AIE fluorescent probe based on tetraphenylethylene and morpholine-thiourea structures for detection of HClO.

As an important signal molecule in the living body, hypochlorous acid (HClO) participates in various physiological processes. However, excessive hypochlorous acid will cause some oxidative damage. The organic aggregation-induced emission luminogens (AIEgens) based on tetraphenylethylene (TPE) structures have recently become research hotspots as fluorescent probe materials. In this paper, a kind of water-soluble fluorescent probe TPE-M based on TPE and morpholine-thiourea structures were designed and synthesized for the detection of HClO. Due to the introduction of morpholine structures, the TPE-M showed excellent water solubility. The fluorescence properties of the TPE-M were strongly affected by the polarity of the solvent. Besides, the cation-anion and reactive oxygen species recognition experiments indicated that the fluorescent probe TPE-M displayed a single recognition characteristic for HClO because of the existence of thiourea structures. The limit of detection for HClO was calculated to be 0.25 µM. The particle size distribution measurement under the water phase revealed that the particle size of the TPE-M was mainly centered at 150 nm. The recognition mechanism of HClO by the probe TPE-M was proposed and explained by mass spectra and Gaussian calculation. Furthermore, a cell imaging experiment proved that the TPE-M probe successfully detected HClO in Hela cells.

Photoluminescence, thermal and surface properties of triarylimidazole-containing polyimide nanocomposite films.

In this work, a triarylimidazole-containing diamine 2-(4-methylphenyl)-4,5-bis(4-(4-amino-2-trifluoromethylphenoxy)phenyl)imidazole (MPBAI) was firstly synthesized and polymerized with 1,2,3,4-cyclobutanetetracarboxylic dianhydride (CBDA) to prepare transparent polyimide (PI) films by means of thermal imidization. Then, inorganic nanoparticles including silica (SiO2), alumina (Al2O3) and silicon nitride (Si3N4) were separately introduced into the PI(MPBAI-CBDA) with different mass fractions of 0.02%, 0.10%, 0.50% and 2.50% to obtain three series of PI nanocomposite films. All these films were close to colorless and transparent, although the light transmittance showed a downward trend due to the introduction of nanoparticles. Moreover, as the content of inorganic nanoparticles increased, the fluorescence intensities of these films were increased. Comparatively, the improvement effect of nano-SiO2 was the most obvious. When the content of SiO2 was 2.50%, the maximum intensity of the fluorescence absorption peak was increased by 9.6 times, and the absolute fluorescence quantum yield reached 17.2%, about 5.2 times that of the original PI film. Moreover, the maximum absorption peak produced a red shift of 85 nm due to the addition of 2.50% Si3N4, which was probably caused by the weakening of fluorescence quenching effect and high permittivity. The nanocomposites exhibited high glass transition temperatures of around 300 °C and excellent thermal stabilities. The surface hydrophobicity was changed by adjusting the mass and type of nanoparticles. Thus, this work provided a simple way to improve the photoluminescence effect by introducing the nanoparticles. The functional films will be expected to be applied in some optical applications.

Enhanced gas separation and mechanical properties of fluorene-based thermal rearrangement copolymers.

A series of thermal rearrangement (TR) copolymer membranes were prepared by the copolymerization of 9,9-bis(3-amino-4-hydroxyphenoxyphenyl) fluorene (BAHPPF), 9,9-bis(3-amino-4-hydroxyphenyl)fluorene (BAHPF) and 2,2'-bis(3,4'-dicarboxyphenyl)hexafluoropropane dianhydride (6FDA), followed by thermal imidization and further thermal rearrangement. The effects of molar ratio of diamines on the structure and properties of copolymer membranes were studied. The copolymer precursors CP-4:6 and CP-5:5 exhibited excellent mechanical properties. The mechanical properties of precursor membranes rapidly decreased with the increase of thermal treatment temperatures, but the tensile strength of TRCP-4:6 still reached 21.2 MPa. In general, the gas permeabilities of TR copolymers increased with the increase of BAHPF content. Comparatively, TRCP-3:7 and TRCP-4:6 showed higher gas permeabilities, coupled with high O2/N2 and CO2/CH4 selectivities. Especially, the H2, CO2, O2, N2 and CH4 permeabilities of TRCP-4:6 reached 244.4, 269.0, 46.8, 5.20 and 4.60 Barrers respectively, and the selectivities for CO2/CH4 and O2/N2 were 58.48 and 9.00, which exceeded the 2008 upper bound. Therefore, these TR copolymer membranes are expected to be one of the candidate materials for gas separation applications.

Phthalide-containing poly(ether-imide)s based thermal rearrangement membranes for gas separation application.

The diamine monomer 3,3-bis[4-(3-hydroxy-4-amino-phenoxy)phenyl]phthalide (BHAPPP) was firstly synthesized by the nucleophilic substitution of 5-fluoro-2-nitrophenol and phenolphthalein, followed by a reduction reaction. A series of phthalide-containing poly(ether imide)s (PEI) were then prepared through the polycondensation of BHAPPP with six kinds of dianhydrides, including 4,4'-(hexafluoroisopropylidene)diphthalic anhydride (6FDA), 3,3',4,4'-benzophenone tetracarboxylic dianhydride (BTDA), 3,3',4,4'-biphenyl tetracarboxylic dianhydride (BPDA), 4,4'-oxydiphthalic dianhydride (ODPA), 1,2,3,4-cyclobutane tetracarboxylic dianhydride (CBDA) and pyromellitic dianhydride (PMDA), as well as thermal imidization. After further thermal treatment, the corresponding thermal rearrangement (TR) membranes were obtained. Due to the existence of the phthalide lactone ring, the PEIs probably underwent TR and crosslinking simultaneously. With the increase of thermal treatment temperature, the mechanical properties of the TR membranes dramatically decreased, but the gas separation properties obviously increased. When the PEIs were treated at 450 °C for 1 h, the CO2, H2, O2, N2 and CH4 permeability of TR(BHAPPP-6FDA) reached 258.5, 190.5, 38.35, 4.25 and 2.15 Barrers, respectively. Meanwhile, the CO2/CH4 selectivity of 120.2 sharply exceeded the 2008 Robeson limit, and O2/N2 selectivity was 9.02, close to the 2015 upper limit. Therefore, the TR membranes derived from phthalide-containing PEIs exhibit superior gas separation performance, andare expected to be applied in the field of gas separation.

Solubility, thermal and photoluminescence properties of triphenyl imidazole-containing polyimides.

In this paper, three kinds of triphenyl imidazole-containing diamines including 2-phenyl-4,5-bis(4-(4-amino-2-trifluoromethylphenoxy)phenyl)imidazole (PBAI), 2-(4-methylphenyl)-4,5-bis(4-(4-amino-2-trifluoromethyl phenoxy)phenyl)imidazole (MPBAI) and 2-(4-trifluoromethylphenyl)-4,5-bis(4-(4-amino-2-trifluoromethylphenoxy)phenyl)imidazole (TFPBAI) were synthesized. Then, a series of polyimide (PI) films were prepared by the solution polymerization of the three diamines and various dianhydrides, such as 4,4'-(hexafluoroisopropylidene)diphthalic anhydride (6FDA), 1,2,4,5-pyromellitic dianhydride (PMDA) and 1,2,3,4-cyclobutanetetracarboxylic dianhydride (CBDA), followed by thermal imidization. The effects of chemical structures on the solubilities and thermal, optical and electrochemical properties of polyimides were explored. All the polyimides exhibited higher glass transition temperatures around 300 °C and excellent solubilities in common polar solvents. The polyimide films derived from CBDA or 6FDA showed better optical properties with light color and transparent characteristics. The fluorescence test showed that the photoluminescence color of CBDA-based polyimide films is in the blue range in the CIE 1931 spectrum, while the polyimide film based on PMDA and 6FDA presented black or weak yellow light. However, all these polyimides in solution exhibited similar blue luminescence. Electrochemical tests indicated that the HOMO and LUMO values of these films were around -6.5 and -3.6 eV, and the energy gap difference was about 3.0 eV. Therefore, the triphenyl imidazole-containing polyimides exhibit comprehensive performance, which will be expected as a new kind of functional material for certain application in the optical and optoelectronics fields.

Synthesis and gas permeation properties of thermally rearranged poly(ether-benzoxazole)s with low rearrangement temperatures.

The diamine monomer, 9,9-bis[4-(4-amino-3-hydroxylphenoxy)phenyl] fluorene (bis-AHPPF) was successfully synthesized according to our modified method. A series of hydroxyl-containing poly(ether-imide)s (HPEIs) were prepared by polycondensation of the bis-AHPPF diamine with six kinds of dianhydrides, including 1,2,3,4-cyclobutanetetracarboxylic dianhydride (CBDA), pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyl tetracarboxylic diandhydride (BPDA), 3,3',4,4'-oxydiphthalic anhydride (ODPA), 3,3',4,4'-benzophenonetetracarboxylic dianhydride (BTDA) and 4,4'-(hexafluoroisopropylidine)diphtalic anhydride (6FDA) followed by thermal imidization. The corresponding thermally rearranged (TR) membranes were obtained by solid state thermal treatment at high temperature under a nitrogen atmosphere. The chemical structure, and physical, thermal and mechanical properties of the HPEI precursors were characterized. The effects of heat treatment temperature and dianhydrides on the gas transport properties of the poly(ether-benzoxazole) (PEBO) membranes were also investigated. It was found that these HPEIs showed excellent thermal and mechanical properties. All the HPEI precursors underwent thermal conversion in a N2 atmosphere with low rearrangement temperatures. The gas permeabilities of the PEBO membranes increased with the increase of thermal treatment temperature. When HPEI-6FDA was treated at 450 °C for 1 h, the H2, CO2, O2 and N2 permeabilities of the membrane reached 239.6, 196.04, 46.41 and 9.25 Barrers coupled with a O2/N2 selectivity of 5.02 and a CO2/N2 selectivity of 21.19. In six TR-PEBOs, PEBO-6FDA exhibited the lowest rearrangement temperature and largest gas permeabilities. Therefore, thermally rearranged membranes from bis-AHPPF-based HPEIs are expected to be promising materials for gas separation.

Synthesis, photophysical, electrochemical and electroluminescent properties of a novel iridium(III) complex based on 2-phenylbenzo[d]oxazole derivative.

A new phosphorescent iridium (III) complex based on 2-(4-tert-butylphenyl)-5-methylbenzo[d]oxazole as main ligand, i.e. bis(2-(4-tert-butylphenyl)-5-methylbenzo[d]oxazole-N,C(2'))iridium(acetylacetonate) [(tmbo)2Ir(acac)], was synthesized for organic light-emitting diodes (OLEDs), and its photophysical, electrochemical and electroluminescent properties were investigated. The complex displayed strong phosphorescence emission, high decomposition temperature, short phosphorescent lifetime and reversible redox electrochemical behavior. The OLEDs based on (tmbo)2Ir(acac) as dopant emitter exhibited maximum luminance efficiency of 26.1cdA(-1) and high luminance of 16,445 cd m(-2). Interestingly, highly doped device based on (tmbo)2Ir(acac) showed high efficiency with negligible roll-off under a wide range of driving current density, which was mainly attributed to the effect of bulky steric hindrance of multi-methyl groups on this complex and its short phosphorescent lifetime.

(Z)-3ß-(2-Chloro-anilino)-17(20)-pregnene.

In the pregnene fragment of the title compound, C27H38ClN, the three six-membered rings exhibit chair conformations and the five-membered ring has a distorted envelope form with the fused C atom not bearing a methyl group as the flap atom. The amino group is involved in the formation of an intra-molecular N-H⋯Cl hydrogen bond. The crystal packing exhibits no short inter-molecular contacts.

Application of hinokitiol potassium salt for wood preservative.

The decay of wood and other cellulosic materials by fungi cause significant economic loss. The widely used chromated copper arsenate was prohibited for the environmental impact and safety of arsenic and chromium. It was found that natural product hinokitiol (HK) had fungicidal and insecticidal activities, and its toxicity was bearable for the environment. We described the practical synthesis of HK-K salt. According to the GB/T18261-2000 and LY/T1283-1998, wood preservative performance of HK-K salt was tested. The results showed that the best inhibitory concentration of HK-K salt was 50 mg/L, for which the prevention effectiveness on mold is better, the killed value is between 0 and 1, and the corrosion-resistant for wood-rotting fungi is grade A.

12α-Hy-droxy-3,27-dioxooleanano-28,13-lactone.

There are two independent mol-ecules in the asymmetric unit of the title compound, C(30)H(44)O(5). They comprise a triterpenoid skeleton of five six-membered rings and a five-membered lactone ring. The five six-membered rings are all trans-fused. In both independent mol-ecules the D rings adopt a slightly distorted half-chair conformation due the presence of the lactone ring while the other four six-membered rings all adopt chair conformations. The characteristic carbon-carbon double bond of the oleanoic skeleton is absent. Inter-molecular O-H⋯O hydrogen bonds between the hy-droxy and carbonyl groups occur in the crystal structure.

4-[4,5-Bis(pyridin-2-yl)-1H-imidazol-2-yl]phenol monohydrate.

In the title hydrate, C(19)H(14)N(4)O·H(2)O, the dihedral angle between the two pyridine rings is 38.0 (2)°. The dihedral angle between the imidazole and benzene rings is 25.3 (2)°. The crystal structure is stabilized by inter-molecular O-H⋯O, O-H⋯N and N-H⋯O hydrogen bonds.

cis-Bis[2-(1,3-benzothia-zol-2-yl)-1-(4-fluoro-phen-yl)ethen-yl](pentane-2,4-dionato-κO,O')iridium(III).

In the title compound, [Ir(C(15)H(9)FNS)(2)(C(5)H(7)O(2))], the Ir atom is hexa-coordinated by three chelating ligands, with two cyclo-metalated 2-(1,3-benzothia-zol-2-yl)-1-(4-fluoro-phen-yl)ethenyl ligands showing N,C-bidentate coordination and an O,O'-bidenate pentane-2,4-dionate anion, thereby forming a distorted octa-hedral enviroment.