A Review on the Traditional Applications, Phytochemistry, and Pharmacology of the Genus Physochlaina G. Don.

Physochlaina is a genus of flowering plants belonging to the family Solanaceae and consists of 10 species distributed in various Asian countries. The species of the genus have been traditionally used to cure a variety of illnesses due to their highly valuable medicinal properties, including cancer, asthma, cough, weakness, stomachache, diarrhea, swelling, spasms, toothache, boils, ulcers, rheumatic pain, chronic bronchitis, gastric problems, abdominal pain, palpitation, and insomnia. The species have gained significant attention due to their remarkable ethnopharmacological and ethnomedicinal significance. The researchers have isolated so far 71 biologically active secondary metabolites from different Physochlaina species, which include flavonoids, alkaloids, coumarins, phenolic acids, iridoids, and sterols. These compounds exhibit diverse biological activities, such as antibacterial, anti-oxidant, anti-inflammatory, cytotoxic, and anticancer properties. The present review has been compiled with the intention of providing a comprehensive overview of the botany, distribution, traditional uses, phytochemical profile, and biological activities of the genus Physochlaina for future exploration of plant-based drugs and therapeutic approaches. The present review contributes to understanding the significant pharmacological potential of Physochlaina species and unraveling their chemical composition, highlighting their relevance in developing therapeutic agents. Till date, numerous pharmacological properties and isolated phytochemicals of Physochlaina species that support the species traditional and ethnobotanical history have been documented in a number of scientific publications. However, greater emphasis should be paid to in vivo investigations on various extracts and their phytoconstituents as well as mechanistic analysis to help drug developers better understand how to use Physochlaina species as significant therapeutic resources for herbal formulations using various techniques.

Synthesis, Characterization, Analytical Application, and Theoretical Studies of a Schiff Base, (E)-2-(2-aminophenylthio)-N-(Thiophen-2-yl-methylene) Benzenamine.

In this study, a new Schiff base, (E)-2-(2-aminophenylthio)-N-(thiophen-2-yl-methylene) benzenamine was synthesized for selective detection of Hg2+. This Schiff base was characterized by proton nuclear magnetic resonance (1HNMR), carbon-13 nuclear magnetic resonance (13CNMR), and Fourier-transform infrared (FTIR) spectroscopy. Binding interaction between (E)-2-(2-aminophenylthio)-N-(thiophen-2-yl-methylene)benzenamine and various metal ions has been studied by UV-Vis spectroscopic measurements and shows promising coordination towards Hg2+ and almost no interference from other metal ions (Ag+, Mn2+, Fe3+, Al3+, Co2+, Ni2+, Cu2+, Zn2+, Cd2+, Fe2+ and Cr3+).This Schiff base exhibiting detection limit of 3.8 × 10- 8 M. The Schiff base newly synthesized in this study was successfully applied to the determination of Hg2+ in water samples. In addition to the experimental study, a theoretical study was conducted using Gaussian 09 program to support the experimental findings. FTIR, NMR, bond angle, bond length, torsional angles, and structural approximation were studied using theoretical consideration.

Amine-decorated Zirconium Based Metal Organic Framework for Ultrafast Detection of 2,4,6-Trinitrophenol in Aqueous Samples.

An amine-decorated zirconium based metal organic framework (MOF) UiO-66-NH2 with rod shape morphology was synthesized by solvothermal process using 2-aminoterephthalic acid as an organic linker. Crystallinity of synthesized MOF material was confirmed with PXRD technique. MOF was employed as selective and sensitive sensor for ultra-trace detection of 2,4,6-trinitrophenol (TNP) in aqueous matrix, even in coexistence with other competitive nitroaromatic analytes. High value of Stern-Volmer quenching constant Ksv (1.106 × 105 M- 1), plausible photoluminescent quenching efficiency (97.8%) and lower detection limit (0.95 µM/217ng mL- 1) ascertained extraordinary sensitivity of developed MOF for TNP. Density functional theory calculations and electrostatic interactions (i.e. ionic interaction, H-bonding and π-π interaction) indicated that electron and energy transfer processes play a key role in turn-off quenching response of UiO-66-NH2 sensor. Spiked real samples were analysed to validate the developed method, which satisfactorily established the developed MOF sensor as an efficient tool for analysis.

Fluorescence "Turn-off" Sensing of Iron (III) Ions Utilizing Pyrazoline Based Sensor: Experimental and Computational Study.

A simple pyrazoline-based ''turn off'' fluorescent sensor 5-(4-methoxyphenyl)-3-(5-methylfuran-2-yl)-1-phenyl-4,5-dihydro-1H-pyrazole (PFM) was synthesized and well characterized by different techniques such as FT-IR, 1H-NMR, 13C-NMR, and mass spectrometry. The synthesized sensor PFM was utilized for the detection of Fe3+ ions. Fluorescence emission selectively quenched by Fe3+ ions compared to other metal ions (Mn2+, Al3+, Fe2+, Hg2+, Cu2+, Co2+, Ni2+, Cd2+, Pb2+, and Zn2+) via paramagnetic fluorescence quenching and showed good anti-interference ability over the existence of other tested metals. Under optimum conditions, the fluorescence intensity of sensor quenched by Fe3+ in the range of 0 to 3 µM with detection limit of 0.12 µM. Binding of Fe3+ ions to PFM solution were studied by fluorescent titration, revealed formation of 1:1 PFM-Fe metal complex and binding constant of complex was found to be of 1.3 × 105 M-1. Further, the fluorescent sensor has been potentially used for the detection of Fe3+ in environmental samples (river water, tap water, and sewage waste water) with satisfactory recovery values of 99-101%.

Bis(thiophen-2-yl-methylene) Benzene-1, 4-Diamine as Fluorescent Probe for the Detection of Fe3+ in Aqueous Samples.

A Schiff base bis(thiophen-2-yl-methylene)benzene-1, 4-diamine (L) was synthesized and used for selective and sensitive detection of Fe3+. L exhibited enhanced fluorescence response at excitation of 365 nm and emission wavelength of 440 nm for Fe3+. The formation of a 1:1 complex between L and Fe3+ was suggested by Job's plot by fluorescence titration and from optimized structures using Density functional theory (DFT). The fluorescence intensity was directly proportional to concentration of Fe3+ (R2 = 0.999) with the detection limit of 3.8 × 10-7 M and the binding constant of 1.20 × 104 M-1 at pH = 6.0. The probe was used to detect Fe3+ in different water samples with the percentage recovery of 99.7-103%. The interference of the other cations are < 5%.

Progress in pre-treatment and extraction of organic and inorganic pollutants by layered double hydroxide for trace-level analysis.

Continuous release of pollutants into the environment poses serious threats to environmental sustainability and human health. For trace-level analysis of pollutants, layered double hydroxide (LDH) is an attractive option to impart enhanced sorption capability and sensitivity toward pollutants because of its unique layered structure, tunable interior architecture, high anion-exchange capacities, and high porosity (e.g., Zn/Cr LDH/DABCO-IL, Ni/Al LDH, CS-Ni/Fe LDH, SDS-Fe3O4@SiO2@Mg-Al LDH, Boeh/Mg/Al LDH/pC, and Fe@NiAl LDH). In concert with the well-defined analytical methodologies (e.g., HPLC and GC), the LDH materials can be employed to detect trace-level targets (e.g., as low as âˆ¼ 20 fg/L for phenols) in aqueous environments. This review highlights LDH as a promising material for pre-treatment of a variety of organic and inorganic target pollutants in complex real matrices. Challenges and future requirements for research into LDH-based analytical methods are also discussed.

Preparation and evaluation of a porous molecularly imprinted polymer for selective recognition of the antiepileptic drug carbamazepine.

A novel and porous molecularly imprinted polymer (PMIP) was synthesized and used as a solid-phase extraction adsorbent for preconcentration of carbamazepine (CBZ) prior to its quantitation by high-performance liquid chromatography (HPLC) in various sample forms (e.g., drinking water, river water, hospital wastewater, and pharmaceuticals). PMIP-CBZ was applied to a polymerization process in which polystyrene spheres were coated with a silica layer. Removal of polystyrene spheres and formation of porous silica facilitated the recovery of CBZ (99.4%) during the extraction process. Site accessibility to the surface of PMIP-CBZ increased the density of high-recognition sites. PMIP-CBZ was characterized by Fourier-transform infrared spectroscopy and scanning electron microscopy. The key variables influencing the extraction efficiency of PMIP (e.g., adsorbent loading, eluent type, eluent volume, reusability of the adsorbent, and cross-reactivity) were optimized. The optimized protocol was successfully employed to quantify CBZ with limit of detection and limit of quantification as 0.082 and 0.270 ng/mL, respectively (linear detection range: 0.5-250 ng/mL and a relative standard deviation:  < 5%). Use of the PMIP adsorbent resulted in a sensitive and stable method for efficiently quantitation of CBZ from various real sample matrices.

Surfactant-modified Zn/Al-layered double hydroxides for efficient extraction of alkyl phenols from aqueous samples.

Zn/Al-layered double hydroxides (LDHs) modified by sodium dodecylsulfate (SDS) were synthesized as a hydrophobic organic sorbent via urea hydrolysis. LDHs were applied as adsorbent for solid phase extraction (SPE) analysis to determine three alkylphenols (namely, p-tert-amylphenol (PTAP), p-cumylphenol (PCP), and p-n-octylphenol (POP)) in water samples using gas chromatography-mass spectrometry. The extraction efficiency was optimized by adjusting key variables of eluent volume, eluent type, sample flow rate, adsorbent amount, pH, and the effect of salt addition. Under the optimal conditions, APs showed excellent linearity (1-250 ng/mL: R2 > 0.99) and reproducibility (relative standard deviation: <5%). The detection limits for PTAP, PCP, and POP were 19, 16, and 33 pg/mL, respectively. LDHs based SPE method offered high recovery for aqueous samples (e.g., 83.2-99.46%) with enhanced reusability (e.g., up to 10 cycles). The feasibility of the developed method has thus been validated for quantitation of three alkyl phenols (i.e., PTAP, PCP, and POP) in aqueous environmental samples with high sensitivity and good stability.

Blending polydopamine-derived imprinted polymers with rice straw-based fluorescent carbon dots for selective detection and adsorptive removal of ibuprofen.

Dual-functioning probes capable of detecting and removing hazardous substances have recently received increased attention compared to exclusive sensory probes. Herein, a new composite is synthesized by blending polydopamine imprinted polymers with fluorescent carbon dots (PIP-FCDs) for the selective recognition and adsorption of Ibuprofen (IBF). IBF is a nonsteroidal anti-inflammatory drug and is excessively released in the pharmaceutical wastes. The PIP-FCDs consist of confined pockets for encasing IBF and quenches fluorescence signal when contact with the molecule. PIP-FCDs show high sensitivity (limit of detection = 1.58 × 10-5 µM) and selectivity towards IBF in the presence of other pharmaceutical drugs i.e., aspirin, ketoprofen, norfloxacin, and levofloxacin. The adsorption studies show an adsorption capacity of 209.8 mg g-1 with an extraction efficiency of around 99.9 %. Furthermore, PIP-FCDs are utilized to determine IBF levels in various aqueous pharmaceutical samples. This development provides a simple and dual-functioning probe for the detection and adsorption of IBF from various matrices.

A Review of Sensing Applications of Molecularly Imprinted Fluorescent Carbon Dots for Food and Biological Sample Analysis.

Molecularly imprinted fluorescent carbon dots (MI-FCDs) find numerous applications in analytical chemistry due to their outstanding photoluminescent properties and having specific pockets for the recognition of target molecules. Despite significant advances, practical applications of MI-FCDs-based fluorescent sensors are still in their initial stages. Therefore, the topical developments in the synthesis, working, and application of MI-FCDs for sensing various target species (e.g., pharmaceuticals, biomolecules, pesticides, food additives, and miscellaneous species) in food and biological media have been highlighted. Moreover, a careful evaluation has been made to select the best methods based on their performance in terms of analytical parameters. To expand the horizons of this field, important challenges and future directions for developing MI-FCDs for practical use are also presented. This review will highlight important aspects of MI-FCDs-based fluorescent sensors for their applicability in food science, material science, environmental science, nanoscience, and biotechnology.

A Review of the Analysis of Phthalates by Gas Chromatography in Aqueous and Food Matrices.

As a commonly well-known industrial chemical, phthalates are produced in high volumes to be used in various consumer products (e.g., plasticizers, medical devices, construction materials, and toys) to enhance softness, durability, transparency, and flexibility. Phthalates are generally not chemically bonded to the polymer chain of the plastic in which they are mixed. Thus, they may leach, migrate, or evaporate into indoor/outdoor air, and foodstuffs. In this review, a comprehensive overview of several sample preparation methods coupled with gas chromatography for the analysis of phthalates in various kinds of complex matrices, with a focus on the last 20 years' worth of papers. The review begins by highlighting the environmental significance of phthalate pollution along with the various routes to their exposure to general population. Then, the discussion is extended to cover the pretreatment and extraction techniques for phthalates for their quantitation based on gas chromatographic approach. Finally, the present and future challenges for the detection of phthalates in aqueous and food matrices are discussed.

Selective quantification of diclofenac from groundwater and pharmaceutical samples by magnetic molecularly imprinted polymer-based sorbent coupled with the HPLC-PDA detection.

Diclofenac (DCF) is a pharmaceutical contaminant of water bodies and therefore, improvement of analytical techniques for its removal and quantitation is one of the current interests of analysts. Herein, DCF selective magnetic molecularly imprinted polymer (MMIP) has been fabricated and characterized by Fourier transform-infrared spectroscopy, thermogravimetric analysis, vibrating scanning magnetometer, scanning electron microscopy, high-resolution transmission electron microscope, energy-dispersive X-ray spectroscopy, and Brunauer-Emmett-Teller analyzer. Furthermore, the protocol for the quantification of DCF using MMIP-HPLC-PDA combo has been optimized by investigating the effect of the amount of MMIP, type and volume of eluent, and variation of pH. The optimized protocol suggested a method detection limit of 0.042 ng mL-1 and linearity of results in the range 0.1-100 ng mL-1 (R2 = 0.99). The fabricated material offered recovery of DCF up to 96.38-99.46% from groundwater and pharmaceutical samples with a relative standard deviation of <4%. In addition, the material was found selective and sensitive for DCF among its analogous drugs like mefenamic acid, ketoprofen, fenofibrate, aspirin, ibuprofen, and naproxen.

Biomass-Derived Core-Shell Carbon Dots with Embedded Tripodal Receptors for the Selective Recognition of Mefenamic Acid in Pharmaceutical Formulations and Urine.

A tripodal amine (TPA) with -OH, N, and S donors is synthesized to functionalize a core-shell carbon dot composite (FCDs@SiO2-TPA) for sensing application. The TPA is characterized by spectroscopic and spectrometric techniques, and the composite is characterized by Fourier transform infrared spectroscopy (FT-IR), thermogravimetric analysis (TGA), Brunauer-Emmett-Teller (BET), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and energy-dispersive X-ray spectra (EDS) techniques. The composite has the ability to recognize mefenamic acid (MFA) selectively even in the presence of other drugs like ibuprofen sodium, acetylsalicylic acid, naproxen sodium, diclofenac sodium, and ketoprofen. It can also be used for the quantification of MFA by recording the emission quenching response of the sample at λexc. = 350 nm and λems. = 460 nm (linear range = 1-8 µM and LOD = 197 nM). The density functional theory calculations and 1H NMR titration suggest quenching of the emission signal due to photoinduced electron transfer via hydrogen bonding between the probe and MFA. The composite FCDs@SiO2-TPA has been demonstrated as a reliable and cost-effective sensing probe for the detection of MFA in pharmaceutical formulations, water samples, and cow urine samples.

Self-polymerized polydopamine-imprinted layer-coated carbon dots as a fluorescent sensor for selective and sensitive detection of 17ß-oestradiol.

The compound 17ß-oestradiol (E2) is a steroidal oestrogen used extensively in food processing and animal husbandry. As E2 is well-known as a typical endocrine disrupting chemical, its release, penetration, and exposure create serious environmental concerns. Carbon dots (CDs) have attracted great attention due to their excellent fluorescent and non-toxic properties. To help improve the selectivity of CDs, they can be combined with molecularly-imprinted polymers (MIPs). In light of the limitations involved in the fabrication of MIP layer on CDs (e.g., time consumption and low controllability of imprinted layer), the mussel inspired dopamine self-polymerization can be considered as an alternative option. As functional monomer in molecular imprinted technology, dopamine can be used efficiently to polymerize in weak alkaline condition (e.g., formation of polydopamine). In this research, a new method was developed for selective and sensitive fluorescent detection of E2 based on self-polymerization of dopamine (functional monomer) on fluorescent carbon dots (CDs@MI-PDA). The developed sensor selectively binds with E2 to quench the fluorescence intensity of CDs by photo-induced electron transfer. The sensor showcases a detection limit of E2 as 0.34 ng/mL with a linearity over 1-50 ng/mL. Furthermore, the probe was successfully applied to water (tap and river water) and milk samples with recoveries of 96.4-102.2 %. This study is expected to open a new path for the development of a simple and convenient detection approach for E2 present in complex matrices.

Magnesium/aluminum layered double hydroxides intercalated with starch for effective adsorptive removal of anionic dyes.

In this research, the adsorptive performance of a starch-magnesium/aluminum layered double hydroxide (S-Mg/Al LDH) composite was investigated for different organic dyes in single-component systems by conducting a series of batch mode experiments. S-Mg/Al LDH composite showed preferential adsorption of anionic dyes than cationic dyes. The marked impact of key process variables (e.g., contact time, adsorbent dosage, pH, and temperature) on its adsorption was investigated. Multiple isotherms, kinetics, and thermodynamic models were applied to describe adsorption behavior, diffusion, and uptake rates of the organic dyes over S-Mg/Al LDH composite. A better fitting of the non-linear Langmuir model reflects the predominance of monolayered adsorption of dye molecules on the composite surface. Partition coefficients (mg g-1 µM-1) for S-Mg/Al LDH were observed in the following descending order: Amaranth (665) > Tartrazine (186) > Sunset yellow (71) > Eosin yellow (65). Furthermore, comparative evaluation of the adsorption enthalpy, entropy, and Gibbs free energy values indicates that the adsorption process is spontaneous and exothermic. S-Mg/Al LDH composite maintained a stable adsorption/desorption recycling process over six consecutive cycles with the advantages of low cost, chemical/mechanical stability, and easy recovery. The results of this study are expected to expand the application of modified LDHs toward wastewater treatment.

Mesoporous silica imprinted carbon dots for the selective fluorescent detection of triclosan.

A molecularly imprinted fluorescence sensor built as a mesoporous structured silica imprinted layer on the surface of carbon dots (CDs@m-MIP) was employed for the selective detection of triclosan (TRI). The fluorescence of this CDs@m-MIP was affected sensitively and selectively by TRI via an electron transfer-induced fluorescence quenching mechanism with a detection limit of TRI at 1.08 nM (range 1.72-138 nM) under the optimum setup (e.g., pH, response time, and CDs@m-MIP dose). This approach was used successfully to detect TRI in real water samples (e.g., sewage, river, and tap water). The recoveries of TRI were satisfactory in spiked river and tap water (in 94.7-99.5 %). The outcome of this research is thus expected to help develop highly efficient fluorescent sensing systems towards diverse hazardous compounds including TRI.

Chitosan-Ni/Fe layered double hydroxide composites as an efficient solid phase extraction sorbent for HPLC-PDA monitoring of parabens in personal care products.

There is a dire need for development of efficient and sensitive methods to efficiently screen parabens. In this research, we focused on quantification of four parabens (i.e., methylparaben (MP), ethylparaben (EP), propylparaben (PP), and butyl paraben (BP)) using chitosan intercalated nickel/iron layered double hydroxide (CS-Ni/Fe-LDH) composites as solid phase extraction sorbent prior to HPLC-PDA analysis. CS-Ni/Fe LDH composites with a heterogeneous, porous texture, and coral reef-like structure exhibit appealing extraction efficiency for the target parabens due to the enhanced possibility for the formation of hydrogen bonding and hydrophobic interactions. The performance of the composites was assessed and optimized for solid phase extraction of parabens from standard samples and real samples (rose water, cream, toothpaste, hair serum, and sunscreen). The LDH-SPE-HPLC method exhibited a wide linear range (e.g., 100-50,000 ng L-1), good linearity (R2 ≥ 0.999), and good precision (relative standard deviation (RSD) < 3%). This method successfully enriched selected parabens with remarkable recovery above 85.95% and a good RSD (0.01-2.90%). The quantitation of MP, EP, PP, and BP was made at detection range (and limits of detection (LOD)) of 5-15 (9.8), 11-21 (16.2), 6-18 (12.4), and 10-20 (15.6) ng L-1, respectively. The prepared composites also displayed excellent performance with enhanced reusability/durability (n = 30 cycles) and reproducibility (n = 5).

Hollow porous molecularly imprinted polymers as emerging adsorbents.

Hollow porous molecularly imprinted polymers (HPMIPs) are identified as promising adsorbents with many advantageous properties (e.g., large number of imprinted cavities, highly accessible binding sites, controllable pore structure, and fast mass transfer). Because of such properties, HPMIPs can exhibit improved binding capacity and kinetics to make analyte molecules readily interact with a greater number of recognition sites on the imprinted shell. This review highlights the synthesis and utility of HPMIPs as adsorbents to cover diverse targets of interest (e.g., endocrine disrupting chemicals, pharmaceuticals, pesticides, and heavy metal ions). The overall potential of HPMIPs is thus discussed in the context of analytical chemistry with particular focus on the efficient extraction of trace-level targets from complex matrices.

Dual-template magnetic molecularly imprinted polymer-based sorbent for simultaneous and selective detection of phenolic endocrine disrupting compounds in foodstuffs.

In this research, an efficient (94.9-99.4%) and fast (5 min) method has been developed and validated for simultaneous identification and quantification of phenolic endocrine disrupting compounds with an emphasis on bisphenol A (BPA) and 4-cumylphenol (4-CP) in food stuffs using a dual-template magnetic, molecularly-imprinted polymer (dt-MMIP). The dt-MMIP was synthesized by a sol-gel method using Fe3O4@SiO2 (as the core) and BPA and 4-CP (as templates). The dt-MMIP was coupled with magnetic solid phase extraction to simultaneously detect BPA and 4-CP in food samples. BPA was measured from bottled water and fruit juice samples samples at 0.36 and 0.24 ng mL-1, respectively, while 4-CP in those samples was 0.33 and 0.16 ng mL-1, respectively. Their detection limits were estimated as 0.04 and 0.05 ng mL-1, respectively. The developed dt-MMIP method was highly reproducible, while maintaining a good cyclability up to 20 cycles.

Starch-Mg/Al layered double hydroxide composites as an efficient solid phase extraction sorbent for non-steroidal anti-inflammatory drugs as environmental pollutants.

Using a co-precipitation method, starch-Mg/Al layered double hydroxide (S-Mg/Al LDH) composites were synthesized. Their physicochemical properties were assessed by Fourier-transform infrared spectroscopy, X-ray diffraction, scanning electron microscopy, and thermo-gravimetric analysis. The quantification of six non-steroidal anti-inflammatory drugs (NSAIDs) was conducted using real samples (e.g., hospital waste water, river water, sewage treatment plant water, and tablet formulations) by gas chromatography-mass spectrometry. For the development of this method, the system was optimized in terms of several key variables (e.g., pH, flow rate, and eluent type/volume). The developed method for NSAIDs exhibited good resolution, sensitivity, reproducibility, and specificity even in complex matrices with limits of detection between 4 and 20 pg/mL. Hence, S-Mg/Al LDH composites were proven to be efficient and fast solid phase extraction (SPE) sorbents for NSAIDs. In addition, each LDH-SPE cartridge showed good reusability without a noticeable change in performance (e.g., up to 30 cycles) and target recoveries between 99.5 - 82.9 %. This work should open up new opportunities for a sesnsitive and sustainable quantitative method for the determination of NSAIDs in complex samples.