Fabrication of Nanobioengineered Interfaces Utilizing Quaternary Nanocomposite for Highly Efficient and Selective Electrochemical Biosensing of Urea.

Nanobioengineered interfaces have gained attention owing to their small size and high surface area-to-volume ratio for utilization as a platform for highly selective and sensitive biosensing applications owing to the integration of biological molecules with engineered nanomaterials/nanocomposites. In this work, a novel Ag-complex, [(PPh3)2Ag(SCOf)]-based quaternary Ag-S-Zn-O nanocomposites (NCs), was synthesized through an environmentally-friendly process. The results revealed the formation of the NCs with an average crystallite size and particle size of 36.08 and 40.22 nm, respectively. In addition, this is the first study to utilize such NCs synthesized via a single-source precursor method, offering enhanced sensor performance due to their unique structural properties. Further, these NCs were used to fabricate a urease (Ur)/Ag-S-Zn-O NCs/ITO nanobioengineered electrode for precise and sensitive electrochemical biosensing of urea. The interfacial kinetic studies revealed quasi-reversible processes with high electron transfer rates and linear current responses, indicating efficient reaction dynamics. A high diffusion coefficient and low surface concentration suggested a fast diffusion-controlled process, affirming the electrode's potential for rapid and sensitive urea detection. The biosensor demonstrated notable sensing properties such as high sensitivity (12.56 µA mM-1 cm-2) and a low detection limit (0.54 mM). The fabricated bioelectrode was highly selective and reproducible and demonstrated stability for up to 60 days. These results validate the potential of this nanobioengineered interface for next-generation biosensing applications, paving the way for advanced point-of-care diagnostics and real-time health monitoring.

Boron-Salphen Conjugate based Molecular Probe Exhibiting Fluorescence On-Off-On Response in Detection of Cu2+ and ATP through Displacement Approach.

Synthesis and photophysical properties of a fluorescent probe HBD is described. Probe upon interaction with metal ions, anions and nucleoside pyrophosphates (NPPs) showed fluorescence quenching with Cu2+ due to chelation enhanced quenching effect (CHEQ). Moreover, interaction of ensemble HBD.Cu2+ with anions and NPPs showed fluorescence "turn-On" response with ATP selectively. "On-Off-On" responses observed with Cu2+ and ATP is attributed to an interplay between ESIPT and TICT processes. Cyclic voltammogram of probe exhibited quasi-reversible redox behaviour with three oxidation and two reduction potentials and the change in band gaps of probe suggested the interaction with Cu2+ and ATP. The 2 : 1 and 1 : 1 binding stoichiometry for an interaction between probe and Cu2+ (LOD, 62 nM) and ensemble, HBD.Cu2+ with ATP (LOD, 0.4 µM) respectively are realised by Job's plot and HRMS data. Cell imaging studies carried out to detect Cu2+ and ATP in HeLa cells. Also, the output emission observed with Cu2+ and ATP is utilized to construct an implication (IMP) logic gate. Test paper strips showed naked-eye visible color responses to detect Cu2+ and ATP. In real water samples probe successfully detected copper (0.03 µM) between 5-6.5 ppb level (ICP-MS method).

Synthesis and structural features of indium(III) furan-2-thiocarboxylates showing efficient catalytic activity toward multicomponent reactions via Knoevenagel condensation.

A series of furan-2-thiocarboxylate complexes of indium(III), Et3NH[In(SCOf)4] (1), iPr2NH2[In(SCOf)4] (2), [In(2,2'-bipy)(SCOf)3] (3a), and [In(1,10-phen)(SCOf)3] (3b), have been synthesized and structurally characterized. Complex 4, [In(TMEDA)(SCOf)(SH)2], was obtained by the partial hydrolysis of [In(TMEDA)(SCOf)3] (3). Heterobimetallic complexes [(SCOf)2In(µ-SCOf)2Cu(PPh3)2] (5) and [(SCOf)2In(µ-SCOf)2Ag(PPh3)2] (6), were also synthesized and characterized. In an attempt to synthesize the binary compound, In(SCOf)3 (7), a thioester fCOSCH2SCOf (8) was obtained serendipitously; thus, a novel convenient approach for thioester synthesis is introduced. The catalytic activities of all the complexes were assessed for Knoevenagel condensation and Knoevenagel initiated MCRs for the synthesis of chromene and imidazopyrimidine derivatives and it was found that complex 2 is a very efficient catalyst (much superior to the previously reported ones).

Synthesis of a Series of a Few Hydrosulfide Complexes of Cu(I). A µ3-SH-Bridged Rare Cubane-like Tetramer Showing Efficient Catalytic Activity toward Azide-Alkyne Cycloaddition.

A cubane-like tetranuclear hydrosulfido complex of Cu(I), [Cu4(SH)4(PPh3)4] (1), has been synthesized by the reaction of Cu(NO3)2·3H2O, NaSCOPh, and Cu(PPh3)2NO3 and characterized structurally. Complex 1 represents the first example of crystallographically characterized µ3-SH-bridged cubanoid hydrosulfide. By direct reactions of [(PPh3)2Cu(NO3)] and NaSH, neutral hydrosulfide complexes [Cu(SH)(PPh3)2]·C6H6 (2), [Cu2(SH)2(PPh3)3] (3), and [Cu2(SH)2(PPh3)4] (4) have also been synthesized and structurally characterized. Complex 2 is monomeric with a terminal hydrosulfide ligand. The other two, 3 and 4, are µ2-SH-bridged unsymmetrical and symmetrical dinuclear complexes, respectively. In the symmetric one (4), both Cu(I) ions are tetrahedrally coordinated while in the unsymmetric one (3), one Cu(I) ion is tetrahedral and the other one has a trigonal-planar coordination geometry. The catalytic activity of a hydrosulfido complex in a "click" azide-alkyne cycloaddition reaction has been explored for the first time, and complex 1 is found to be an efficient catalyst for the regioselective synthesis of glycoconjugate triazoles.

Pure shift HMQC: Resolution and sensitivity enhancement by bilinear rotation decoupling in the indirect and direct dimensions.

The heteronuclear multiple-quantum coherence in the indirect dimension of the two-dimensional HMQC experiment evolves under the passive 1H-1H J-couplings leading to multiplet structures in the F1 dimension. Besides, 1H-1H J-multiplets appear in the direct dimension as well. Thus, multiplets along both dimensions lower the resolution and sensitivity of this technique, when high resolution is required along both dimensions. An efficient broadband homodecoupling scheme along the F1 dimension of the HMQC experiment has not been realized to date. We have implemented broadband homonuclear decoupling using bilinear rotation decoupling (BIRD) by adding a 1H SQ evolution period followed by BIRD before the 1H-13C multiple-quantum evolution period in the HMQC. In the direct time domain, BIRD is implemented using a real-time or single-scan scheme, which further improves resolution and sensitivity of this technique. The resulting pure shift HMQC provides singlet peak per chemical site along F1 as well as F2 axes and, hence, better resolution and sensitivity than conventional HMQC spectrum for all peaks except diastereotopic methylene protons. Due to the incorporation of the BIRD, the indirect time domain becomes double in length compared to the conventional HMQC. However, slow relaxation of small molecules favors better sensitivity for ps-HMQC relative to conventional HMQC under all conditions. We also found that the sensitivity of ps-HMQC is only slightly less than ps-HSQC for small molecules.

Perfecting band selective homo-decoupling for decoupling two signals coupled within the same band.

Recently, pure shift NMR methods have delivered ultrahigh resolution broadband proton NMR spectra that display singlet peak per chemical site. BASH/HOBS (band selective homo-decoupling/homonuclear band selective) decoupling is the only method that provides singlet only spectrum for a selected signal or a group of signals with a sensitivity higher than regular proton NMR, and an order of magnitude higher than broadband pure shift techniques. It is this aspect that makes this technique important. In the present work, we show that perfect echo (PE) when combined with band selective homo-decoupling (BASHD) permits increasing the bandwidth of the BASH/HOBS decoupling resulting in reduced experimental time for this class of experiments. Using new PE-BASHD technique two closely resonating coupled signals could be decoupled in a single experiment which otherwise demands two separate BASHD experiments. In polypeptides, it also allows decoupling of Hα and HN signals simultaneously from each other as well as from the side chain protons reducing experimental time. Further, pseudo 2D based PE-BASHD scheme provides spectrum superior to the real-time BASHD spectrum when applied to closely resonating coupled signals. Numerical simulation as well as experimental results indicate that the PE-BASHD sequence display good quality singlet only spectrum even in the presence of moderate strong coupling.

A dinuclear copper(i) thiodiacetate complex as an efficient and reusable 'click' catalyst for the synthesis of glycoconjugates.

We report herein the facile synthesis and structural characterization of a highly stable dinuclear Cu(i) complex, [(PPh3)2Cu(µ-tda)Cu(PPh3)2]·6H2O 1 (tda = thiodiacetate anion), in which the Cu-Cu distance is 7.197 Å. This "pre-formed" complex serves as an extremely efficient and recyclable homogeneous catalyst (2 mol%, 30 min) for CuAAC in dichloromethane solvent. The synthesis of a variety of glycoconjugates under ambient conditions is successfully achieved using 1 as a catalyst. The products are obtained in high yields and very short reaction times while complying with the "click protocols". A simpler procedure solely involving the mixing of substrates with 1 (i.e. base free and solvent free) gave the corresponding glycoconjugate in 10 min using 2 mol% of the catalyst.

Analyses of Complex Mixtures by F1 Homo-Decoupled Diagonal Suppressed Total Correlation Spectroscopy.

A diagonal suppressed F1 decoupled total correlation spectroscopy(TOCSY) experiment is developed for analyses of complex mixtures. In 2D homonuclear correlation, assignment of the cross peaks is crucial for structure elucidation. However, when cross peaks are close to the diagonal peaks in overcrowded spectral regions, their assignment becomes tedious. In complex mixtures, the presence of multiple spectra along with broad and complex proton multiplets owing to homonuclear scalar couplings degrade the resolution to the extent that assignment of various cross peaks becomes tedious or impossible. Herein, a diagonal suppressed total correlation technique with F1 decoupling is presented to improve the resolution of the cross peaks. The resolution of the cross peaks is improved by both diagonal suppression as well as the collapse of the multiplets to singlets. Application of the method to a few mixtures of organic compounds reveals better identification of the cross peaks relative to other TOCSY variants.

Geometrically unprecedented 3-, 5- and 7-membered Hg(II)-Cu(I) and Hg(II)-Ag(I) thiolate clusters: precursors to intermetallics.

The syntheses of three polynuclear heterobimetallic complexes through the use of a homoleptic mercuric thiolate anion as a template for the assembly of coinage metal are presented. The complexes, [(PPh3)3Ag3(µ-SPh)7Hg2] (1), [Hg(µ-SPh)4{Cu(PPh3)2}2] (2) and [(dppe)2Cu5(µ-SPh)7Hg2(SPh)2] (3) were utilized as precursors for the fabrication of Hg-Ag and Hg-Cu intermetallics.

A Cu(II) mediated new desulfurization pathway involving elimination of ethylene sulfide.

Reaction of thiodiacetate anion (tda) with [Cu(TMEDA)(NO3)2] (TMEDA = N,N,N'N'-tetramethyl ethylene-diamine) in a stoichiometric ratio afforded the complex {[Cu(TMEDA)(tda)]·(H2TMEDA)(NO3)2·H2O} (1). When [Cu(TMEDA)(NO3)2] was added in excess, it yielded a µ-oxalato complex {[Cu2(TMEDA)2(µ-ox)(H2O)2](NO3)2·2CH3CN} (2). The reaction involves a facile room temperature desulfurization of the thiodiacetate moiety via elimination of ethylene sulfide (thiirane).

ROS and RNS induced apoptosis through p53 and iNOS mediated pathway by a dibasic hydroxamic acid molecule in leukemia cells.

Anticancer drugs induce apoptosis to cancer cells and also exhibit undesired toxicity to normal cells. Therefore development of novel agents triggering apoptosis and have low toxicity towards normal cells is most important. Hydroxamic acids suppress tumour cell growth through apoptosis but the underlying mechanism is poorly understood. Herein, we describe the apoptotic potential of a dibasic hydroxamic acid derivative, viz., oxayl bis (N-phenyl) hydroxamic acid (OBPHA), which induces apoptosis through generation of both ROS and NO in doxorubicin resistant T-lymphoblastic leukemia, CEM/ADR5000 cells. Present study discloses that OBPHA selectively kills cancerous cells irrespective of their drug resistant phenotype. We also determined the crystal structure of OBPHA to understand the structural requirements for apoptosis; the study reveals that the presence of substituted hydroxamic acid groups (-CO-NH-OH) favours the generation of NO possibly through auto degeneration. Along with the induction of caspase 3 mediated intrinsic apoptosis; OBPHA also activates p53 dependent signalling cascade and downregulates HDAC3 expression in a time dependent manner possibly due to increased ROS and NO production and simultaneous decrease in cellular GSH level. Thus ROS and NO mediated downstream signalling are essential for the anticancer effect of OBPHA. Therefore OBPHA, having a structurally relevant pharmacophore provides important insight into the development of new ROS and RNS generating chemicals inducing p53 dependent apoptosis.

Synthesis of glycoconjugate benzothiazoles via cleavage of benzotriazole ring.

A concise and efficacious benzotriazole-mediated novel two-step protocol has been developed for easy access to glycoconjugate benzothiazoles from protected carbohydrates. The benzotriazolemethanethione 3, prepared by the reaction of free alcohol with bis(1H-benzo[1,2,3]triazol-1-yl)methanethione, on treatment with silanes or stannane under heating or microwave irradiation undergoes free radical ß-scission of N-N bond and affords diverse range of 2-O-substituted benzothiazoles 4 via cyclative elimination of molecular nitrogen. The structures of all of the compounds have been elucidated using IR, NMR, MS, and elemental analysis, and five of them have been characterized by single-crystal X-ray analysis.

Studies of synthesis, structural features of Cu(I) thiophene-2-thiocarboxylates and unprecedented desulfurization of Cu(II) thiocarboxylate complexes.

Thiophene-2-thiocarboxylate complexes of Cu(I), [(Ph(3)P)(2)Cu(SCOth)] (1) and H[(Ph(3)P)(2)Cu(SCOth)(2)] (2) (where th = thiophene) were synthesized and characterized structurally by X-ray crystallography. Electronic absorption and emission spectral properties of the two compounds have been studied. Cu(II) complexes, [(TMEDA)Cu(SCOth)(2)] (3b) and [(Phen)Cu(SCOth)(2)] (4a) (where TMEDA = tetramethylethylenediamine; Phen = 1,10-phenanthroline) were prepared and characterized by spectroscopic measurements. 3b and 4a underwent desulfurization under ambient conditions readily yielding the corresponding carboxylate complexes [(TMEDA)Cu(O(2)Cth)(2)] (3a) and [(Phen)Cu(O(2)Cth)(2)·H(2)O] (4b). 3a and 4b have been characterized crystallographically.

The chemistry of cadmium-thiocarboxylate derivatives: synthesis, structural features, and application as single source precursors for ternary sulfides.

Novel heterobimetallic complexes [(PPh(3))(2)Cu(µ-SCOPh)(2)Cd(SCOPh)] (2a), [(PPh(3))(2)Cu(µ-SCOth)(2)Cd(SCOth)] (2b), [(PPh(3))(2)Ag(µ-SCOth)(2)Cd(SCOth)] (3a), [(PPh(3))(2)Ag(µ-SCOth)(2)Cd(H(2)O)(SCOth)] (3b), [(PPh(3))(2)Ag(µ-SCOPh)(2)Cd(SCOPh)] (3c), and a bimetallic complex [PPh(3)Cd(µ-SCOth)SCOth](2)·CH(2)Cl(2) (5) (th = thiophene) were prepared and characterized by single crystal X-ray diffraction analysis. A coordination polymer [Cd(SCOPh)(2)](n) (4) has also been characterized structurally that exhibited metal-like electrical conductivity. The heterobimetallic complexes on pyrolyzing under controlled conditions yielded ternary sulfides of composition CuCd(7)S(8), CuCd(10)S(11), Ag(2)Cd(8)S(9), and Ag(2)Cd(5)S(6), which have been characterized by SEM-EDX and X-ray diffractometry. Photophysical properties and electrical conductivities of the sulfides have also been studied.

Synthesis and structural studies of an electron deficient hexatitanium cluster dication stabilized by novel tritin anions.

A reaction of Cp(2)Ti(SH)(2) with n-BuSnCl(OH)(2) gave two unusual ionic compounds; the cation in both is a hexatitanium cluster, [Cp(6)Ti(6)O(8)](2+), while the anion is a six membered cyclic (chair form) [n-Bu(3)Sn(3)Cl(SH)(3)(S)(3)](-) in one and acyclic [n-Bu(3)Sn(3)Cl(3)(SH)(3)(S)(2)](-) in the other. Besides X-ray crystallography, theoretical studies have also been completed to understand the structures of these complexes.

Novel heterobimetallic thiocarboxylato complexes: synthesis, characterization and application as single source precursor for ternary chalcogenides.

Heterobimetallic complexes, (PPh(3))(2)M(mu-SCOPh)(2)Pb(SCOPh) [where, M = Cu(I) (1) or Ag(I) (2)] have been synthesized and characterized by FTIR, (1)H, (13)C and (31)P NMR spectroscopy. Molecular structures in solid state have been determined by single crystal X-ray diffraction. Electronic spectra of the compounds have been recorded and explained on the basis of TDDFT calculations. Luminescence and redox properties of the complexes have also been studied. Following the thermogravimetric analysis data the compounds were pyrolysed and one of the decomposition products has been characterized as Pb(4)Cu(5)O(22.6) (3) by SEM-EDX and X-ray diffraction studies.

Synthesis of a one-dimensional coordination polymer containing pendant hydrosulfide groups.

In view of the recent interest in compounds containing M-SH units, an organotin hydrosulfide compound, Me2Sn(SH)(O2CMe) (1) was prepared by controlled hydrolysis of the diorganotin thioacetate. Under similar mild hydrolytic conditions the corresponding benzoate could not be isolated. Instead, the thiobenzoate complex, Me2Sn(SOCPh)2 (3) was obtained in excellent yields indicating that there was no hydrolysis. Both 1 and 3 were characterized by X-ray crystallography. Some properties of the polymeric compound 1, such as spectral, electrical conductivity and NLO response were also studied. The reactivity and properties were explained using density functional calculations.

Some new butylthiobenzoatotin(IV) compounds: spectral studies and analysis of ligand's bonding.

Five new monorganotin(IV) compounds with thiobenzoate ligand, [BuSn(SOCPh)2]2O (1), [BuSn(O)(SOCPh)]2 (2), BuSn(Cl)(SOCPh)2 (3), BuSn(Cl)2(SOCPh) (4) and [BuSn(OH)(Cl)(SOCPh)]2 (5) were synthesized and characterized by elemental analyses, IR, 1H and 13C NMR spectroscopy. 119Sn NMR spectroscopy was used to determine the coordination geometry around Sn(IV) in the cases of 2 and 4. 1, 2 and 5 are dimeric while 3 and 4 are monomeric. In all these molecules the thiobenzoate ion is coordinated only through its sulfur atom. Molecular structures of the compounds have been optimized by MM2 calculations. Semi-empirical quantum mechanical calculations (PM3 method) were performed to explain the monodentate-bonding pattern of thiobenzoate ligand.

Mixed-ligand Ru(II) complexes with 2,2'-bipyridine and aryldiazo-beta-diketonato auxillary ligands: synthesis, physico-chemical study and antitumour properties.

The complexes of Ru(II)-2,2'-bipyridyl with substituted diazopentane-2,4-diones (L1H-L5H) were synthesized and characterized by elemental analyses, conductance, FAB (fast atom bombardment) mass and spectral (IR, UV/Vis (UV/visible), NMR) studies. Molecular geometry optimization of the complexes was also made. None of the complexes luminesce. However, facilitated oxidation of Ru(II) to Ru(III) was evidenced from their lower reduction potential data. The ligands and their complexes were tested for their antitumour activity against a variety of tumour cell lines. Though activity is found to vary with the type of tumour cell lines used, yet complex 5 with naphtyldiazopentane-2,4-dione as co-ligand was found to be a potential compound as it showed in general significant activity against all cell lines studied.

Pentacoordinated Cu(II)/Zn(II) complexes bearing macrocyclic skeleton: synthesis, spectroscopic and molecular structure optimization studies.

2,6-Diacetylpyridine and 1,2-diaminoethane in the presence of copper(II) and zinc(II) chlorides containing a few drops of acetic acid were condensed into compositions [CuLH2]2.2HCl.H2O (1), [Cu2LPyz]2.2HCl.4CH3COCH3 (2) [CuZnLPyz]2.2HCl.2CH3COCH3.10H2O (3) and [ZnL'Cl]3.3HCl.3H2O (4) substantiated by elemental analyses, IR, UV-vis, 1H NMR and FAB mass spectral data. Demetallation of a Ni(II) complex (isolated as above) afforded macrocyclic skeleton LH4, whereas L' symbolizes a skeleton of the ligand containing only ethylenediamine and 2,6-diacetylpyridine. Molecular structure optimization using MM2 force field calculations for the complexes revealed distorted square pyramidal geometry around Cu(II) centers in complexes 1 and 2 and tetrahedral geometry around Cu(II) and Zn(II) centers with different degrees of distortion in complex 3 whereas three Zn(II) atoms (each in distorted square pyramidal geometry) attached via Cl bridges form a cyclic structure in complex 4. In complexes 1 and 2,Cu-Cu = 2.63-2.66 angstroms indicated the possibility of coupling between the two Cu(II) centers which has been supported by lower magnetic moment as well as ESR spectra showing half-field signal.