Transition-Metal-Free One-Pot [3+3] Heteroannulative Coupling of Thioamides with Epichlorohydrin: Access to Diverse 1,3-Thiazinanes

An operationally simple and efficient cascade approach to access a series of 1,3-thiazinanes has been developed through intermolecular [3+3] heteroannulative coupling employing β-ketothioamide as a C1 N1S1 unit and epichlorohydrin as a C3 unit at room temperature for the first time. The reaction proceeds by nucleophilic attack of thiocarbonyl sulfur to less hindered primary carbon of oxirane followed by sequential intramolecular N-cyclization and dehydrochlorination enabling the coupling by cleavage of C−O bond and formation of two new C−S and C−N bonds in one stretch. This protocol not only avoids potential toxicity and tedious work up procedures, but also features open atmosphere, good to high yields, gram-scalability, and easy performance from inexpensive, readily available starting materials under transition-metal-free conditions. A probable mechanism for the formation of 1,3-thiazinanes has been suggested.     

Supramolecular non-symmetric dimers derived from cholesterol: synthesis and phase transitional properties

Three series of novel dimeric supramolecules, possessing both inter- as well as intramolecular H-bonding, have been prepared and investigated for their thermal properties. They were obtained in excellent yields by condensing cholesteryl ω-(3-hydroxy-4-formylphen-oxy)alkanoates with 4-(n-alkoxy)benzohydrazides, 3,4-bis(n-decyl-oxy)benzohydrazide and 3,4,5-tris(n-decyloxy)benzohydrazide. The influence of increase in the number of terminal n-alkoxy tails from one to three and the length and parity of the flexible spacer on phase transitional behaviour have been thoroughly investigated with the aid of microscopic, calorimetric and X-ray diffraction (XRD) techniques. The results of these complementary studies clearly illustrate the dependence of thermal behaviour of the dimers on these structural factors. The rigid intermolecular association via H-bonds through complementary benzohydrazide component enforce their self-assembly into frustrated and polar smectic phases; H-bond force coupled with the bulkiness of steroid moiety affects the electrical switching property of this fluid polar structure.     

s‐Triazine‐Based Functional Discotic Liquid Crystals: Synthesis,Mesomorphism and Photoluminescence

A new series of C₃‐symmetric, π‐conjugated molecules was designed, synthesized and characterized. The materials were derived from electron‐accepting s‐triazine, appended covalently to electron‐donating styrylbenzene arms, and were readily prepared in excellent yield with high purity by means of three‐fold condensation of triphosphonate with n‐alkoxybenzaldehydes under Horner–Wadsworth–Emmons reaction conditions. Examination of the phase transitional properties by several complementary techniques evidenced self‐assembly into a hexagonal columnar phase, occurring over wide and reasonable thermal ranges. The photophysical properties were studied both in solution and in the fluid/frozen columnar states by UV/Vis absorption and photoluminescence spectroscopy. The emission spectra obtained as a function of the temperature rule out the breaking‐up of larger columns and a non‐radiative, thermally activated process. A study carried out on thin films of the glassy columnar state, which accounts for conserved fluorescence, defect‐free orientation, and freezing ionic species, with the help of atomic force microscopy (AFM) images, suggested a homogeneous granular morphology comprising fibrillar structures. Dissimilarities in the surface morphology and birefringence of thin films of the solid and frozen columnar states were clearly shown by Raman spectroscopy. An electrochemical investigation revealed a LUMO energy of ?4.0 eV. Thus, the discotic motifs presented herein meet certain criteria of organic materials, which are essential for developing electronic devices.     

Chiral discrimination of a gemini-type surfactant with rigid spacer at the air-water interface

Spontaneous separation of chiral phases was observed in the monolayers of a racemate of gemini-type twin-tailed, twin-chiral amphiphiles, (2R,3R)-(+)-bis(decyloxy)succinic acid and (2S,3S)-(-)-bis(decyloxy)succinic acid. The pressure-area isotherms of the interfacial monolayers formed at the liquid-air interface, and the 2D lattice structures studied through surface probe measurements revealed that the racemate exhibits a homochiral discrimination of the enantiomers in two dimensions. An enantiomeric excess (e,e) of 20% was sufficient to break the chiral symmetry at the air-water interface for a homochiral interaction. Langmuir monolayers on ZnCl2 and CaCl2 subphases manifested chiral discrimination with Zn2+ evidencing homochiral interaction with a chelate-type complex, whereas Ca2+ resulted in a heterochiral interaction forming an ionic-type complex. For the chiral asymmetric units, oblique and rectangular unit cells of the racemic monolayer had exclusive requirements of homo- and heterochiral recognitions for Zn2+ and Ca2+ ions, respectively. Monolayers transferred from the condensed phase at 25 mN/m onto hydrophilic Si(100) and quartz substrates revealed the formation of bilayers through transfer-induced monolayer buckling. The emergence of homochiral discrimination was explained using the effective-pair-potential (EPP) approach.     

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.     

Movement of drops on a solid surface due to a contact angle gradient

Experimental results on the motion of liquid drops on horizontal surfaces resulting from a contact angle gradient are presented. Silicon surfaces were modified using dodecyltrichlorosilane to generate the gradient. Water drops with initial diameters of 0.31 ‐ 0.5 mm (15 ‐ 65 nl) were placed on the surface, their movement videotaped, and subsequently analyzed. To characterize the gradient surface the static contact angle was measured along the surface.     

Application of combined Monte Carlo and molecular dynamics method to simulation of dipalmitoyl phosphatidylcholine lipid bilayer

We describe a new equilibration procedure for the atomic level simulation of a hydrated lipid bilayer. The procedure consists of alternating molecular dynamics trajectory calculations in a constant surface tension and temperature ensemble with configurational bias Monte Carlo moves to different regions of the configuration space of the bilayer, in a constant volume and temperature ensemble. The procedure is described in detail and is applied to a bilayer of 100 molecules of dipalmitoyl phosphatidylcholine (DPPC) and 3205 water molecules. We find that the hybrid simulation procedure enhances the equilibration of the bilayer as measured by the convergence of the area per molecule and the segmental order parameters, as compared with a simulation using only molecular dynamics (MD). Progress toward equilibration is almost three times as fast in CPU time, compared with a purely MD simulation. Equilibration is complete, as judged by the lack of energy drift in three separate 200-ps runs of continuous MD started from different initial states. Results of the simulation are presented and compared with experimental data and with other recent simulations of DPPC. ©1999 John Wiley & Sons, Inc. J Comput Chem 20: 1153–1164, 1999     

Influence of sol-gel precursors on the electrochemical performance of NaMn<Subscript>0.33</Subscript>Ni<Subscript>0.33</Subscript>Co<Subscript>0.33</Subscript>O<Subscript>2</Subscript> positive electrode for sodium-ion battery

Among the various cathode materials explored for sodium-ion batteries (SIBs), NaMn_0.33Ni_0.33Co_0.33O₂, with a layered oxide structure, is a promising material due to its high theoretical capacity (240 mAhg^?1). We have synthesized NaMn_0.33Ni_0.33Co_0.33O₂ using two different types of precursors, namely metal acetates and metal nitrates by the sol-gel method. XRD patterns confirm the formation of a stable phase of the material at 900 °C. Coupled TGA-FTIR analysis was used to optimize the calcination conditions and to understand the hydrolysis and condensation mechanism of the sol-gel precursors. FTIR spectra extracted at different temperatures reveal the polymer network-forming tendency of the acetate ligands whereas the polymerization is inhibited in the nitrate precursors. SEM analysis shows spherical and platelet morphologies of samples synthesized from nitrate and acetate precursors, respectively. Using in situ impedance and galvanostatic charge/discharge studies, we observed that the precursors used to synthesize the cathode material influence the electrochemical properties of the material, as in this case, where we observe a 20 % improvement in terms of capacity by using acetate precursors instead of nitrate precursors.