Ezzat Khan

Phytoremediation of heavy metals—Concepts and applications

The mobilization of heavy metals by man through extraction from ores and processing for different applications has led to the release of these elements into the environment. Since heavy metals are nonbiodegradable, they accumulate in the environment and subsequently contaminate the food chain. This contamination poses a risk to environmental and human health. Some heavy metals are carcinogenic, mutagenic, teratogenic and endocrine disruptors while others cause neurological and behavioral changes especially in children. Thus remediation of heavy metal pollution deserves due attention. Different physical and chemical methods used for this purpose suffer from serious limitations like high cost, intensive labor, alteration of soil properties and disturbance of soil native microflora. In contrast, phytoremediation is a better solution to the problem. Phytoremediation is the use of plants and associated soil microbes to reduce the concentrations or toxic effects of contaminants in the environments. It is a relatively recent technology and is perceived as cost-effective, efficient, novel, eco-friendly, and solar-driven technology with good public acceptance. Phytoremediation is an area of active current research. New efficient metal hyperaccumulators are being explored for applications in phytoremediation and phytomining. Molecular tools are being used to better understand the mechanisms of metal uptake, translocation, sequestration and tolerance in plants. This review article comprehensively discusses the background, concepts and future trends in phytoremediation of heavy metals.

What are heavy metals? Long-standing controversy over the scientific use of the term ‘heavy metals’ – proposal of a comprehensive definition

ABSTRACT The term ‘heavy metals’ is commonly used in the environmental literature to refer to metals and metalloids associated with environmental pollution, toxicity and adverse effects on biota. The term has been diversely defined, mostly in terms of density, relative atomic mass and atomic number. This diversity of definitions has raised questions about the nomenclature of these elements. The inclusion of the metalloid As and the nonmetal Se with heavy metals is also an important issue. Some people have called the term as meaningless, imprecise and poorly defined and have suggested abandoning the use of the term. The term itself may not be problematic but the careless and inconsistent use of terminology has led to a confusion about the meaning of the term. The use of the term may be continued but it should be defined in a more comprehensive and scientific way. Here, a more comprehensive definition of the term ‘heavy metals’ is suggested as ‘naturally occurring metals having atomic number (Z) greater than 20 and an elemental density greater than 5 g cm−3.’ A screening of the Periodic Table according to this definition yields 51 elements to be called ‘heavy metals.’ As and Se are excluded from heavy metals.

Environmental chemistry in the twenty-first century

Human society actually faces many environmental challenges such as environmental pollution, climate changes and loss of biodiversity. These issues induce major risks for ecosystems and are a serious threat for further life on Earth. Anthropogenic pressure may continue to exacerbate the present-day problems. Prevention and mitigation of environmental issues demands sound science and dedicated political support. For that, environmental chemistry is a central and multidisciplinary science that will provide new concepts and applied methods to solve actual environmental issues. Here, we outline the scope of environmental chemistry. The Anthropocene era and major chemical disasters are discussed. We present also the challenges of atmospheric chemistry, analytical chemistry, statistics and chemometrics, and education in environmental chemistry.

Isolation, crystal structure determination and cholinesterase inhibitory potential of isotalatizidine hydrate from Delphinium denudatum

Abstract Context: Delphinium denudatum Wall (Ranunculaceae) is a rich source of diterpenoid alkaloids and is widely used for the treatment of various neurological disorders such as epilepsy, sciatica and Alzheimer’s disease. Objective: The present study describes crystal structure determination and cholinesterase inhibitory potential of isotalatazidine hydrate isolated from the aerial part of Delphinium denudatum. Materials and methods: Phytochemical investigation of Delphinium denudatum resulted in the isolation of isotalatazidine hydrate in crystalline form. The molecular structure of the isolated compound was established by X-ray diffraction. The structural data (bond length and angles) of the compound were calculated by Density Functional Theory (DFT) using B3LYP/6-31 + G (p) basis set. The cholinesterase inhibitory potential of the isolated natural product was determined at various concentrations (62.5, 125, 250, 500 and 1000 μg/mL) followed by molecular docking to investigate the possible inhibitory mechanism of isotalatazidine hydrate. Results: The compound crystallized in hexagonal unit cell with space group P65. Some other electronic properties such as energies associated with HOMO-LUMO, band gaps, global hardness, global electrophilicity, electron affinity and ionization potential were also calculated by means of B3LYP/6-31 + G (p) basis set. The compound showed competitive type inhibition of both acetylcholinesterase (AChE) and butyrylcholinesterase (BChE) with IC50 values of 12.13 μM and 21.41 μM, respectively. Discussion and conclusion: These results suggest that isotalatazidine hydrate is a potent dual cholinesterase inhibitor and can be used as a target drug in Alzheimer diseases. This is first report indicating isotalatazidine hydrate with anticholinesterase potential.

Synthesis, NMR characterization and reactivity of 1-silacyclohex-2-ene derivatives

AbstractThe chloro functionality of allyldichlorosilane (HSiCl2(C3H5)) and allyldichloromethylsilane (MeSiCl2(C3H5)) were replaced by alkynyl groups and new compounds, allyldialkynylsilane 1 and allyldialkynylmethylsilane 2, were obtained. These silanes, which served as starting materials for the onward reactions, were purified by fractional distillation. They were further subjected to hydroboration with 9-BBN (9-borabicyclo[3.3.1]nonane) and were converted into 1-silacyclohex-2-ene derivatives 5 and 6. The competition between C≡C and C=C in the reaction was studied. The hydroborating reagent 9-BBN was expected to prefer terminal C=C bonds and to leave C≡C bond untouched. This hypothesis of preferable hydroboration was experimentally proved, and hence, 1-silacyclohex-2-ene derivatives were obtained in reasonably pure form. The reaction of allyldialkynylsilane 2 with one equivalent of 9-BBN affords 1-silacyclohex-2-ene bearing Si-C≡C-function, ready to be hydroborated further with one equivalent of 9-BBN. The obtained compound bears two C-B bonds, which are attractive synthones for further transformations. This study aims to highlight the chemistry of C-B and Si-H functional groups. All new compounds obtained were colorless air and moisture sensitive oils, and they were studied by multinuclear magnetic resonance spectroscopy (1H, 13C, 11B, 29Si NMR) in solution.

Synthesis and NMR spectroscopic characterization of Si-substituted 1-silacyclobutene derivatives

Hydroboration of trialkyn-1-yl(organo)silanes with one equivalent and two equivalents of 9-borabicyclo[3.3.1]nonane, 9-BBN afford dialkyn-1-ylsilanes and alkyn-1-ylsilanes, respectively. The alkyn-1-ylsilane derivatives are stable at room temperature and can be store under dry argon for prolong period of time. These compounds are attractive materials for further rearrangements to afford novel 1-silacyclobutene derivatives bearing Si-alkenyl or Si-alkynyl functionalities. The hydroboration reaction is well controlled by the Si-R1 function, i.e., the starting silanes with R1 = Ph selectively afford hydroboration of one Si-C≡C bond with one equivalent of 9-BBN, leaving the other two functionalities untouched. Under mild reaction conditions (25°C), the starting silanes with R1 = Me lead to mixture containing dialkyn-1-ylsilane, alkyn-1-ylsilane and their respective 1-silacyclobutene derivatives. All new compounds are sensitive towards air and moisture and were studied by multinuclear magnetic resonance spectroscopy (1H, 13C, 11B, 29Si NMR) in solution.

Assessment of potentially toxic heavy metals and health risk in water, sediments, and different fish species of River Kabul, Pakistan

ABSTRACT Contamination of freshwater bodies and consequently freshwater fish with toxic heavy metals is a serious environmental issue. The trophic transfer of potentially toxic heavy metals in the human food chains, especially in fish has important implications for human health. The present research study was designed to assess the concentrations of the heavy metals Cr, Ni, Cd, and Pb in the water, sediments, and different freshwater fish species of River Kabul, Pakistan. The heavy metals were quantified in the samples with Atomic Absorption Spectrophotometer. Heavy metal contamination in fish muscles was characterized in terms of metal pollution index and biota-sediments accumulation factor, while human health risk was assessed through calculation of estimated weekly intake. The average concentrations of Cr, Ni, Cd, and Pb in muscle samples of the analyzed fish species at different sampling sites of the river ranged from 12.3 to 33.0, 33.2 to 109.2, 0.98 to 1.5, and 13.9 to 29.6 mg kg−1 wet weight, respectively. Based on the current study data, consumption of the analyzed freshwater fish species from River Kabul was generally safe in terms of potential risk from Cd and Pb but the observed Ni accumulation may pose a potential health risk to regular/excessive fish consumers.

Syntheses, molecular structure, and electrochemical investigations of cobalt(II), copper(II), palladium(II), and zinc(II) complexes with 3-methylpyrazole

Mononuclear complexes of 3-methylpyrazole with general formulas (3-Mepz)4CuCl2 (1), (3-Mepz)4CoCl2 (2), (3-Mepz)2PdCl2 (3), and (3-Mepz)2ZnCl2 (4) were prepared by reaction of the corresponding MCl2 salt (M = Cu, Co, Pd, and Zn) with 3-methylpyrazole in appropriate amounts using acetonitrile as solvent at ambient temperature. The X-ray crystal structure determination reveals that 1 and 2 possess octahedral geometry, while 3 and 4 are square planar and tetrahedral, respectively. All the synthesized compounds have the MCl2 fragment, thus making the synthesized compounds attractive synthons for further transformation. The cyclic voltammograms of the synthesized complexes were obtained and the voltammetric signatures of 1, 2, and 4 showed a single irreversible pH-dependent cathodic peak, while 3 has two reversible cathodic peaks. Involvement of protons accompanying the electron transfer processes was ascertained from differential pulse voltammetric results, indicating peak potential shift as a function of pH. Graphical Abstract Complexes of M(II) with 3-methylpyrazole as ligand were prepared at ambient temperature using MCl2 metal salts (M = Cu, Co, Pd, and Zn). Reactions led to the formation of octahedral (Cu, Co), square-planar (Pd), and tetrahedral (Zn) mononuclear complexes. All reactions were straightforward and no appreciable amount of side products was detected. X-ray structures were determined for all the complexes. The cyclic voltammetric investigations indicate the involvement of proton during electron transfer reactions of these complexes.

Bioaccumulation of non-essential hazardous heavy metals and metalloids in freshwater fish. Risk to human health

Contamination of freshwater fish with toxic heavy metals and metalloids is a major environmental issue in terms of public health. For instance, Cd, Pb, Hg and As are biologically non-essential elements with known adverse effects. Consumption of fish contaminated with metals thus poses a risk to human health. Here we review the bioaccumulation of Cd, Pb, Hg and As in freshwater fish, and we discuss the associated risk to human health. We present possible routes for uptake of heavy metals and metalloids in fish. Various factors affect bioaccumulation in fish, such as fish feeding guilds. We also present various indices used to assess risk to human health, such as metal pollution index, health risk index, target hazard quotient and hazard index.

Synthesis, Crystal Structure, and DFT Calculations of 1,3-Diisobutyl Thiourea

1,3-Diisobutyl thiourea was synthesized and characterized by single crystal X-ray diffraction. It gives a monoclinic (α = γ = 90 and β  ≠ 90) structure with the space group P21/c. The unit cell dimensions are a = 11.5131 (4) A, b = 9.2355 (3) A, c = 11.3093 (5) A, α = 90°, β = 99.569° (2), γ = 90°, V = 1185.78 (8) A3, and Z = 4. The crystal packing is stabilized by intermolecular (N–H⋯S) hydrogen bonding in the molecules. The optimized geometry and Mullikans charges of the said molecule calculated with the help of DFT using B3LYP-6-311G model support the crystal structure.