium salt], TEAC [6-hydroxy-2, 5, 7, 8-tetramethylchroman-2-carboxylic acid (Trolox)-equivalent antioxidant capacity] assays have been used to evaluate antioxidant activity of honey. The antioxidant activity of honey is also measured by ascorbic acid content and different enzyme assays like Catalase (CAT), Glutathione Peroxidase (GPO), Superoxide Dismutase (SOD). Among the different methods available, methods that have been validated, standardized and widely reported are recommended.
The aim of the present study was to evaluate the physicochemical and antioxidant properties of Malaysian monofloral honey samples-acacia, pineapple and borneo honey-and compare them with tualang honey. Acacia and pineapple honey are produced by Apis mellifera bees while borneo and tualang honey are produced by Apis cerana and Apis dorsata bees, respectively.
Ionic liquids (ILs), a potentially attractive "green," recyclable alternative to environmentally harmful volatile organic compounds, have been increasingly exploited as solvents and/or cosolvents and/or reagents in a wide range of applications, including pretreatment of lignocellulosic biomass for further processing. The enzymatic delignification of biomass to degrade lignin, a complex aromatic polymer, has received much attention as an environmentally friendly process for clean separation of biopolymers including cellulose and lignin. For this purpose, enzymes are generally isolated from naturally occurring fungi or genetically engineered fungi and used in an aqueous medium. However, enzymatic delignification has been found to be very slow in these conditions, sometimes taking several months for completion. In this chapter, we highlight an environmentally friendly and efficient approach for enzymatic delignification of lignocellulosic biomass using room temperature ionic liquids (ILs) as (co)solvents or/and pretreatment agents. The method comprises pretreatment of lignocellulosic biomass in IL-aqueous systems before enzymatic delignification, with the aim of overcoming the low delignification efficiency associated with low enzyme accessibility to the solid substrate and low substrate and product solubilities in aqueous systems. We believe the processes described here can play an important role in the conversion of lignocellulosic biomass-the most abundant renewable biomaterial in the world-to biomaterials, biopolymers, biofuels, bioplastics, and hydrocarbons. Graphical Abstract.
Background The cardinal area of managing fire wounds is guided by adequately evaluating the burn-induced lesion's profundity and size. Superficial second-degree burns are often treated through daily reinstating with fresh sterile bandaging with appropriate topical antimicrobials to allow rapid spontaneous epithelialization. Around the world, a wide variety of substances are used to treat these wounds, from honey to synthetic biological dressings. Objective This study intended to determine honey's therapeutic potential compared with 1% silver sulfadiazine (Ag-SD) in arsenal-caused contusion medicament fulfillment. Methods A total of 70 cases were evaluated in this research work after fulfilling the required selection criteria during the study period of January 2014 to December 2014 and January 2017 to December 2017. Purposive selection criteria were adopted in the study to select research patients. The patients in Group-1 (n = 35) relied on honey as medication, while patients in Group-2 (n = 35) relied on 1% Ag-SD. Results In Group-1, exudation (68.4%) and sloughing (82.9%) were substantially reduced by Days 3 and 5 of therapeutic intervention, respectively. However, in Group-2, a reduction of exudation (17.1%) and sloughing (22.9%) occurred after Days 3 and 5 of treatment, respectively. Completion of the epithelialization process was observed among Group-1 and Group-2 cases. It was detected after Days 7 and 10 of treatment at 36.3% and 77% (Group-1) and 27% and 67% (Group-2), respectively. Around 3 ml of 1% honey was required per body surface area per dressing in Group-1. On the other hand, in Group-2, 2 gm Ag-SD was needed per body surface area per dressing. Conclusion Patients treated with honey found better clinical outcomes in managing superficial partial-thickness burns.
An inductively tuned modified split-ring resonator-based metamaterial (MTM) is presented in this article that provides multiple resonances covering S, C, X, and Ku-bands. The MTM is designed on an FR-4 substrate with a thickness of 1.5 mm and an electrical dimension of 0.063λ × 0.063λ where wavelength, λ is calculated at 2.38 GHz. The resonator part is a combination of three squared copper rings and one circular ring in which all the square rings are modified shaped, and the inner two rings are interconnected. The resonance frequency is tuned by adding inductive metal strips in parallel two vertical splits of the outer ring that causes a significant shift of resonances towards the lower frequencies and a highly effective medium ratio (EMR) of 15.75. Numerical simulation software CST microwave studio is used for the simulation and performance analysis of the proposed unit cell. The MTM unit cell exhibits six resonances of transmission coefficient (S21) at 2.38, 4.24, 5.98, 9.55, 12.1, and 14.34 GHz covering S, C, X, and Ku-bands with epsilon negative (ENG), near-zero permeability, and near-zero refractive index (NZI). The simulated result is validated by experiment with good agreement between them. The performance of the array of the unit cells is also investigated in both simulation and measurement. The equivalent circuit modeling has been accomplished using Advanced Design Software (ADS) that shows a similar S21 response compared to CST simulation. Noteworthy to mention that with the copper backplane, the same unit cell provides multiband absorption properties with four major absorption peaks of 99.6%, 95.7%, 99.9%, 92.7% with quality factors(Q-factor) of 28.4, 34.4, 23, and 32 at 3.98, 5.5, 11.73 and 13.47 GHz, respectively which can be applied for sensing and detecting purposes. The application of an array of the unit cells is investigated using it as a superstrate of an antenna that provides a 73% (average) increase of antenna gain. Due to its simple design, compact dimension with high EMR, ENG property with near-zero permeability, this multiband NZI metamaterial can be used for microwave applications, especially for multiband antenna gain enhancement.
In this paper, a tuned metamaterial (MTM) consisting of a symmetric split ring resonator is presented that exhibits epsilon negative (ENG), near zero permeability and refractive index properties for multiband microwave applications. The proposed metamaterial is constituted on a Rogers (RT-5880) substrate with 1.57 mm thickness and the electrical dimension of 0.14λ × 0.14λ, where wavelength, λ is calculated at 4.2 GHz. The symmetric resonating patch is subdivided into four equal and similar quartiles with two interconnecting split rings in each quartile. The quartiles are connected at the center of the substrate with a square metal strip with which four tuning metal strips are attached. These tuning metal strips are acted as spacers between four quartiles of the resonator patch. Numerical simulation of the proposed design is executed in CST microwave studio. The proposed MTM provides four resonances of transmission coefficient (S21) at 4.20 GHz, 10.14 GHz, 13.15 GHz, and 17.1 GHz covering C, X and Ku bands with negative permittivity, near zero permeability and refractive index. The calculated effective medium ratio (EMR) is 7.14 at 4.2 GHz indicates its compactness. The resonance frequencies are selective in nature which can be easily tuned by varying the length of the tuning metal stubs. The equivalent circuit of the proposed MTM is modelled in Advanced Design Software (ADS) that exhibits a similar S21 compared with CST simulation. Surface current, electric and magnetic fields are analyzed to explain the frequency tuning property and other performances of the MTM. Compact size, ENG with near zero permeability and refractive index along with frequency selectivity through tuning provides flexibility for frequency selective applications of this MTM in wireless communications.
The transdermal delivery of hydrophilic drugs remains challenging owing to their poor ability to permeate the skin; formulation with oil media is difficult without adding chemical permeation enhancers or co-solvents. Herein, we synthesized 12 oil-miscible ionic liquid (IL) drugs comprising lidocaine-, imipramine-, and levamisole (Lev)-hydrochloride with fatty acid permeation enhancers, i.e., laurate, oleate, linoleate, and stearate as counterions. A set of in vitro and in vivo studies was performed to investigate the potency and deliverability of the transdermal drug formulations. All of the synthesized compounds were freely miscible with pharmaceutically acceptable solvents/agents (i.e., ethanol, N-methyl pyrrolidone, Tween 20, and isopropyl myristate (IPM)). In vitro permeation studies revealed that the oleate-based Lev formulation had 2.6-fold higher skin permeation capability than the Lev salts and also superior ability compared with the laurate-, linoleate-, and stearate-containing samples. Upon in vivo transdermal administration to mice, the peak plasma concentration, elimination half-life, and area under the plasma concentration curve values of Lev-IL were 4.6-, 2.9-, and 5.4-fold higher, respectively, than those of the Lev salt. Furthermore, in vitro skin irritation and in vivo histological studies have demonstrated that Lev-IL has excellent biocompatibility compared with a conventional ionic liquid-based carrier. The results indicate that oil-miscible IL-based drugs provide a simple and scalable strategy for the design of effective transdermal drug delivery systems.
The thermal kinetic modeling is crucial for development of sustainable processes where lignocellulosic fuels are a part of chemical system and their thermal degradation eventuates. In this paper, thermal decomposition of three lignocellulosic materials (bagasse, rice husk, and wheat straw) was obtained by the thermogravimetric (TG) technique and kinetics was analyzed by both model-fitting and isoconversional (model-free) methods to compare their effectiveness. Two models selected from each class include Arrhenius and Coats-Redfern (model-fitting), and Kissinger-Akahira-Sunose (KAS) and Flynn-Wall-Ozawa (FWO) (model-free). The formal model-fitting approach simulating the thermal decomposition of solids by assuming a fixed mechanism was found to be unduly facile. However, activation energy (E) values calculated from two model-fitting techniques were considerably different from each other with a percentage difference in the range of 1.36% to 7.65%. Particularly, both model-fitting methods predicted different reaction mechanism for thermal disintegration of lignocellulosic materials (two-dimensional diffusion (D2) by Arrhenius and one-dimensional diffusion (D1) by Coat-Redfern method). Conversely, the model-free routine offers a transformation of mechanism and activation energy values throughout reaction and is, therefore, more authentic to illustrate the complexity of thermal disintegration of lignocellulosic particles. Based on the model-free kinetic analysis, the lignocellulosic materials may be devised in following order of activation energy: rice husk > bagasse > wheat straw, by both KAS and FWO methods with a percentage difference no more than 0.84% for fractional conversion up to 0.7. Isoconversional approach could be recommended as more realistic and precise for modeling non-isothermal kinetics of lignocellulosic residues compared to model-fitting approach.
The evolution of petroleum-derived polymers is one of the crowning accomplishments of the past century. Although the significant economic gains from this industrial model of resource utilization are achieved, the environmental impacts are fatal. One of the principles of sustainable development is to replace such polymers with potential alternatives derived from renewable materials. Biopolymers derived from natural resources afford a new, versatile, environmentally benign feedstock that could exhibit closed-loop life cycles as part of a future material's industrial ecology. However, the solubility and processability of biopolymer materials provoke a serious bottleneck owing to their dense networks of inter - and intramolecular bondings and structural heterogeneity. Recently, ionic liquids (ILs) have emerged as promising green solvents and acquired augmented appreciation for their peerless power of biopolymer processing. Among the fourteen principle of green chemistry, the two key elements encourage the exploitation of renewable raw materials by using environmentally benign solvents that cover in dissolution of biopolymers using ILs. This mini review represents a brief overview of the comprehensive ILs assisted extraction and processing of various biopolymeric materials for value-added applications.
Glycerol pretreatment is a promising method for the environmentally-friendly transformation of lignocellulosic materials into sustainable cellulose-rich raw materials (i.e., biopolymer) to fabricate biocomposites. Here, a comparison of aqueous acidified glycerol (AAG) pretreatment of wheat straw (WS) with alkaline, hot water, and dilute acid pretreatments on the thermal and mechanical characteristics of their fabricated composite board is presented. A comparison of total energy expenditure during WS pretreatment with AAG and other solutions was estimated and a comparative influence of AAG processing on lignocellulosic constituents and thermal stability of WS fiber was studied. Results imply that AAG pretreatment was superior in generating cellulose-rich fiber (CRF) as compared to other pretreatments and enhanced the cellulose contents by 90% compared to raw WS fiber. Flexural strength of acidic (40.50 MPa) and hot water treated WS composite (38.71 MPa) was higher compared to the value of 33.57 MPa for untreated composite, but AAG-treated composites exhibited lower values of flexural strength (22.22 MPa) compared to untreated composite samples. Conversely, AAG pretreatment consumed about 56% lesser energy for each kg of WS processed as compared to other pretreatments. These findings recognize that glycerol pretreatment could be a clean and new pretreatment strategy to convert agricultural waste into high-quality CRF as a sustainable raw material source for engineered biocomposite panels.
Recently, a great attention has been paid to advanced microwave technology that can be used to markedly enhance the biodiesel production process. Ceiba pentandra Seed Oil containing high free fatty acids (FFA) was utilized as a non-edible feedstock for biodiesel production. Microwave-assisted esterification pretreatment was conducted to reduce the FFA content for promoting a high-quality product in the next step. At optimum condition, the conversion was achieved 94.43% using 2wt% of sulfuric acid as catalyst where as 20.83% conversion was attained without catalyst. The kinetics of this esterification reaction was also studied to determine the influence of factors on the rate of reaction and reaction mechanisms. The results indicated that microwave-assisted esterification was of endothermic second-order reaction with the activation energy of 53.717kJ/mol.
Ibuprofen (Ibf) is a biologically active drug (BADs) and an emerging contaminant of concern (CECs) in aqueous streams. Due to its adverse effects upon aquatic organisms and humans, the removal and recovery of Ibf are essential. Usually, conventional solvents are employed for the separation and recovery of ibuprofen. Due to environmental limitations, alternative green extracting agents need to be explored. Ionic liquids (ILs), emerging and greener alternatives, can also serve this purpose. It is essential to explore ILs that are effective for recovering ibuprofen, among millions of ILs. The conductor-like screening model for real solvents (COSMO-RS) is an efficient tool that can be used to screen ILs specifically for ibuprofen extraction. The main objective of this work was to identify the best IL for the extraction of ibuprofen. A total of 152 different cation-anion combinations consisting of eight aromatic and non-aromatic cations and nineteen anions were screened. The evaluation was based upon activity coefficients, capacity, and selectivity values. Furthermore, the effect of alkyl chain length was studied. The results suggest that quaternary ammonium (cation) and sulfate (anion) have better extraction ability for ibuprofen than the other combinations tested. An ionic liquid-based green emulsion liquid membrane (ILGELM) was developed using the selected ionic liquid as the extractant, sunflower oil as the diluent, Span 80 as the surfactant, and NaOH as the stripping agent. Experimental verification was carried out using the ILGELM. The experimental results indicated that the predicted COSMO-RS and the experimental results were in good agreement. The proposed IL-based GELM is highly effective for the removal and recovery of ibuprofen.
In the present investigation, a total of 108 combinations of ionic liquids (ILs) were screened using the conductor-like screening model for real solvents (COSMO-RS) with the aid of six cations and eighteen anions for the extraction of succinic acid (SA) from aqueous streams through dispersive liquid-liquid microextraction (DLLME). Using the screened ILs, an ionic liquid-based DLLME (IL-DLLME) was developed to extract SA and the role of different reaction parameters in the effectiveness of IL-DLLME approach was investigated. COSMO-RS results suggested that, quaternary ammonium and choline cations form effective IL combinations with [OH¯], [F¯], and [SO42¯] anions due to hydrogen bonding. In view of these results, one of the screened ILs, tetramethylammonium hydroxide [TMAm][OH] was chosen as the extractant in IL-DLLME process and acetonitrile was adopted as the dispersive solvent. The highest SA removal efficiency of 97.8% was achieved using 25 μL of IL [TMAm][OH] as a carrier and 500 μL of acetonitrile as dispersive solvent. The highest amount of SA was extracted with a stir time of 20 min at 300 rpm, followed by centrifugation for 5 min at 4500 rpm. Overall, the findings showed that IL-DLLME is efficient in extracting succinic acid from aqueous environments while adhering to the first-order kinetics.