Two-Dimensional Supramolecular Polymerization of a Bis-Urea Macrocycle into a Brick-Like Hydrogen-Bonded Network

We report on a dendronized bis-urea macrocycle 1 self-assembling via a cooperative mechanism into two-dimensional (2D) nanosheets formed solely by alternated urea-urea hydrogen bonding interactions. The pure macrocycle self-assembles in bulk into one-dimensional liquid-crystalline columnar phases. In contrast, its self-assembly mode drastically changes in CHCl₃ or tetrachloroethane, leading to 2D hydrogen-bonded networks. Theoretical calculations, complemented by previously reported crystalline structures, indicate that the 2D assembly is formed by a brick-like hydrogen bonding pattern between bis-urea macrocycles. This assembly is promoted by the swelling of the trisdodecyloxyphenyl groups upon solvation, which frustrates, due to steric effects, the formation of the thermodynamically more stable columnar macrocycle stacks. This work proposes a new design strategy to access 2D supramolecular polymers by means of a single non-covalent interaction motif, which is of great interest for materials development.     

电解质对两性药物分子盐酸氯丙嗪的胶团生长的影响

The effect of electrolytes on the micellar behavior of an amphiphilic drug,chlorpromazine(CPZ)hydroehloride,was studied using cloud point(CP)and dye solubilization techniques.In the presence of KBr,increase because of deprotonation of drug molecules at high pH. The visible absorbance increased(due to dye solubilization)with the increase in pH from 6.5 to 6.9,which indicated micellar growth.At fixed pH(6.7),addition of inorganic salts(KF,KC1,effecfiveness being in the order:F-Na >K ,which Was explained by considering cognizance of their hydrated radii.Compared with anions,their effect was small.Increase in[CPZ]caused micellar growth and hence the CP as well as the visible absorbance increased.The overall behavior Was discussed in terms of electrostatic interactions and micellar growth.     

Linear hydrogen‐bonded molecular tapes in the cocrystals of squaric acid with 4,4′‐dipyridylacetylene and 1,2‐bis(4‐pyridyl)ethylene

The title compounds, 4,4′‐(ethyne‐1,2‐diyl)­dipyridinium bis(squarate), C₁₂H₁₀N₂²⁺·2C₄HO₄^?, and 4,4′‐(ethene‐1,2‐diyl)­dipyridinium bis­(squarate), C₁₂H₁₂N₂²⁺·2C₄HO₄^?, are isomorphous and crystallize in space group P. The cocrystals contain linear hydrogen‐bonded molecular tape structures along the [120] direction. The squarate monoanions form a ten‐membered dimer linked by two intermolecular O—H?O hydrogen bonds. Each component mol­ecule forms a segregated stack along the c axis. The bond lengths of the squarate monoanion indicate delocalization of the enolate anion.     

4,7‐Bis(4‐pyridyl­ethynyl)‐2,1,3‐benzo­thia­diazo­le and its dipyridinium diperchlorate

The title compound, C₂₀H₁₀N₄S, and its dipyridinium salt, 4,4′‐(2,1,3‐benzo­diazol‐4,7‐diyl­diethynyl)­dipyridinium diperchlorate, C₂₀H₁₂N₄S²⁺·2ClO₄^?, display bond alternation in the 2,1,3‐benzo­thia­diazo­le rings, which suggests their quinonoid character. The dipyridinium dication mol­ecules stack along the a axis and form a dimer with short S?N interheteroatom contacts [3.146 (4) Å] between the two 1,2,5‐thia­diazo­le rings. The dimer is surrounded by the perchlorate anions with which it forms a large number of intermolecular N—H?O and C—H?O hydrogen bonds.     

Competing forward and reversed chain reactions in one-dimensional molecular line growth on the Si(100)-(2 x 1)-H surface

To explore the role of competing forward and reversed chain reactions in the growth of a one-dimensional (1D) molecular line on the Si(100)-(2 x 1)-H surface, controlled experiments were performed with various alkene molecules by scanning tunneling microscopy (STM) at various temperatures. It was observed that the end dangling bond (DB) of a styrene line, fabricated by a chain reaction on the Si(100)-(2 x 1)-H surface at 300 K, initiated a reverse chain reaction at 400 K, leading to the complete disappearance of the styrene line with zero-order desorption kinetics (rate constant k = 1.17 x 10-2 s-1 at 400 K). In the case of 2,4-dimethylstyrene, the reversed chain reaction was observed even at 300 K. These results suggest that the appearance of a molecular line in an STM image is determined by the rates of competing forward and reversed chain reactions at a given temperature. As predicted, 1D lines formed by the DB-initiated chain reaction of 1-hexene and 1-heptene on Si(100)-(2 x 1)-H were observed at 180 K because of the reduced desorption rate, despite the fact that those molecules showed no line growth at 300 K. These results indicate that the scope of forming 1D molecular lines on the Si(100)-(2 x 1)-H surface with various alkenes is much wider than anticipated in previous studies.     

Reversible colorimetric probes for mercury sensing

The selectivity and sensitivity of two colorimetric sensors based on the ruthenium complexes N719 [bis(2,2'-bipyridyl-4,4'-dicarboxylate)ruthenium(II) bis(tetrabutylammonium) bis(thiocyanate)] and N749 [(2,2':6',2' '-terpyridine-4,4',4' '-tricarboxylate)ruthenium(II) tris(tetrabutylammonium) tris(isothiocyanate)] are described. It was found that mercury ions coordinate reversibly to the sulfur atom of the dyes' NCS groups. This interaction induces a color change in the dyes at submicromolar concentrations of mercury. Furthermore, the color change of these dyes is selective for mercury(II) when compared with other ions such as lead(II), cadmium(II), zinc(II), or iron(II). The detection limit for mercury(II) ions--using UV-vis spectroscopy--in homogeneous aqueous solutions is estimated to be approximately 20 ppb for N719 and approximately 150 ppb for N749. Moreover, the sensor molecules can be adsorbed onto high-surface-area mesoporous metal oxide films, allowing reversible heterogeneous sensing of mercury ions in aqueous solution. The results shown herein have important implications in the development of new reversible colorimetric sensors for the fast, easy, and selective detection and monitoring of mercuric ions in aqueous solutions.     

Topochemical Transformations of CaX2 (X=C,Si, Ge) to Form Free‐Standing Two‐Dimensional Materials

Topochemical transformations of layered materials CaX₂ (X=Si, Ge) are the method of choice for the high‐yield synthesis of pristine, defect‐free two‐dimensional systems silicane and germanane, which have advanced electronic properties. Based on solid‐state dispersion‐corrected calculations, mechanisms for such transformations are elucidated that provide an in‐depth understanding of phase transition in these layered materials. While formation of such layered materials is highly favorable for silicane and germanane, a barrier of 1.2 eV in the case of graphane precludes its synthesis from CaC₂ topochemically. The energy penalty required for distorting linear acetylene into a trans‐bent geometry accounts for this barrier. In contrast it is highly favorable in the heavier analogues, resulting in barrierless topochemical generation of silicane and germanane. Photochemical generation of the trans‐bent structure of acetylene in its first excited state (S₁) can directly generate graphane through a barrierless condensation. Unlike the buckled structure of silicene, the phase‐h of CaSi₂ with perfectly planar silicene layers exhibits the Dirac cones at the high symmetry points K and H. Interestingly, topochemical acidification of the cubic phase of calcium carbide is predicted to generate the previously elusive platonic hydrocarbon, tetrahedrane.     

Dye‐Sensitized Solar Cell Counter Electrodes Based on Carbon Nanotubes

Dye‐sensitized solar cells (DSSCs) have received significant attention from the scientific community since their discovery in 1991. However, the high cost and scarcity of platinum has motivated researchers to seek other suitable materials for the counter electrode of DSSCs. Owing to their exceptional properties such as high conductivity, good electrochemical activity, and low cost, carbon nanotubes (CNTs) have been considered as promising alternatives to expensive platinum (Pt) in the counter electrode of DSSCs. Herein, we provide a Minireview of the CNTs use in the counter electrode of DSSCs. A brief overview of Pt‐based counter electrodes is also discussed. Particular attention is given to the recent advances of counter electrodes with CNT‐based composite structures.     

Domain reorientation dynamics of sol–gel derived strontium doped PLZT (8/65/35)

Polycrystalline samples of PLSZT with the composition Pb_0.92−x La_0.08Sr _x (Zr_0.65Ti_0.35)O₃ (where x = 0, 0.02, 0.04, 0.06, 0.08, and 0.10) have been synthesized by sol–gel technique. DTA analysis confirms that all the organic constituents get decomposed and final PLZT is formed at 545 °C. The XRD analysis suggests the formation of single rhombohedral perovskite phase with decreasing unit cell parameter. Crystallite size calculated, using Scherrer’s equation, was found to decrease with Sr doping due to smaller ionic radii of Sr than Pb. Compact uniform grain distribution was observed from SEM micrographs. The ferroelectric to paraelectric phase transition temperature, maximum dielectric constant and remanent polarization (P _r) were found to decrease with Sr doping along with increasing diffuse nature of phase transformation. Detailed domain reorientation dynamics study suggests that Sr doping increases the percentage backswitching and decreases the normalized coercivity by decreasing the viscous nature of composition.     

Liquid Chromatographic Determination of NSAIDs in Urine After Dispersive Liquid–Liquid Microextraction Based on Solidification of Floating Organic Droplets

An environmentally benign method of sample preparation based on dispersive liquid–liquid microextraction and solidification of floating organic droplets (DLLME-SFO) coupled with high-performance liquid chromatography with ultraviolet detection has been developed for analysis of non-steroidal anti-inflammatory drugs (NSAIDs) in biological fluids. A low-toxicity solvent was used to replace the chlorinated solvents commonly used in conventional DLLME. Seven conditions were investigated and optimized: type and volume of extraction solvent and dispersive solvent, extraction time, effect of addition of salt, and sample pH. Under the optimum conditions, good linearity was obtained in the range 0.01–10 µg mL⁻¹, with coefficients of determination (r ²) >0.9949. Detection limits were in the range 0.0034–0.0052 µg mL⁻¹ with good reproducibility (RSD) and satisfactory inter-day and intra-day recovery (95.7–115.6 %). The method was successfully used for analysis of diclofenac, mefenamic acid, and ketoprofen in human urine. Analysis of urine samples from a patient 2 and 4 h after administration of diclofenac revealed concentrations of 1.20 and 0.34 µg mL⁻¹, respectively.