Synthesis, Characterization, and X-Ray Diffraction Analysis of Triethylenetetraammonium Tetrathiomolybdate

The reaction of gaseous H₂S with aqueous ammonium heptamolybdate in the presence of triethylenetetramine (trien) gave a red complex. The complex was recrystallized in hot water and characterized by element analysis and UV, visible, IR, and ¹H NMR spectroscopy. PMR has revealed accidental magnetic equivalence, resulting from the proximity of [MoS₄]^2- species in one complex molecule to the open triethylenetetramine ligand of another molecule. (TrienH₂)[MoS₄] crystallizes in the orthorhombic crystal system, space group Pca2₁, a=13.045(2), b=16.461(3), c=13.754(2) , =90, =90, =90°, V=2953.5(9) ³, Z=8, R₁=0.0323, wR₂=0.0730. The structure consists of the tetrahedral tetrathiomolybdate anions, forming an extended 3D framework in solids due to the interactions with triene cations via Mo-S...H-N hydrogen bonds.     

Camouflaging Structural Diversity: Co‐crystallization of Two Different Nanoparticles Having Different Cores But the Same Shell

Two ligand‐protected nanoscale silver moieties, [Ag₄₆(SPhMe₂)₂₄(PPh₃)₈](NO₃)₂ and [Ag₄₀(SPhMe₂)₂₄(PPh₃)₈](NO₃)₂ (abbreviated as Ag₄₆ and Ag₄₀, respectively) with almost the same shell but different cores were synthesized simultaneously. As their external structures are identical, the clusters were not distinguishable and become co‐crystallized. The occupancy of each cluster was 50 %. The outer shell of both is composed of Ag₃₂S₂₄P₈, which is reminiscent of fullerenes, and it encapsulates a well‐studied core, Ag₁₄ and a completely new core, Ag₈, which correspond to a face‐centered cube and a simple cube, respectively, resulting in the Ag₄₆ and Ag₄₀ clusters. The presence of two entities (Ag₄₀ and Ag₄₆ clusters) in a single crystal and their molecular formulae were confirmed by detailed electrospray ionization mass spectrometry. The optical spectrum of the mixture showed unique features which were in good agreement with the results from time‐dependent density functional theory (TD‐DFT).     

Synthesis of fused indolines by interrupted Fischer indolization in a microfluidic reactor

This study describes our development of a microfluidic reaction scheme for the synthesis of fused indoline ring systems found in several bioactive compounds. We have utilized a continuous-flow microfluidic reactor for the reaction of hydrazines with latent aldehydes through the interrupted Fischer indolization reaction to form fused indoline and azaindoline products. We have identified optimal conditions and evaluated the scope of this microfluidic reaction using various hydrazine and latent aldehyde surrogates. This green chemistry approach can be of general utility to rapidly produce indoline scaffolds and intermediates in a continuous manner.     

Stimuli‐Responsive Supramolecular Hydrogels and Their Applications in Regenerative Medicine

Supramolecular hydrogels are a class of self‐assembled network structures formed via non‐covalent interactions of the hydrogelators. These hydrogels capable of responding to external stimuli are considered to be smart materials due to their ability to undergo sol–gel and/or gel–sol transition upon subtle changes in their surroundings. Such stimuli‐responsive hydrogels are intriguing biomaterials with applications in tissue engineering, delivery of cells and drugs, modulating tissue environment to promote innate tissue repair, and imaging for medical diagnostics among others. This review summarizes the recent developments in stimuli‐responsive supramolecular hydrogels and their potential applications in regenerative medicine. Specifically, various structural aspects of supramolecular hydrogelators involved in self‐assembly, the role of external stimuli in tuning/controlling their phase transitions, and how these functions could be harnessed to advance applications in regenerative medicine are focused on. Finally, the key challenges and future prospects for these versatile materials are briefly described.     

Modulation of the PGE2-Mediated Pathway in the Eclosion Blocking Effect of Flumethrin and Terpenoid Subfraction Isolated from Artemesia nilagirica in Rhipicephalus annulatus

Prostaglandins are a group of important cell-signaling molecules involved in the regulation of ovarian maturation, oocyte development, egg laying and associated behaviors in invertebrates. However, the presence of prostaglandin E₂ (PGE₂), the key enzymes for PGE₂ biosynthesis and its interference by drugs were not investigated previously in the ovary of ticks. The present study was undertaken to assess the modulation of the PGE₂-mediated pathway in the eclosion blocking effect of flumethrin and terpenoid subfraction isolated from Artemisia nilagirica in Rhipicephalus annulatus ticks. The acaricidal activities and chemical profiling of the terpenoid subfraction were performed. The localization of the cyclooxygenase1 (COX1) and prostaglandin E synthase (PGES) enzymes and the quantification of PGE₂ in the ovaries of the ticks treated with methanol (control), flumethrin and terpenoid subfraction were also undertaken. In addition, the vitellogenin concentration in hemolymph was also assayed. Both flumethrin and the terpenoid subfraction of A. nilagirica elicited a concentration-dependent inhibition of fecundity and blocking of hatching of the eggs. The COX1 could not be detected in the ovaries of treated and control ticks, while there was no significant difference observed in the concentration of vitellogenin (Vg) in them. The presence of PGES in the oocytes of control ticks was confirmed while the immunoreactivities against PGES were absent in the vitellogenic oocytes of ticks treated with flumethrin and terpenoid subfraction. The levels of PGE₂ were below the detection limit in the ovaries of the flumethrin-treated ticks, while it was significantly lower in the ovaries of the terpenoid subfraction-treated ticks. Hence, the prostaglandin E synthase and PGE₂ were identified as very important mediators for the signaling pathway for ovarian maturation and oviposition in ticks. In addition, the key enzyme for prostaglandin biosynthesis, PGES and the receptors for PGE₂ can be exploited as potential drug targets for tick control. The detection of PGES by immunohistochemistry and quantification of PGE₂ by LC-MSMS can be employed as valuable tools for screening newer compounds for their eclosion blocking acaricidal effects.     

DNA-directed artificial light-harvesting antenna

Designing and constructing multichromophoric, artificial light-harvesting antennas with controlled interchromophore distances, orientations, and defined donor-acceptor ratios to facilitate efficient unidirectional energy transfer is extremely challenging. Here, we demonstrate the assembly of a series of structurally well-defined artificial light-harvesting triads based on the principles of structural DNA nanotechnology. DNA nanotechnology offers addressable scaffolds for the organization of various functional molecules with nanometer scale spatial resolution. The triads are organized by a self-assembled seven-helix DNA bundle (7HB) into cyclic arrays of three distinct chromophores, reminiscent of natural photosynthetic systems. The scaffold accommodates a primary donor array (Py), secondary donor array (Cy3) and an acceptor (AF) with defined interchromophore distances. Steady-state fluorescence analyses of the triads revealed an efficient, stepwise funneling of the excitation energy from the primary donor array to the acceptor core through the intermediate donor. The efficiency of excitation energy transfer and the light-harvesting ability (antenna effect) of the triads was greatly affected by the relative ratio of the primary to the intermediate donors, as well as on the interchromophore distance. Time-resolved fluorescence analyses by time-correlated single-photon counting (TCSPC) and streak camera techniques further confirmed the cascading energy transfer processes on the picosecond time scale. Our results clearly show that DNA nanoscaffolds are promising templates for the design of artificial photonic antennas with structural characteristics that are ideal for the efficient harvesting and transport of energy.     

Synthesis, characterization, and electronic structure of new type of heterometallic boride clusters

The reaction of [Cp*TaCl(4)], 1 (Cp* = η(5)-C(5)Me(5)), with [LiBH(4)·THF] at -78 °C, followed by thermolysis in the presence of excess [BH(3)·THF], results in the formation of the oxatantalaborane cluster [(Cp*Ta)(2)B(4)H(10)O], 2 in moderate yield. Compound 2 is a notable example of an oxatantalaborane cluster where oxygen is contiguously bound to both the metal and boron. Upon availability of 2, a room temperature reaction was performed with [Fe(2)(CO)(9)], which led to the isolation of [(Cp*Ta)(2)B(2)H(4)O{H(2)Fe(2)(CO)(6)BH}], 3. Compound 3 is an unusual heterometallic boride cluster in which the [Ta(2)Fe(2)] atoms define a butterfly framework with one boron atom lying in a semi-interstitial position. Likewise, the diselenamolybdaborane, [(Cp*Mo)(2)B(4)H(4)Se(2)], 4 was treated with an excess of [Fe(2)(CO)(9)] to afford the heterometallic boride cluster [(Cp*MoSe)(2)Fe(6)(CO)(13)B(2)(BH)(2)], 5. The cluster core of 5 consists of a cubane [Mo(2)Se(2)Fe(2)B(2)] and a tricapped trigonal prism [Fe(6)B(3)] fused together with four atoms held in common between the two subclusters. In the tricapped trigonal prism subunit, one of the boron atoms is completely encapsulated and bonded to six iron and two boron atoms. Compounds 2, 3, and 5 have been characterized by mass spectrometry, IR, (1)H, (11)B, (13)C NMR spectroscopy, and the geometric structures were unequivocally established by crystallographic analysis. The density functional theory calculations yielded geometries that are in close agreement with the observed structures. Furthermore, the calculated (11)B NMR chemical shifts also support the structural characterization of the compounds. Natural bond order analysis and Wiberg bond indices are used to gain insight into the bonding patterns of the observed geometries of 2, 3, and 5.     

η4‐HBCC‐σ,π‐Borataallyl Complexes of Ruthenium Comprising an Agostic Interaction

Thermolysis of [Cp*Ru(PPh₂(CH₂)PPh₂)BH₂(L₂)] 1 (Cp*=η⁵‐C₅Me₅; L=C₇H₄NS₂), with terminal alkynes led to the formation of η⁴‐σ,π‐borataallyl complexes [Cp*Ru(μ‐H)B{R‐C=CH₂}(L)₂] ( 2 a – c ) and η²‐vinylborane complexes [Cp*Ru(R‐C=CH₂)BH(L)₂] ( 3 a – c ) ( 2 a , 3 a : R=Ph; 2 b , 3 b : R=COOCH₃; 2 c , 3 c : R=p‐CH₃‐C₆H₄; L=C₇H₄NS₂) through hydroboration reaction. Ruthenium and the HBCC unit of the vinylborane moiety in 2 a – c are linked by a unique η⁴‐interaction. Conversions of 1 into 3 a – c proceed through the formation of intermediates 2 a – c . Furthermore, in an attempt to expand the library of these novel complexes, chemistry of σ‐borane complex [Cp*RuCO(μ‐H)BH₂L] 4 (L=C₇H₄NS₂) was investigated with both internal and terminal alkynes. Interestingly, under photolytic conditions, 4 reacts with methyl propiolate to generate the η⁴‐σ,π‐borataallyl complexes [Cp*Ru(μ‐H)BH{R‐C=CH₂}(L)] 5 and [Cp*Ru(μ‐H)BH{HC=CH‐R}(L)] 6 (R=COOCH₃; L=C₇H₄NS₂) by Markovnikov and anti‐Markovnikov hydroboration. In an extension, photolysis of 4 in the presence of dimethyl acetylenedicarboxylate yielded η⁴‐σ,π‐borataallyl complex [Cp*Ru(μ‐H)BH{R‐C=CH‐R}(L)] 7 (R=COOCH₃; L=C₇H₄NS₂). An agostic interaction was also found to be present in 2 a – c and 5 – 7 , which is rare among the borataallyl complexes. All the new compounds have been characterized in solution by IR, ¹H, ¹¹B, ¹³C NMR spectroscopy, mass spectrometry and the structural types were unequivocally established by crystallographic analysis of 2 b , 3 a – c and 5 – 7 . DFT calculations were performed to evaluate possible bonding and electronic structures of the new compounds.     

Self-assembled hybrid polymer-TiO2 nanotube array heterojunction solar cells

Films comprised of 4 microm long titanium dioxide nanotube arrays were fabricated by anodizing Ti foils in an ethylene glycol based electrolyte. A carboxylated polythiophene derivative was self-assembled onto the TiO2 nanotube arrays by immersing them in a solution of the polymer. The binding sites of the carboxylate moiety along the polymer chain provide multiple anchoring sites to the substrate, making for a stable rugged film. Backside illuminated liquid junction solar cells based on TiO2 nanotube films sensitized by the self-assembled polymeric layer showed a short-circuit current density of 5.5 mA cm-2, a 0.7 V open circuit potential, and a 0.55 fill factor yielding power conversion efficiencies of 2.1% under AM 1.5 sun. A backside illuminated single heterojunction solid state solar cell using the same self-assembled polymer was demonstrated and yielded a photocurrent density as high as 2.0 mA cm-2. When a double heterojunction was formed by infiltrating a blend of poly(3-hexylthiophene) (P3HT) and C60-methanofullerene into the self-assembled polymer coated nanotube arrays, a photocurrent as high as 6.5 mA cm-2 was obtained under AM 1.5 sun with a corresponding efficiency of 1%. The photocurrent action spectra showed a maximum incident photon-to-electron conversion efficiency (IPCE) of 53% for the liquid junction cells and 25% for the single heterojunction solid state solar cells.     

Self-location of acceptors as "isolated" or "stacked" energy traps in a supramolecular donor self-assembly: a strategy to wavelength tunable FRET emission

Control over supramolecular assemblies of donor and acceptor arrays in nanoscale dimension that facilitate efficient energy transfer resulting in tunable emission is an outstanding challenge. In pursuit of this goal, we have designed a supramolecular donor-acceptor organogel with tunable emission from green to red through controlled energy transfer by simply varying the acceptor concentration. Temperature-dependent UV/vis absorption, XRD, and AFM studies of the coassembly of 1 (donor) and 2 (acceptor) revealed the intercalation of 2 within the self-assembly of 1. Upon excitation of the decane gels of 1 with 0-2 mol % of 2, quenching of the emission of the former at 509 nm with the formation of the monomer emission of the latter at 555 nm is observed. Upon further addition of 2 (2-20 mol %), the emission was continuously red-shifted to 610 nm, which corresponds to the aggregate emission of 2. Consequently, a 98% quenching of the donor emission was observed at 509 nm. Fluorescence microscopic studies provided visual evidence for the color tuning of the FRET emission. Thus efficient trapping of excitons by "isolated" or "aggregated" acceptors through a subtle control of the self-assembly and the photophysical properties of the donor-acceptor building blocks allowed a continuous shifting of the emission color anywhere between green and red (lambdamax, 509-610 nm) in a supramolecular light harvesting system.