Directing the Assembly of Multicomponent Organic Crystals. Synthesis, characterisation and structural analysis of multicomponent organic systems formed from dynamic processes.

Directed assembly of molecular solids continues to attract widespread interest with its fundamental application in a wide range of commercial settings where control of the crystalline state of materials corresponds with product performance. These arenas include pharmaceuticals, personal care formulations, foods, paints and pigments and explosives. In recent times, the assembly of multicomponent organic systems has achieved considerable impetus with the widespread interest in co-crystal systems. However, cogent assembly (or engineering) of multicomponent materials is still in its infancy. Considerable advances in crystal design have been made through consideration of intermolecular ‘synthons’ – identifiable motifs utilising hydrogen bonds – but the translation of other molecular information (conformation, chirality, etc.) into solid state properties (e.g. long-range (translational) symmetry, crystal chirality) remains poorly understood. In this study, we have attempted to evaluate the influence of a chiral centre adjacent to molecular synthons to identify potential translation of information into the solid form. We have compared the co-crystallisation of nicotinamide with both the racemic mixture of malic acid against that with an enantiomerically pure form of the acid (L-malic acid). As well as DL-phenyllactic acid and L-phenyllactic acid. iii It is apparent that recognition between enantiomeric molecular forms play a significant role in the assembly of these systems. This mechanism can be considered independently from the H-bonding networks supporting the hetero-molecular interactions (e.g. acid-amide recognition). Discrimination and control of such interactions may play a role in transmitting chiral molecular information into solid state multi-component assemblies. In order to develop an understanding of co-crystal formation in chiral and achiral forms with intermolecular interactions, the CSD and crystal structures were obtained to do the analysis of how co-crystals pack. This study has also investigated the use of boronic acids. The aim of this study was to investigate the modification of the hydrogen bonding environment within the hydrogen bonded multi-component systems of boroxines. The study also attempted to determine how the starting materials drive the systems between the boronic acid co-crystal and the boroxine adduct

Evaluation of Groundwater and Grey Water Contamination with Heavy Metals and Their Adsorptive Remediation Using Renewable Carbon from a Mixed-Waste Source

The contamination of water sources with heavy metals is a serious challenge that humanity is facing worldwide. The aim of this work was to evaluate and remediate the metal pollution in groundwater and greywater resources from Riyadh, Saudi Arabia. In addition, we investigated the application of ultrasonic power before adsorption to assess the dispersion of renewable carbon from mixed-waste sources (RC-MWS) as an adsorbent and enhance the water purification process. The renewable carbon adsorbent showed high ability to adsorb Pb(II), Zn(II), Cu(II), and Fe(II) from samples of the actual water under study. The conditions for the remediation of water polluted with heavy metals by adsorptive-separation were investigated, including the pH of the adsorption solution, the concentration of the heavy metal(s) under study, and the competition at the adsorption sites. The enhanced adsorption process exhibited the best performance at a pH of 6 and room temperature, and with a contact time of 60 min. Kinetic studies showed that the pseudo-second-order kinetic model was fitted with the adsorption of Pb(II), Zn(II), Cu(II), and Fe(II) onto the RC-MWS. The adsorption data were well fitted by Langmuir isotherms. The Freundlich isotherm was slightly fitted in the cases of Cu(II), Zn(II), and Fe(II), but not in the cases of Pb(II). The developed adsorption process was successfully applied to actual water samples, including water samples from Deria and Mozahemia and samples from clothes and car washing centers in Riyadh city

Rapid detection and quantification of paracetamol and its major metabolites using surface enhanced Raman scattering

Paracetamol (also known as acetaminophen) is an over-the-counter (OTC) drug that is commonly used as an analgesic for mild pain, headache, cold and flu. While in the short term it is a safe and effective medicine, it is sometimes used for attempted suicides particularly in young adults. In such circumstances it is important for rapid diagnosis of overdoses as antidotes can be given to limit liver damage from one of its primary metabolites N-acetyl-p-benzoquinone imine (NAPQI). Unfortunately, the demand for rapid and sensitive analytical techniques to accurately monitor the abuse of OTC drugs has significantly risen. Ideally these techniques would be highly specific, sensitive, reproducible, portable and rapid. In addition, an ideal point of care (PoC) test would enable quantitative detection of drugs and their metabolites present in body fluids. While Raman spectroscopy meets these specifications, there is a need for enhancement of the signal because the Raman effect is weak. In this study, we developed a surface-enhanced Raman scattering (SERS) methodology in conjunction with chemometrics to quantify the amount of paracetamol and its main primary metabolites (viz., paracetamol sulfate, p-acetamidophenyl β-D-glucuronide and NAPQI) in water and artificial urine. The enhancement of the SERS signals was achieved by mixing the drug or xenometabolites with a gold nanoparticle followed by aggregation with 0.045 M NaCl. We found that the SERS data could be collected directly, due to immediate analyte association with the Au surface and colloid aggregation. Accurate and precise measurements were generated, with a limit of detection (LoD) of paracetamol in water and artificial urine at 7.18 × 10-6 M and 2.11 × 10-5 M, respectively, which is well below the limit needed for overdose and indeed normal levels of paracetamol in serum after taking 1 g orally. The predictive values obtained from the analysis of paracetamol in water and artificial urine were also excellent, with the coefficient of determination (Q2) being 0.995 and 0.996, respectively (1 suggests a perfect model). It was noteworthy that when artificial urine was spiked with paracetamol, no aggregating agent was required due to the salt rich medium, which led to spontaneous aggregation. Moreover, for the xenometabolites of paracetamol excellent LoDs were obtained and these ranged from 2.6 × 10-4 M to 5 × 10-5 M with paracetamol sulfate and NAPQI having Q2 values of 0.934 and 0.892 and for p-acetamidophenyl β-D-glucuronide this was slightly lower at 0.6437

Efficient nanostructured materials to reduce nutrient leaching to overcome environmental contaminants

Abstract Nutrient leaching is a major reason for fresh and ground water contamination. Menthol is the major bioactive ingredient of Mentha arvensis L. and one of the most traded products of global essential oil market. The indigenous production of menthol crystals in developing countries of the world can prove to be the backbone for local growers and poor farmers. Therefore, present research was designed to check the effects of nano-structured plant growth regulators (PGRs) (28-homobrassinolide and ethephon) with reduced leaching potentials on the essential oil and menthol (%) of Mentha arvensis L. The prepared nano-formulations were characterized by Fourier transform infrared (FTIR) spectroscopy, Laser induced breakdown spectroscopy (LIBS), Differential scanning colorimetry-thermal gravimetric analysis (DSC-TGA), Scanning electron microscopy (SEM), Atomic absorption spectrometry (AAS) and Zeta potential and Zeta size analysis. The menthol (%) was determined by modified spectrophotometric and gas chromatographic (GC) method. The highest essential oil (%) was obtained by the application of 28-homobrassinolide-Zn-NPs-L-II (0.92 ± 0.09%) and ethephon-Ca-NPs-L-III (0.91 ± 0.05%) as compared to the control (0.65 ± 0.03%) and blank (0.62 ± 0.09%). The highest menthol (%) was obtained by applying 28-homobrassinolide-Ca-NPs-L-I (80.06 ± 0.07%), 28-homobrassinolide-Ca-NPs-L-II (80.48 ± 0.09%) and 28-homobrassinolide-Ca-NPs-L-III (80.84 ± 0.11%) and ethephon-Ca-NPs-L-III (81.53 ± 0.17%) and ethephon-Zn-NPs-L-II (81.93 ± 0.26%) as compared to control (67.19 ± 0.14%) and blank (63.93 ± 0.17%)

Simultaneous Multiplexed Quantification of Banned Sudan Dyes Using Surface Enhanced Raman Scattering and Chemometrics

Azo compounds such as the Sudan dyes I–IV are frequently used illegally as colorants and added to a wide range of foods. These compounds have been linked to a number of food safety hazards. Several methods have been proposed to detect food contamination by azo compounds and most of these are laboratory based; however, the development of reliable and portable methods for the detection and quantification of food contaminated by these chemicals in low concentration is still needed due to their potentially carcinogenic properties. In this study, we investigated the ability of surface enhanced Raman scattering (SERS) combined with chemometrics to quantify Sudan I–IV dyes. SERS spectra were acquired using a portable Raman device and gold nanoparticles were employed as the SERS substrate. As these dyes are hydrophobic, they were first dissolved in water: acetonitrile (1:10, v/v) as single Sudan dyes (I–IV) at varying concentrations. SERS was performed at 785 nm and the spectra were analyzed by using partial least squares regression (PLS-R) with double cross-validations. The coefficient of determination (Q2) were 0.9286, 0.9206, 0.8676 and 0.9705 for Sudan I to IV, respectively; the corresponding limits of detection (LOD) for these dyes were estimated to be 6.27 × 10−6, 5.35 × 10−5, 9.40 × 10−6 and 1.84 × 10−6 M. Next, quadruplex mixtures were made containing all four Sudan dyes. As the number of possible combinations needed to cover the full concentration range at 5% intervals would have meant collecting SERS spectra from 194,481 samples (214 combinations) we used a sustainable solution based on Latin hypercubic sampling and reduced the number of mixtures to be analyzed to just 90. After collecting SERS spectra from these mixture PLS-R models with bootstrapping validations were employed. The results were slightly worse in which the Q2 for Sudan I to IV were 0.8593, 0.7255, 0.5207 and 0.5940 when PLS1 models (i.e., one model for one dye) was employed and they changed to 0.8329, 0.7288, 0.5032 and 0.5459 when PLS2 models were employed (i.e., four dyes were modelled simultaneously). These results showed the potential of SERS to be used as a high-throughput, low-cost, and reliable methods for detecting and quantifying multiple Sudan dyes in low concentration from illegally adulterated samples.</jats:p

Bio‐fabrication of silver nanoparticles using an aqueous extract of Quercus baloot: Preparation, characterization and in vitro antimicrobial evaluation

Abstract In the current study, a novel method was used to synthesize silver nanoparticles (AgNPs) by utilizing Quercus baloot aqueous extract as a reducing agent. The biosynthesized AgNPs were then subjected to various physicochemical characterizations to assess their effectiveness against microbial familiarity. The characterization techniques included ultraviolet‐visible spectro‐photometry (UV‐Vis), scanning electron microscopy (SEM), transmission electron microscopy (TEM), X‐ray diffractometer (XRD), and Fourier‐transform infrared spectroscopy (FTIR). The UV‐Vis analysis revealed a distinctive spectral peak at 420 nm, indicating the presence of silver nanoparticles. SEM imaging displayed the nanoparticle size range of about 100 nm at a magnification of 30,000x, while TEM demonstrated that the nanoparticles had a spherical morphology with a size of approximately 100 nm. Moreover, the crystalline structure of the silver nanoparticles was confirmed by XRD analysis, further validating their successful synthesis. Additionally, FTIR analysis provided evidence of the presence of phytochemicals involved in synthesizing the AgNPs. the biosynthesized silver nanoparticles (AgNPs) were evaluated for antibacterial and antifungal activities. The AgNPs displayed substantial efficacy against common bacterial strains, including Staphylococcus aureus (71%), Escherichia coli (59%), and Klebsiella pneumoniae (64%). Furthermore, they demonstrated significant antifungal activity against plant pathogenic fungi, namely Aspergillus niger (65%), Aspergillus flavus (70%) and Fusarium oxysporum (61%)

Biomass-Derived Adsorbent for Dispersive Solid-Phase Extraction of Cr(III), Fe(III), Co(II) and Ni(II) from Food Samples Prior to ICP-MS Detection

A biomass-derived adsorbent was simply prepared and applied as efficient and low-cost solid-phase supports. The adsorbent material was characterized by scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), X-ray diffraction (XRD), surface area analysis and Fourier transform infrared (FTIR) spectroscopy. The amorphous structure of the prepared adsorbent was indicated from the XRD. The prepared adsorbent exhibited surface functional groups such as carbonyl and hydroxyl groups, which enhance the application of DSPE. An accurate separation and preconcentration of Cr(III), Fe(III), Co(II) and Ni(II) prior to ICP-MS detection was achieved using the biomass-derived adsorbent. The extraction process was performed at pH 4 using 1 mL of 0.5 N nitric acid for elution and recovery of ions. The prepared biomass-derived adsorbent showed efficient performance for extraction application, exhibiting a preconcentration factor of 50 and LODs of 1.4, 2.4, 1.9 and 3.0 mu g.L-1 for Cr(III), Fe(III), Co(II) and Ni(II), respectively, while the LOQs were reported as 4.1, 7.3, 5.7 and 8.9 mu g.L-1 for Cr(III), Fe(III), Co(II) and Ni(II), respectively. The DSPE procedure presented was successfully applied to the determination of the Cr(III), Fe(III), Co(II) and Ni(II) contamination in some food samples

Deep Eutectic Solvent-Based Microextraction of Lead(II) Traces from Water and Aqueous Extracts before FAAS Measurements

Microextraction procedures for the separation of Pb(II) from water and food samples extracts were developed. A deep eutectic solvent composed of alpha-benzoin oxime and iron(III) chloride dissolved in phenol was applied as a phase separator support. In addition, this deep eutectic mixture worked as an efficient extractor of Pb(II). The developed microextraction process showed a high ability to tolerate the common coexisting ions in the real samples. The optimum conditions for quantitative recoveries of Pb(II) from aqueous extracts were at pH 2.0, conducted by adding 150 mu L from the deep eutectic solvent. The quantitative recoveries were obtained with various initial sample volumes up to 30 mL. Limits of detection and limits of quantification of 0.008 and 0.025 mu g L-1 were achieved with a relative standard deviation (RSD%) of 2.9, which indicates the accuracy and sensitivity of the developed procedure. Recoveries from the reference materials, including TMDA 64.2, TMDA 53.3, and NCSDC-73349, were 100%, 97%, and 102%, respectively. Real samples, such as tap, lake, and river water, as well as food samples, including salted peanuts, chickpeas, roasted yellow corn, pistachios, and almonds, were successfully applied for Pb(II) analysis by atomic absorption spectroscopy (AAS) after applying the developed deep eutectic solvent-based microextraction procedures

Role of Biosynthesized Silver Nanoparticles with <i>Trigonella foenum-graecum</i> Seeds in Wastewater Treatment

As the human population continues to escalate, its requirement for clean water is also increasing. This has resulted in an increased dependency on wastewater effluent to maintain the base flow of urban streams, especially in water-stressed regions. The present study reports the synthesis of AgNPs with green credentials using an aqueous extract of Trigonella foenum-graecum seeds. The observance of surface plasmon resonance (SPR) with UV–Vis spectrophotometry confirmed the presence of spherical/oblong particles with a mean diameter of 43.8 nm and low polydispersity index (PDI) of 0.391 measured by transmission electron microscopy (TEM) and DLS (dynamic light scattering) technique, respectively. The elemental map of AgNPs was demonstrated with energy-dispersive spectroscopy (EDS) and the constituent functional groups were identified by the FTIR spectra, which were similar to the bulk seed extract with a slight shift in the pattern. The emission spectrum of nanoparticles was recorded for the excitation wavelength of 349 using fluorescence microscopy and the crystalline structure was assessed using X-ray diffraction. The potential wastewater remedial efficacy of the synthesized AgNPs was evaluated based on the water quality parameters (pH, EC, BOD, COD) of the sewage effluent collected from a local Sewage Treatment Plant (STP). Furthermore, the photo degradative efficacy was investigated using the degradation percentage of Crystal Violet (CV) dye, which was recorded as 94.5% after 20 min. In addition, the antimicrobial activity of the NPs versus bulk seed extract was assessed against two bacterial strains, Escheria coli and Staphylococcus aureus, using the disc diffusion method. The AgNPs showed a profound modulatory effect on the water quality parameters, coupled with marked antimicrobial and photodegradative activity. Thus, the biogenically synthesized AgNPs offer a prospective potential for use in wastewater remediation strategies