Selective and Recyclable Congo Red Dye Adsorption by Spherical Fe3O4 Nanoparticles Functionalized with 1,2,4,5-Benzenetetracarboxylic Acid.

In this study, the new material Fe3O4@BTCA has been synthesized by immobilization of 1,2,4,5-Benzenetetracarboxylic acid (BTCA) on the surface of Fe3O4 NPs, obtained by co-precipitation of FeCl3.6H2O and FeCl2.4H2O in the basic conditions. Characterization by P-XRD, FE-SEM, and TEM confirm Fe3O4 has a spherical crystalline structure with an average diameter of 15 nm, which after functionalization with BTCA, increases to 20 nm. Functionalization also enhances the surface area and surface charge of the material, confirmed by BET and zeta potential analyses, respectively. The dye adsorption capacity of Fe3O4@BTCA has been investigated for three common dyes; Congo red (C.R), Methylene blue (M.B), and Crystal violet (C.V). The adsorption studies show that the material rapidly and selectively adsorbs C.R dye with very high adsorption capacity (630 mg/g), which is attributed to strong H-bonding ability of BTCA with C.R dye as indicated by adsorption mechanism study. The material also shows excellent recyclability without any considerable loss of adsorption capacity. Adsorption isotherm and kinetic studies suggest that the adsorption occurs by the Langmuir adsorption model following pseudo-second-order adsorption kinetics.

Catalytic CO2 Fixation over a Robust Lactam-Functionalized Cu(II) Metal Organic Framework.

A porous, Cu(II)-metal organic framework (Cu-MOF) constituted of a rigid lactam functionalized ditopic ligand (H2L) was synthesized at room temperature under slow evaporation conditions {H2L = (5-(1-oxo-2,3-dihydro-1H-inden-2-yl)isophthalic acid)}. The single crystal X-ray structure revealed the formation of a 3D framework of Cu-MOF with one-dimensional (1D) channels decorated with lactam groups and exposed metal centers in the crystallographic c-axis. Interestingly, Cu(II) coordinated DMF molecules were eliminated from the Cu(II) metal center on activation of Cu-MOF at a temperature of 150 °C under high vacuum to generate a solvent free framework with pores lined with unsaturated Lewis acidic Cu(II) ions, i.e., Cu-MOF'. The lactam functionalized channels inclined toward the CO2, which interact with the Cu(II) metal sites lined in the channels of Cu-MOF' and exhibit fascinating solvent-free heterogeneous catalytic conversion of CO2 to cyclic carbonates at atmospheric pressure of CO2, under mild conditions. Furthermore, the Cu-MOF' catalyst was easily recycled and reused for several cycles without a significant loss in catalytic activity.

Preparation of the Ru3(CO)8-pyridine-alcohol cluster and its use for the selective catalytic transformation of primary to secondary amines.

The synthesis of pyridine alcohol based ruthenium carbonyl clusters Ru3(hep)2(CO)8 (1), Ru3(hpp)2(CO)8 (2), and Ru3(bhmp-H)2(CO)8 (3) {hep-H = 2-(2-hydroxyethyl)pyridine, hpp-H = 2-(3-hydroxypropyl)pyridine and bhmp-H2 = 2,6-bis(hydroxymethyl)pyridine} has been carried out by the reaction of the corresponding pyridine-alcohol ligands with Ru3(CO)12. Clusters 1-3 have been characterized using elemental analysis, NMR, FT-IR, mass spectrometry and single-crystal X-ray structures. The clusters were explored for the selective catalytic transformation of primary amines into secondary amines using alcohols as the mono-alkylating agents via hydrogen transfer reactions. All three display efficient catalytic activity with 1 being the most effective.

Varying structural motifs in the salen based metal complexes of Co(ii), Ni(ii) and Cu(ii): synthesis, crystal structures, molecular dynamics and biological activities.

Herein, we report the structural and biological activities of a deprotonated Schiff base ligand (H2L) {H2L = 1,1'-(1E,1'E)-(2,4,6-trimethyl-1,3-phenylene)bis(azan-1-yl-1-ylidene)bis(methan-1-yl-1-ylidene)dinaphthalen-2-ol} towards Co(ii), Ni(ii) and Cu(ii) complexes obtained under different conditions. Four new metal complexes have been synthesized: isostructural dimers [Co(L)]2 (1)/[Cu(L)]2 (3), a monomer (Cl3NiH2L)·(Et3NH) (2) and a tetramer [Cu(L)]4 (4). The bioactivity of 1-3 has been investigated through molecular docking with DNA and various proteins, known to be involved in the proliferation of viral diseases or progression of cancer. Complex 1 shows the best results, through a strong binding affinity with NS2B/NS3 protease (dengue virus) in terms of binding energy (-11.21 kcal mol-1) and inhibition constant (6.02 nM). The experimental evidence for the effective binding of 1-4 with the Bovine Serum Albumin (BSA) protein and calf thymus DNA (CT-DNA) is in agreement with our molecular docking results. In addition, the cytotoxicity and antibacterial activity of 1-4 were examined and found to be compatible with biological systems, with 4 showing the highest antibacterial activity. All four complexes were analyzed by elemental analysis and UV/vis analysis, and their molecular structures were authenticated by single crystal X-ray studies.

The development of fluorescence turn-on probe for Al(III) sensing and live cell nucleus-nucleoli staining.

The morphology of nucleus and nucleolus is powerful indicator of physiological and pathological conditions. The specific staining of nucleolus recently gained much attention due to the limited and expensive availability of the only existing stain "SYTO RNA-Select". Here, a new multifunctional salen type ligand (L1) and its Al3+ complex (1) are designed and synthesized. L1 acts as a chemosensor for Al3+ whereas 1 demonstrates specific staining of nucleus as well as nucleoli. The binding of 1 with nucleic acid is probed by DNase and RNase digestion in stained cells. 1 shows an excellent photostability, which is a limitation for existing nucleus stains during long term observations. 1 is assumed to be a potential candidate as an alternative to expensive commercial dyes for nucleus and nucleoli staining.

Varying coordination modes of amide ligand in group 12 Hg(II) and Cd(II) complexes: synthesis, crystal structure and nonlinear optical properties.

Reactions of the amide ligand, H2L (H2L = N,N'-bis[2-(2-pyridyl)methyl]pyridine-2,6-dicarboxamide) with CdCl2 and Hg(CH3COO)2, in 1 : 1 ratio, at 298 K yield dimeric [Hg(L)]2 (1) and trimeric [Cd3(H2L)4Cl6] (2), respectively. In 1, the H2L is coordinated to Hg(II) via six N-atoms of central and terminal pyridines as well as of deprotonated amido groups, whereas the carbonyl groups remain free. However, in 2, the H2L is coordinated to Cd(II) through terminal pyridine N atoms and O atoms from carbonyl groups, whereas the nitrogen atoms of the central pyridine, two terminal pyridine and of all amido groups remain free. Molecular structures of 1 and 2 are confirmed by single crystal X-ray studies. The varying coordination modes of H2L give rise to different electrochemical behavior of 1 and 2, which has also been rationalized by theoretical calculations. Moreover, nonlinear optical (NLO) behavior of both complexes has been investigated using ultra-short femtosecond laser pulses, which ensures that the NLO response is exclusively from their electronic component.

Channel characteristics and planform dynamics in the Indian Terai, Sharda River.

The Sharda River creates and maintains the ecologically diverse remnant patches of rare Terai ecosystem in northern India. This study used repeat satellite imagery and geographic information system analysis to assess the planform dynamics along a 60 km length of the Sharda River between 1977 and 2001 to understand the altered dynamics and its plausible causes in this data-poor region. Analyses revealed that the Sharda River has undergone significant change corresponding to enhanced instability in terms of increased number of neck cut-offs and consistent occurrence of avulsions in subsequent shorter assessment periods. An increased channel area (8%), decreased sinuosity (15%), increased braiding intensity, and abrupt migrations were also documented. The river has migrated toward the east with its west bankline being more unstable. The maximum shifts were 2.85 km in 13 years (1977-1990), 2.33 km in next 9 years (1990-1999), and a substantial shift of 2.39 km in just 2 years (1999-2001). The altered dynamics is making the future of critical wildlife habitats in Kishanpur Wildlife Sanctuary and North Kheri Forest Division precarious and causing significant economic damage. Extensive deforestation and expansion of agriculture since the 1950s in the catchment area are presumed to have severely impacted the equilibrium of the river, which urgently needs a management plan including wildlife habitat conservation, control, and risk reduction. The present study provides a strong foundation for understanding channel changes in the Sharda River and the finding can serve as a valuable information base for effective management planning and ecological restoration.

Formation of a 1D-polymeric chain of Hg building blocks through C-C coupling under ambient conditions.

A novel C-C coupled 1D-polymeric chain (1) is obtained by reaction of HgCl2 and hmp-H (2-(2-hydroxymethyl pyridine)) (1 : 1) in MeOH at ambient temperature. However, a new class of µ-oxo and µ-chloro bridged polymers (2) has been obtained by altering the metal : ligand ratio to 1 : 2.

Biomimetic sensor for certain catecholamines employing copper(II) complex and silver nanoparticle modified glassy carbon paste electrode.

A dimeric Cu(II) complex [Cu(µ(2)-hep)(hep-H)](2)·2ClO(4) (1) containing bidentate (hep-H=2-(2-hydroxyethyl)pyridine) ligand was synthesized and characterized by single crystal X-ray diffraction studies. Each Cu-ion in 1 is in a distorted square pyramidal geometry. Further 1 along with silver nanoparticles (SNPs) have been used as modifier in the construction of a biomimetic sensor (1-SNP-GCPE) for determining certain catecholamines viz., dopamine (DA), levodopa (l-Dopa), epinephrine (EP) and norepinephrine (NE) using cyclic voltammetry, chronocoulometry, electrochemical impedance spectroscopy and adsorptive stripping square wave voltammetry (AdSSWV). Finally, the catalytic properties of the sensor were characterized by chronoamperometry. Employing AdSSWV, the calibration curves showed linear response ranging between 10(-6) and 10(-9)M for all the four analytes with detection limits (S/N=3) of 8.52×10(-10)M, 2.41×10(-9)M, 3.96×10(-10)M and 3.54×10(-10)M for DA, l-Dopa, EP and NE respectively. The lifetime of the biomimetic sensor was 3 months at room temperature. The prepared modified electrode shows several advantages such as simple preparation method, high sensitivity, high stability, ease of preparation and regeneration of the electrode surface by simple polishing along with excellent reproducibility. The method has been applied for the selective and precise analysis of DA, l-Dopa, EP and NE in pharmaceutical formulations, urine and blood serum samples.

Molecular precursors for the preparation of homogenous zirconia-silica materials by hydrolytic sol-gel process in organic media. Crystal structures of [Zr{OSi(O(t)Bu)3}4(H2O)2]·2H2O and [Ti(O(t)Bu){OSi(O(t)Bu)3}3].

[Zr(OPr(i))(4)·Pr(i)OH] reacts with [HOSi(O(t)Bu)(3)] in anhydrous benzene in 1:1 and 1:2 molar ratios to afford alkoxy zirconosiloxane precursors of the types [Zr(OPr(i))(3){OSi(O(t)Bu)(3)}] (A) and [Zr(OPr(i))(2){OSi(O(t)Bu)(3)}(2)] (B), respectively. Further reactions of A or B with glycols in 1:1 molar ratio afforded six chemically modified precursors of the types [Zr(OPr(i))(OGO){OSi(O(t)Bu)(3)}] (1A-3A) and [Zr(OGO){OSi(O(t)Bu)(3)}(2)] (1B-3B), respectively [where G = (-CH(2)-)(2) (1A, 1B); (-CH(2)-)(3) (2A, 2B) and (-CH(2)CH(2)CH(CH(3)-)} (3A, 3B)]. The precursors A and B are viscous liquids, which solidify on ageing whereas the other products are all solids, soluble in common organic solvents. These were characterized by elemental analyses, molecular weight measurements, FAB mass, FTIR, (1)H, (13)C and (29)Si-NMR studies. Cryoscopic molecular weight measurements of all the products, as well as the FAB mass studies of 3A and 3B, indicate their monomeric nature. However, FAB mass spectrum of the solidified B suggests that it exists in dimeric form. Single crystal structure analysis of [Zr{OSi(O(t)Bu)(3)}(4)(H(2)O)(2)]·2H(2)O (3b) (R(fac) = 11.9%) as well as that of corresponding better quality crystals of [Ti(O(t)Bu){OSi(O(t)Bu)(3)}(3)] (4) (R(fac) = 5.97%) indicate the presence of a M-O-Si bond. TG analyses of 3A, B, and 3B indicate the formation of zirconia-silica materials of the type ZrO(2)·SiO(2) from 3A and ZrO(2)·2SiO(2) from B or 3B at low decomposition temperatures (≤200 °C). The desired homogenous nano-sized zirconia-silica materials [ZrO(2)·nSiO(2)] have been obtained easily from the precursors A and B as well as from the glycol modified precursors 3A and 3B by hydrolytic sol-gel process in organic media without using any acid or base catalyst, and these were characterized by powder XRD patterns, SEM images, EDX analyses and IR spectroscopy.

One pot synthesis of maleimide and hydantoin by Fe(CO)5 catalyzed [2 + 2 + 1] co-cyclization of acetylene, isocyanate and CO.

In the presence of a catalytic amount of Fe(CO)(5), terminal acetylenes, isocyanates and CO undergo [2 + 2 + 1] cyclization to form substituted maleimides and hydantoins; when internal alkynes are used, exclusive maleimide formation is observed. While the maleimides can be obtained as the major products, in up to 90% yield, when the reaction is carried out in CO atmosphere, in absence of CO, the hydantoins are formed in up to 87% yield. Formation of maleimides has been shown to occur via the formation of a ferrole intermediate, whereas the hydantoins are proposed to form through successive insertion of isocyanate into the iron-acetylide bond. All compounds were characterized by spectroscopic methods and molecular structures of some compounds were established by single crystal X-ray diffraction method.

Reversible single-crystal to single-crystal transformations in a Hg(II) derivative. 1D-polymeric chain <=>2D-networking as a function of temperature.

Reactions of HgX(2) (X = Cl(-), Br(-), l(-)) with the ligand hep-H (hep-H = 2-(2-hydroxyethyl)pyridine) in methanol at 298 K result in 1D-polymeric chains of [(X)Hg(mu-X)(2)(hep-H)](infinity), 1-3, respectively, where hep-H binds to the Hg(ii) ions in a monodentate fashion exclusively with the pyridine nitrogen donor and the suitably ortho-positioned -(CH(2))(2)OH group of hep-H remains pendant. The packing diagrams of 1-3 exhibit extensive intramolecular and intermolecular hydrogen bonding interactions leading to hydrogen bonded 2D network arrangement in each case. Though the single crystal of either 2 (X = Br) or 3 (X = I) loses crystallinity upon heating, the single crystal of 1 selectively transforms to a 2D-polymeric network, 4 on heating at 383 K for 1.5 h. The polymeric 4 consists of central dimeric [Hg(mu(3)-Cl)(hep-H)Cl](2) units, which are covalently linked with the upper and lower layers of [-(mu-Cl)(2)-Hg-(mu-Cl)(2)-Hg(mu-Cl)(2)-](n). The packing diagram of 4 reveals the presence of O-H-Cl and C-H-Cl hydrogen bonding interactions which in effect yields hydrogen bonded 3D-network. Remarkably, the single crystals of 4 convert back to the single crystals of parent 1 on standing at 298 K for three days.

Biomimetic sensor for certain phenols employing a copper(II) complex.

A new dimeric Cu(II) complex [Cu(mu(2)-hep)(hep-H)](2).2PF(6) (1) containing a bidentate (hep-H = 2-(2-hydroxyethyl)pyridine) ligand was synthesized and characterized by single crystal X-ray diffraction studies. Each Cu ion in 1 is in a distorted square pyramidal geometry. Further 1 is used as a modifier in the construction of a biomimetic sensor for determining phenols [phenol (Phe), resorcinol (Res), hydroquinone (HQ), and catechol (Cat)] in phosphate buffer by using cyclic voltammetry (CV), chronocoulometry, electrochemical impedance spectroscopy (EIS), differential pulse voltammetry (DPV), and square wave voltammetry (SWV). DPV has been proposed for trace determination of Phe and Res while SWV for HQ and Cat. The method has been applied for the selective and precise analysis of Phe in commercial injections, Res in hair coloring agents, HQ in photographic developers and cosmetics, and Cat in tea samples and guarana tablets. The calibration curves showed a linear response ranging between 10(-6) and 10(-8) M for all four of the analytes with detection limits (3sigma) of 1.04 x 10(-8), 2.31 x 10(-8), 1.54 x 10(-8), and 0.86 x 10(-8) M for Phe, Res, HQ, and Cat, respectively. The lifetime of the biomimetic sensor was 200 days at room temperature (at least 750 determinations). The catalytic properties of 1-CPE were characterized by chronoamperometry and were found to be in good agreement with Michaelis-Menten kinetics.

Single-crystal to single-crystal transformations in discrete hydrated dimeric copper complexes.

The single crystals of discrete hydrated [(OAc)Cu(mu-hep)(2)Cu(OAc)].2H(2)O (.2H(2)O) and [(OAc)Cu(mu-hep)(2) Cu(O(n)Pr)].2H(2)O (.2H(2)O) (the lattice H(2)O molecules exist as a tetrameric water cluster, hep-H = 2-(2-hydroxyethyl)pyridine), OAc(-) = acetate and O(n)Pr(-) = n-propionate) undergo single-crystal to single-crystal (SCSC) transformations to the dehydrated and , respectively, under the influence of heat. The reverse SCSC processes of /-->.2H(2)O/.2H(2)O involving the regeneration of the lattice water tetramers take place on exposure of / to water vapour. However, the blue single crystal of discrete hydrated [(O(n)Pr)Cu(mu-hep)(2)Cu(O(n)Pr)].2H(2)O (.2H(2)O), incorporating the two bulkier O(n)Pr(-) terminal bidentate ligands, irreversibly converts to the green single crystal of a unique discrete tetrameric [Cu(4)(mu(3)hep)(2)(mu-hep)(2)(mu-O(n)Pr)(2)(O(n)Pr)(2)] () with double open cubane core either by heating or by a simple vapour diffusion technique via the breaking and forming of multiple covalent bonds.

Occurrence of phthalic acid esters in Gomti River Sediment, India.

Phthalic acid esters (PAEs) are well-known ubiquitous environmental pollutants and used as plasticizers for the manufacturing of plastic products. During this exploratory study, an attempt has been made to determine the concentration and distribution of five prominent PAEs, viz. di-methyl phthalate (DMP), di-ethyl phthalate (DEP), di-butyl phthalate (DBP), di-(2-ethylhexyl) phthalate (DEHP), and di-octyl phthalate (DOP) in the sediment samples of Gomti River collected from 30 different locations. Identification and quantification of PAEs were performed by high-performance liquid chromatography. The mean concentration values of DMP, DEP, DBP, DEHP, and DOP were found as 10.54, 4.57, 10.41, 31.61, and 5.16 microg/kg, respectively. Limit of detection and limit of quantification for each PAE were also calculated and found in the ranges of 0.09-0.55 and 0.28-1.67 microg/kg. DEHP was the most frequently detected PAE (present in 93.3% samples); however, DOP was found only in 36.7% samples.

Vapor-diffusion-mediated single crystal-to-single crystal transformation of a discrete dimeric copper(II) complex to a discrete tetrameric copper(II) complex.

The symmetric dimeric complex [Cu(mu(2)-hep)(TFA)(H(2)O)](2) (1) has been synthesized from 2-(2-hydroxyethyl)pyridine (hep-H), trifluoroacetic acid (TFA-H), and copper acetate in a 95:5 (v/v) MeOH-H(2)O mixture at 298 K. Each Cu(II) ion in 1 is linked with two mu(2)-alcoholic oxygen atoms and one pyridine nitrogen atom of hep, and the other two coordination sites are occupied by the oxygen donors of TFA and H(2)O. At room temperature, the blue single crystals of 1 transform to the green single crystals of a tetrameric complex, [Cu(4)(mu(3)-hep)(2)(mu(2)-hep)(2)(mu(2)-TFA)(2)(TFA)(2)] (2), in presence of alcoholic vapor. The facile single crystal-to-single crystal (SCSC) transformation of 1 to 2 is accompanied by the removal of coordinated H(2)O molecules in 1 and concomitant formation of four new covalent bonds, two Cu-O(mu(3)-hep) and two Cu-O(mu(2)-TFA). The SCSC transformation of 1 to 2 is selective to the alcoholic vapor; the exposure of single crystals of 1 to heat or light or in vacuum has resulted in an immediate loss in crystallinity.

Reduction of nitrite to NO in an organised triphasic medium by platinum carbonyl clusters and redox active dyes as electron carriers.

Artificial electron donors such as leuco methylene blue and leuco safranin O reduce nitrite ion to nitric oxide. The reaction is effected in a U-tube where nitrite ion and dye in two aqueous layers are separated by a layer of dichloromethane (a close model for a biological liquid membrane) that contains the platinum carbonyl cluster ([Bu(4)N]2[Pt12(CO)24], Chini cluster). On passing dihydrogen an electron transfer chain involving dihydrogen, the dye, the clusters and the nitrite ion is initiated. The cluster catalytically reduces the dye in the presence of dihydrogen, the reduced dye migrates across the phase boundaries and in turn reduces the nitrite ions. The resultant nitric oxide in the effluent gas has been identified by its reactions with cobalamine and myoglobin. When safranin O is the dye, an adduct is formed between the reduced dye and NO. It has been identified by spectroscopic techniques and its probable structure investigated by DFT calculations.

Novel Approach to Mixed Group 15/16 Element Ligands-Formation of Unusual Trichalcogenophosphonato Ligands in Mixed Fe/Cr Clusters.

Trithiophosphonato and triselenophosphonato ligands containing mixed Fe/Cr clusters have been synthesized from the reaction of [Fe3 (CO)9 (µ3 -Y)2 ] (Y=S or Se) with [CpCr(CO)2 (η3 -P3 ] in the presence of trimethylamine oxide. This novel approach leads to new clusters containing the first examples of P(S)S2 and P(Se)Se2 ligands in complexed forms.