Cooperatively assembled liquid crystals enable temperature-controlled Förster resonance energy transfer

Balancing the rigidity of a π-conjugated structure for strong emission and the flexibility of liquid crystals for self-assembly is the key to realizing highly emissive liquid crystals (HELCs). Here we show that (1) integrating organization-induced emission into dual molecular cooperatively-assembled liquid crystals, (2) amplifying mesogens, and (3) elongating the spacer linking the emitter and the mesogen create advanced materials with desired thermal–optical properties. Impressively, assembling the fluorescent acceptor Nile red into its host donor designed according to the aforementioned strategies results in a temperature-controlled Förster resonance energy transfer (FRET) system. Indeed, FRET exhibits strong S-curve dependence as temperature sweeps through the liquid crystal phase transformation. Such thermochromic materials, suitable for dynamic thermo-optical sensing and modulation, are anticipated to unlock new and smart approaches for controlling and directing light in stimuli-responsive devices.

A temperature-sensitive Förster resonance energy transfer system was constructed using a highly emissive liquid crystal co-assembled with Nile red, enabling thermo-optical modulation for controlling and directing light in stimuli-responsive devices.     

One-pot two-step microwave-assisted reaction in constructing 4,5-disubstituted pyrazolopyrimidines

[reaction: see text] A microwave-assisted reaction was developed to facilitate the construction of 4,5-disubstituted pyrazolopyrimidines. This one-pot two-step process involves a sequential S(N)Ar displacement of the C4 chloro substituent with various anilines and amines, followed by a Suzuki coupling reaction with different boronic acids. Using microwave irradiation leads to high product conversion, low side product formation, and shorter reactions.     

模板组装Fe纳米线阵列及其微结构

铝在硫酸溶液中经直流阳极氧化,得到多孔铝阳极氧化膜(AAO). 以AAO膜为模板,通过交流电沉积的方法,在AAO模板孔内成功组装了Fe纳米线.TEM分析表明,Fe纳米线的长度约为2.5 μm,其长度分布十分均匀；粗细均匀,直径约为25 nm. XRD实验分析证实,所制备的Fe纳米线为α-Fe.选区电子衍射（SAED）实验分析表明,α-Fe纳米线具有单晶结构.     

Relaxation dynamics of 2,7- and 3,6-distyrylcarbazoles in solutions and in solid films: mechanism for efficient nonradiative deactivation in the 3,6-linked carbazole

We performed time-resolved spectral investigations of two distyrylcarbazole derivatives, 2,7- and 3,6-distyrylcarbazole (2,7-DPVTCz and 3,6-DPVTCz, respectively), in dilute toluene solution and in solid films mixed with poly(methyl methacrylate) (PMMA). The lifetime of 2,7-DPVTCz in its excited state in solution is approximately 100 times as great as that of 3,6-DPVTCz, consistent with their photophysical nature. The former shows intense emission, but the latter is nearly nonfluorescent in a free environment. Moreover, the lifetime of 3,6-DPVTCz in its excited state increased also approximately 100 times when the molecule was encapsulated in a 3,6-DPVTCz/PMMA solid film, indicating that intramolecular motion of the molecule significantly affects the observed relaxation dynamics in a confined environment. Calculations on the excited states indicate that an efficient intersystem crossing is activated upon twisting of the bridged C-C single bond in a free 3,6-linked carbazole; such efficient deactivation is impractical in 2,7-linked carbazole or for 3,6-linked carbazole in a PMMA matrix. Information obtained from experiments on femtosecond fluorescence enables us to distinguish crucial relaxation processes in the excited state for a profound understanding of the details of vibrational and electronic relaxations of 3,6-DPVTCz in solution.     

Effects of mixed H2O‐CH3CN solvents on the rate of hydrazinolysis of N‐phenylphthalimide: Spectral and kinetic evidence for the occurrence of N‐aminophthalimide on the reaction path

Kinetic study on the cleavage of N‐phenylphthalimide (NPhPT) in the presence of 0.05 M NH₂NH₂ and mixed H₂O‐CH₃CN solvents reveals the occurrence of reaction scheme where A, B, C, C₁, An, E, and F represent NPhPT, o‐CO^?₂C₆H₄CONHC₆H₅, o‐CONHNH₂C₆H₄‐ CONHC₆H₅, N‐aminophthalimide, aniline, o‐CO^?₂C₆H₄CONHNH₂, and o‐CONHNH₂C₆H₄‐CONHNH₂, respectively. But, in the presence of either nonbuffered ?0.20 M NH₂NH₂ hydrazine buffer of pH ～7.30–8.26 with total buffer concentration ([Buf]_T) of >0.02 M, further conversion of F to 2,3‐dihydrophthalazine‐1,4‐dione (DHPD) has been detected depending upon the length of the reaction time (t), the values of [Buf]_T, and pH. It has been shown that the rate of conversion of C₁ to F is much faster than that of C to C₁ which is much faster than that of F to DHPD. The reaction step A → C involves general base (GB) catalysis, while step C → C₁ seems to involve specific base–general acid (GA) and GB‐GB catalysis. © 2005 Wiley Periodicals, Inc. Int J Chem Kinet 37: 147–161, 2005     

Mild and efficient synthesis of (Z)-alpha-chloroalkylidene-beta-lactones via the PdCl2-catalyzed cyclocarbonylation of 2-alkynols

[reaction: see text] A mild and efficient methodology involving PdCl(2)-catalyzed cyclocarbonylation of 2-alkynols with CuCl(2) for the synthesis of (Z)-alpha-chloroalkylidene-beta-lactones was developed. Using the readily available optically active propargylic alcohols allows convenient synthesis of the corresponding (Z)-alpha-chloroalkylidene-beta-lactones with high ee values. cis-Chloropalladation was observed as the major pathway, which is unique as compared to the reported data.     

"Dimers" and "trimers" of tetrahydroindenes and hexahydroazulenes, respectively generated from [2-(1-cycloalkenyl)ethynyl]carbene complexes (M = W, Cr) by cascade cyclization/cycloaddition reactions

A cascade of cyclization/cycloaddition reactions was triggered by addition of protic oxygen nucleophiles ROH 2 (RO = CH3CO2, PhCO2, PhO) to [2-(1-cyclohexenyl)ethynyl]carbene complexes 1b and 1c (M=W, Cr, respectively), affording highly strained "dimers" 11/11' and "trimers" 12 of the carbene ligand. The first reaction step involved the formation of 1-metalla1,3,5-hexatrienes 7, which readily gave tetrahydroindenes 8 by pi cyclization and extrusion of the metal unit. "Dimers" 11/11' were generated from tetrahydroindenes 8 by a highly exo selective [4+2] cycloaddition of compounds 1b and 1c to afford 1-metalla-1,3,5-hexatriene intermediates 9, and a spontaneous pi cyclization of the latter compounds involving the disengagement of the metal unit. Propenylidene cyclohexenes 13/13' were formed in "ene"-type side reactions to the pi cyclization of 1-metalla-1,3,5-hexatrienes 7, by loss of the metal unit. "Dimers" 11 were transformed into "trimers" 12 by a [4+2] cycloaddition and subsequent pi-cyclization of the resulting 1-metalla-1,3,5-hexatriene system. The course of the reaction was elucidated by means of model reactions with (2-phenylethynyl)carbene complex 14, in which 1-metalla-1,3,5-hexatriene intermediates 16 and 17 were isolated and characterized. Alkynyl benzene derivatives 19 were obtained by an unprecedented ring-expansion of a cyclopentadiene unit of "dimers" 11a and 11c, involving the insertion of a carbene carbon atom of compound 14 into a C=C bond. A reaction cascade leading to "dimers" 24/24' could also be triggered by treatment of compounds 2 with [2-(1-cycloheptenyl)ethynyl]carbene tungsten complex 1d.     

Synthesis,structure and DNA-binding studies on the 2-(3-chlorophenyl)imidazo[4,5-f]1,10-phenanthroline-bis(2,2′-bipy ridine)-ruthenium(II) complex

A new polypyridyl ligand, MCP {MCP = 2-(3-chlorophenyl)imidazo[4,5-f]1,10-phenanthroline} and its ruthenium(II) complex, [Ru(bpy)2(MCP)](ClO4)2· 0.5MeCN (bpy = 2,2-bipyridine), have been synthesized and characterized. The structure of the complex was determined by single crystal X-ray diffraction techniques. The MCP ligand is essentially planar and the stacking interactions between the ligands were observed in the crystal. [Ru(bpy)2(MCP)]2+ can strongly bind to Calf thymus DNA through intercalation of MCP ligand. The Cl substitute group has no significant effect on the spectral properties and DNA-binding behaviour of the complex.     

投料顺序对动态硫化PP／EPDM性能影响及其机理的研究

针对ＰＰ降解在ＰＰ／ＥＰＤＭ动态硫化中对体系产生的不利影响。考察了四种不同投料顺序对ＰＰ／ＥＰＤＭ动态硫化物的冲击韧性，加工流动性，交联程度和断面形貌等宏观和微观性能，并进行了不同ＥＰＤＭ含量的动态硫化和非硫化ＰＰ／ＥＰＤＭ的性能比较。结果表明，优化投料顺序能实现对动态硫化体系中化学反应对象和化学反应程度的有效干预。     

Novel routes to 1-aryl-1,4-dihydro-3(2H)-isoquinolinones and 2-substituted or 2,3-disubstituted benzofurans by intramolecular cyclizations

N-(α-Benzotriazolylalkyl)arylacetamides, readily available from an arylacetamide, an aldehyde and benzotriazole, undergo intramolecular cyclization under acidic conditions to give 1-aryl-1,4-dihydro-3(2H)-isoquinolinones in good to excellent yields. Similarly, 2-(benzotriazol-1-yl)-2-(o-hydroxyphenyl)ethanols, obtained by lithiation of 2-(benzotriazol-1-ylmethyl)phenols followed by quenching with aldehydes or ketones, eliminate a molecule of water and a molecule of benzotriazole yielding 2-substituted and 2,3-disubstituted benzofurans.