Deuterium labeling improves the therapeutic index of 3,3'-diselenodipropionic acid as an anticancer agent: insights from redox reactions.

3,3'-Diselenodipropionic acid (DSePA), a selenocystine derivative, has been previously reported as an oral supplement for anticancer/radio-modulation activities. The present study is focused on devising a strategy to synthesize and characterize the deuterated derivative of DSePA and on understanding the effect of deuteration on its therapeutic index by comparing its cytotoxicity in cancerous versus non-cancerous cell types. In this context, the synthesis of 3,3'-diselenodipropionic acid-D8 (D-DSePA) was accomplished in ∼42% yield. Further, the results clearly established that the deuteration of DSePA significantly reduced its cytotoxicity in non-cancerous cell types while retaining its cytotoxicity in cancerous cell lines. Together, D-DSePA displayed a ∼5-fold higher therapeutic index than the non-deuterated derivative for anticancer activity. The biochemical and NMR studies confirmed that the better biocompatibility of D-DSePA than its non-deuterated derivative in non-cancerous cells was due to its ability to undergo slower redox reactions and to cause lesser inhibition of intracellular redox enzymes.

Design and Synthesis of BODIPY-Hetero[5]helicenes as Heavy-Atom-Free Triplet Photosensitizers for Photodynamic Therapy of Cancer.

Designing heavy-atom-free triplet photosensitizers (PSs) is a challenge for the efficient photodynamic therapy (PDT) of cancer. Helicenes are twisted polycyclic aromatic hydrocarbons (PAHs) with an efficient intersystem crossing (ISC) that is proportional to their twisting angle. But their difficult syntheses and weak absorption profile in the visible spectral region restrict their use as heavy-atom-free triplet PSs for PDT. On the other hand, boron-containing PAHs, BODIPYs are highly recognized for their outstanding optical properties. However, planar BODIPY dyes has low ISC and thus they are not very effective as PDT agents. We have designed and synthesized fused compounds containing both BODIPY and hetero[5]helicene structures to develop red-shifted chromophores with efficient ISC. One of the pyrrole units of the BODIPY core was also replaced by a thiazole unit to further enhance the triplet conversion. All the fused compounds have helical structure, and their twisting angles are also increased by substitutions at the boron centre. The helical structures of the BODIPY-hetero[5]helicenes were confirmed by X-ray crystallography and DFT structure optimization. The designed BODIPY-hetero[5]helicenes showed superior optical properties and high ISC with respect to [5]helicene. Interestingly their ISC efficiencies increase proportionally with their twisting angles. This is the first report on the relationship between the twisting angle and the ISC efficiency in twisted BODIPY-based compounds. Theoretical calculations showed that energy gap of the S1 and T1 states decreases in BODIPY-hetero[5]helicene as compared to planar BODIPY. This enhances the ISC rate in BODIPY-hetero[5]helicene, which is responsible for their high generation of singlet oxygen. Finally, their potential applications as PDT agents were investigated, and one BODIPY-hetero[5]helicene showed efficient cancer cell killing upon photo-exposure. This new design strategy will be very useful for the future development of heavy-atom-free PDT agents.

Molecular precursor mediated selective synthesis of phase pure cubic InSe and hexagonal In2Se3 nanostructures: new anode materials for Li-ion batteries.

Indium selenides (InSe and In2Se3) have earned a special place among the 2D layered metal chalcogenides owing to their nontoxic nature and favourable carrier mobility. Additionally, they are also being projected as next generation battery anodes with high theoretical lithium-ion storage capacities. While the development of indium selenide-based batteries is still in its embryonic stage, a simple and easily scalable synthetic pathway to access these materials is highly desirable for energy storage applications. This study reports a controlled synthetic route to nanometric cubic InSe and hexagonal In2Se3 materials through proper choice of coordinating solvents from a structurally characterized air and moisture stable single source molecular precursor: tris(4,6-dimethyl-2-pyrimidylselenolato)indium(III). The crystal structure, phase purity, composition, morphology and band gap of the nanomaterials were thoroughly evaluated by pXRD, energy dispersive X-ray spectroscopy (EDS), electron microscopy (SEM and TEM), and diffuse reflectance spectroscopy (DRS), respectively. The pristine InSe and In2Se3 nanostructures have been employed as anode materials in lithium-ion batteries (LIBs). Both the cells deliver reasonably high initial discharge capacities with a cyclability of 200 and 620 cycles for cubic InSe and hexagonal In2Se3 respectively with ∼100% coulombic efficiency.

Molecular precursor-mediated facile synthesis of phase pure metal-rich digenite (Cu1.8S) nanocrystals: an efficient anode for lithium-ion batteries.

Copper sulfides have gained significant attention as alternative electrodes for rechargeable batteries. A simple and easily scalable synthetic pathway to access these materials is highly desirable. This paper describes the facile synthesis of metal-rich digenite Cu1.8S nanocrystals from a structurally characterized new single-source molecular precursor in various high boiling solvents of varied polarity. The as-prepared nanostructures were thoroughly characterized by PXRD, Raman spectroscopy, EDS, XPS, electron microscopy techniques and diffuse reflectance spectroscopy to understand the crystal structure, phase purity, elemental composition, morphology and band gap. It was found that the reaction solvent has a profound role on their crystallite size, morphology and band gap, however the crystal structure and phase purity remained unaffected. Pristine Cu1.8S nanostructures have been employed as an anode material in lithium-ion batteries (LIBs). The cell delivers a high initial charge capacity of ∼462 mA h g-1 and retains a capacity of 240 mA h g-1 even after 300 cycles at 0.1 A g-1. DFT calculations revealed that multi-size polyhedron layers in the direction perpendicular to the two Li movement channels aid in the sustainable uptake of Li atoms with controlled volume expansion. The structure-mediated flexibility of the metal-rich Cu1.8S lattice during lithiation permits high cyclability with reasonable retention of capacity.

Synthesis of photoresponsive and photoemissive ultrathin 2D nanosheets of In2S3 achieved through a new single source molecular precursor.

Indium sulfide, a two-dimensional semiconductor material, has emerged as a promising candidate for cost-effective and sustainable solar cells. This report deals with the facile preparation of colloidal In2S3 with a new ultrathin nanosheet (NS) morphology. The synthesis was mediated through a new structurally characterized single source molecular precursor. The crystal structure, phase purity, and morphology of the NSs were thoroughly investigated by pXRD, Raman, XPS, and electron microscopic techniques. AFM studies revealed that the NSs have an average thickness of ∼1.76 nm. The optical studies confirm quantum confinement in the as-prepared NSs with a blue shift in the direct band gap, which lies in the optimal range suitable for solar cell application. Furthermore, photoluminescence studies indicate strong emission by these NSs in the blue region. The as-synthesized In2S3 NSs-based prototype photoelectrochemical cell exhibit high photostability and photoresponsivity, which make them suitable candidates for sustainable solar cells.

Facile one pot synthesis of highly photoresponsive coinage metal selenides (Cu1.8Se and Ag2Se) achieved through novel Cu and Ag pyridylselenolates as molecular precursors.

Copper selenide (Cu1.8Se) and silver selenide (Ag2Se) have garnered unprecedented attention as efficient absorber materials for cost-effective and sustainable solar cells. Phase pure preparation of these exotic materials in a nano-regime is highly desirable. This account outlines a simple and easily scalable pathway to Cu1.8Se and Ag2Se nanocrystals using novel complexes [Cu{2-SeC5H2(Me-4,6)2N}]4 (1), [Ag{2-SeC5H2(Me-4,6)2N}]6 (2) and [Ag{2-SeC5H3(Me-5)N}]6·2C6H5CH3 (3·2C6H5CH3) as single source molecular precursors (SSPs). Structural studies revealed that the Cu and Ag complexes crystallize into tetrameric and hexameric forms, respectively. This observed structural diversity in the complexes has been rationalized via DFT calculations and attributed to metal-metal bond endorsed energetics. The thermolysis at relatively lower temperature in oleylamine of complex 1 afforded cubic berzelianite Cu1.8Se and complexes 2 and 3 produced orthorhombic naumannite Ag2Se nanocrystals. The low temperature synthesis of these nanocrystals seems to be driven by the observed preformed Cu4Se4 and Ag6Se6 core in the complexes which have close resemblance with the bulk structure of the final materials (Cu1.8Se and Ag2Se). The crystal structure, phase purity, morphology, elemental composition and band gap of these nanocrystals were determined from pXRD, electron microscopy (SEM and TEM), EDS and DRS-UV, respectively. The band gap of these nanocrystals lies in the range suitable for solar cell applications. Finally, these nanocrystal-based prototype photo-electrochemical cells exhibit high photoresponsivity and stability under alternating light and dark conditions.

Dimethyltin(IV)-4,6-dimethyl-2-pyridylselenolate: an efficient single source precursor for the preparation of SnSe nanosheets as anode material for lithium ion batteries.

The air stable tin(IV) complex [Me2Sn{2-SeC5H2(Me-4,6)2N}2] has been synthesized, characterized by NMR, elemental analysis, and single crystal XRD, and employed as a single source molecular precursor (SSP) for the facile synthesis of orthorhombic SnSe nanosheets. The crystal structure, phase purity, morphology and band gap of the nanosheets were investigated by pXRD, EDS, electron microscopy and diffuse reflectance spectroscopy techniques, respectively. It was found that the preferential orientation of planes and the morphology of the nanosheets rely upon the reaction conditions. The band gaps of the nanosheets were blue shifted with respect to the bulk band gap of the material. The synthesized SnSe nanosheets have been employed as an anode material in lithium ion batteries (LIBs). The material exhibits an initial specific capacity of 1134 mA h g-1 at a current density of 50 mA g-1 and was found to retain a capacity of 380 mA h g-1 even after 70 cycles with 100% efficiency.

Syntheses of Pd(II)/Pt(II) complexes with non-chelating 4-pyridylselenolate ligand ranging from mononuclear to macrocyclic structures and their utility as catalysts in Suzuki C-C coupling reaction.

Treatment of Na2PdCl4 or [MCl2(PhCN)2] with bis(4-pyridyl)diselenide yielded an insoluble product of composition [MCl2(4,4'-(C5H4N)2Se2)]n (1). The reactions of Na2PdCl4 with one and two eq. of Na(4-SeC5H4N) afforded insoluble products [PdCl(4-SeC5H4N)]n (2) and [Pd(4-SeC5H4N)2]n (3), respectively. On treatment with PPh3, 2 and 3 gave trans-[PdCl(4-SeC5H4N)(PPh3)2] (4a) and trans-[Pd(4-SeC5H4N)2(PPh3)2] (5a), respectively. The oxidative addition of bis(4-pyridyl)diselenide to Pt(PPh3)4 exclusively yielded trans-[Pt(4-SeC5H4N)2(PPh3)2] (5b). The treatment of two eq. of Na(4-SeC5H4N) with cis-[PtX2(PR3)2] afforded 5b (X = Cl) and trans-[Pt(4-SeC5H4N)2(PEt3)2] (5c) (X = Cl or CF3SO3). The reactions of cis-[MCl2(P∩P)] and [M2Cl2(µ-Cl)2(PR3)2] with two eq. of Na(4-SeC5H4N) exclusively yielded cis-[M(4-SeC5H4N)2(P∩P)] (M/P∩P = Pd/dppe (6a), Pt/dppm (6b) and Pt/dppp (6c)) and [MCl(4-SeC5H4N)(PR3)]n (7), respectively. The complex trans-[PtCl(4-SeC5H4N)(PEt3)2] (4b) was isolated from the redistribution reaction between 5c and cis-[PtCl2(PEt3)2]. The complex [PdCl(4-SeC5H4N)(PPh3)]n (7b) exists in bi- and tri-nuclear forms, whereas [MCl(4-SeC5H4N)(PEt3)]n (7a, 7c) and [PtCl(4-SeC5H4N)(PMe2Ph)]n (7d) retain their trinuclear structure in solution. Molecular structures of 4a, 4b, 5a, 5c, 6a, 6c, 7a, 7b and 7c were established by single crystal X-ray diffraction analyses. The complexes trans-[PdCl(4-SeC5H4N)(PPh3)2] and [PdCl(4-SeC5H4N)(PPh3)]n can act as catalysts for Suzuki C­C cross coupling reaction.