Recent Advances in Nanomaterials Based Optical Sensors for the Detection of Melatonin and Serotonin.

In this review paper we discussed the detection of melatonin and serotonin by using various optical methods. Melatonin and serotonin are very necessary body hormones these are also called neuroregulatory hormones secreted by pineal gland in brain by pinealocytes and shape of pineal gland is cone like. Sensitive detection of melatonin and serotonin in pharmacological samples and human serum is crucial for human beings, lots of research publications available in literature for melatonin and serotonin and we overviewed these papers. We have deeply reviewed many research papers where sensitively sensing of melatonin and serotonin occurs, by using of various interfering agents and nanomaterials. This review aims presenting colorimetry, fluorometry and spectrophotometric detection of melatonin (MEL) and serotonin (SER) by using different metal oxides, carbon nanomaterials (nanosheets, nanorods, nanofibers) and many other agents. Nanomaterials typically possess favourable optical, electrical and mechanical characteristics, they provide up new avenues for enhancing the efficacy of sensors. It is crucial to provide an optical sensors platform that is dependable, sensitive and low price. The development of sensors and biosensors to use nanomaterials for neurotransmitters has advanced significantly in recent years. There are currently many developing biomarkers in biological fluids, and bionanomaterial-based biosensor systems, as well as clinical and pharmacological settings, have garnered significant interest. Biomarkers have been found using optical devices in a quick, selective and sensitive manner. Our aim is to compile all the data that already published on MEL, SER sensing and comparison of each method, we mainly focused on principle, observations, sensitivity, selectivity, limit of detection, mechanism behind the reaction, effect of temperature, pH and concentration. In the last of this paper, we discuss some challenges of these methods and future projects.

DFT studies of structural and some spectral parameters of copper(II) complexes with N,N,N',N″-tetrakis (2-hydroxyethyl/propyl) ethylenediamine and tris(2-hydroxyethyl)amine.

The structures and some spectral parameters of three copper(II) complexes; [Cu(THEEN)(H2O)](PIC)2 (1), [Cu(THPEN)] (PIC)2 C3H8O (2) and [Cu(TEAH3)(PIC)] (PIC)⋅(H2O) (3), previously synthesized and characterized by X-ray diffraction, are here computationally studied by using density functional theory (DFT) in its hybrid form B3LYP. In these complexes, THEEN is N,N,N',N″-tetrakis(2-hydroxyethyl) ethylenediamine and THPEN is N,N,N',N″-tetrakis(2-hydroxypropyl) ethylenediamine, tetrapodal ligands and TEAH3 is tris(2-hydroxyethyl)amine, a tripodal ligand. The primary coordination sphere of copper(II) ion in complexes (1), (2) and (3) are optimized, structural parameters are calculated, vibrational bands are assigned and energy gaps of frontier orbital (HOMO-LUMO) have been calculated with B3LYP/6-31G/LANL2DZ level of theory using DMSO as solvent. The calculated geometric and spectral results reproduced the experimental data with well agreement. Theoretical calculated molecular orbitals (HOMO-LUMO) and their energies have been calculated that suggest charge transfer occurs within the complexes.

Metal complexes of tetrapodal ligands: synthesis, spectroscopic and thermal studies, and X-ray crystal structure studies of Na(I), Ca(II), Sr(II), and Ba(II) complexes of tetrapodal ligands N,N,N',N'-tetrakis(2-hydroxypropyl)ethylenediamine and N,N,N',N'-tetrakis(2-hydroxyethyl)ethylenediamine.

Twelve complexes 1-12 of general category [M(ligand)(anion)(x)(water)(y)], where ligand = N,N,N',N'-tetrakis(2-hydroxypropyl/ethyl)ethylenediamine (HPEN/HEEN), anion = anions of picric acid (PIC), 3,5-dinitrobenzoic acid (DNB), 2,4-dinitrophenol (DNP), and o-nitrobenzoic acid (ONB), M = Ca(2+), Sr(2+), Ba(2+), or Na(+), x = 1 and 2, and y = 0-4, were synthesized. All of these complexes were characterized by elemental analysis, IR, (1)H and (13)C NMR, and thermal studies. X-ray crystal studies of these complexes 1-12, [Ca(HPEN)(H(2)O)(2)](PIC)(2).H(2)O (1), [Ca(HEEN)(PIC)](PIC) (2), Ba(HPEN)(PIC)(2) (3), [Na(HPEN)(PIC)](2) (4), Ca(HPEN)(H(2)O)(2)](DNB)(2).H(2)O (5),Ca(HEEN)(H(2)O)](DNB)(2).H(2)O (6), [Sr(HPEN)(H(2)O)(3)](DNB)(2) (7), [Ba(HPEN)(H(2)O)(2)](DNB)(2).H(2)O](2) (8), [[Ba(HEEN)(H(2)O)(2)](ONB)(2)](2) (9), [[Sr(HPEN)(H(2)O)(2)](DNP)(2)](2) (10), [[Ba(HPEN)(H(2)O)(2)](DNP)(2)](2) (11), and [Ca(HEEN)(DNP)](DNP) (H(2)O) (12), have been carried out at room temperature. Factors which influence the stability and the type of complex formed have been recognized as H-bonding interactions, presence/absence of solvent, nature of the anion, and nature of the cation. Both the ligands coordinate the metal ion through all the six available donor atoms. The complexes 1 and 5-11 have water molecules in the coordination sphere, and their crystal structures show that water is playing a dual character. It coordinates to the metal ion on one hand and strongly hydrogen bonds to the anion on the other. These strong hydrogen bonds stabilize the anion and decrease the cation-anion interactions by many times to an extent that the anions are completely excluded out of the coordination sphere and produce totally charge-separated complexes. In the absence of water molecules as in 2 and 3 the number of hydrogen bonds is reduced considerably. In both the complexes the anions case interact more strongly with the metal ion to give rise to a partially charge-separated 2 or tightly ion-paired 3 complex. High charge density Ca(2+) forms only monomeric complexes. It has more affinity toward stronger nucleophiles such as DNP and PIC with which it gives partially charge-separated eight-coordinated complexes. But with relatively weaker nucleophile like DNB, water replaces the anion and produces a seven coordinated totally charge-separated complex. Sr(2+) with lesser charge/radius ratio forms only charge-separated monomeric as well as dimeric complexes. Higher coordination number of Sr(2+) is achieved with coordinated water molecules which may be bridging or nonbridging in nature. All charge-separated complexes of the largest Ba(2+) are dimeric with bridging water molecules. Only one monomeric ion-paired complex was obtained with Ba(PIC)(2). Na(+) forms a unique dinuclear cryptand-like complex with HPEN behaving as a heptadentate chelating-cum-bridging ligand.