Carboxylic Acids from <Emphasis Type="Italic">Phyllanthus urinaria</Emphasis>

Five compounds, terephthalic acid mono-[2-(4-carboxy-phenoxycarbonyl)-vinyl] ester (1), (E)-3-(5′-hydroperoxy-2,2′-dihydroxy[1,1′-biphenyl]-4-yl)-2-propenoic acid (2), 3,4,5-trihydroxybenzoic acid (3), succinic acid (or butanedioic acid) (4), and 2,3,4,5,6-pentahydroxybenzoic acid (5), were isolated from Phyllanthus urinaria. The structures of these compounds were elucidated by means of spectral techniques including IR, MS, and 1D/2D NMR. 1 and 2 are new compounds.__________Published in Khimiya Prirodnykh Soedinenii, No. 1, pp. 14–17, January–February, 2005.     

绿色氧化法制备联苯类化合物的研究性实验设计与实践*

以苯甲醛和丙酮为原料,利用Robinson增环反应先制备3-甲基-5-苯基环己-2-烯-1-酮,再引导学生设计并研究了水相绿色氧化3-甲基-5-苯基环己-2-烯-1-酮合成联苯类化合物3-乙氧基-5-甲基-1,1′-联苯的影响因素,利用核磁共振确定了产物结构。该研究性实验教学以绿色化学为中心,结合了2步连续反应,产物易提纯且产率高,并开展了开放式大型分析仪器教学和测试,对学生有机合成实验能力和科学研究能力的培养具有很好的教学效果。     

Morphology and spectral properties of thin films of benzoxazole derivatives of biphenyl

We have studied the spectral properties and morphology of thin films (TVD films) formed by thermal vacuum deposition of 4,4′-bis[(E)-1-(1,3-benzoxazol-2-yl)-2-ethenyl]-1,1′-biphenyl and its substituted derivatives. We have shown that introducing bulky 2,2′-oxyhexyl substituents into the biphenyl units leads to a shift of the fluorescence maximum for the TVD films toward shorter wavelengths, a decrease in their photostability, and aggregation of the films during storage. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 74, No. 3, pp. 300–303, May–June, 2007.     

Photoinduced DNA Interstrand Cross-Linking by 1,1′-Biphenyl Analogues: Substituents and Leaving Groups Combine to Determine the Efficiency of Cross-Linker

Two series of 1,1′-biphenyl analogues with various leaving groups (L=OAc, OCH₃, OCHCH=CH₂, OCH₂Ph, SPh, SePh, and Ph₃P⁺) were synthesized. Their reactivity towards DNA and the reaction mechanism were investigated by determining DNA interstrand cross-link (ICL) efficiency, radical and carbocation formation, and the cross-linking reaction sites. All compounds induced DNA ICL formation upon 350 nm irradiation via a carbocation that was generated from oxidation of the corresponding free radicals. The ICL efficiency and the reaction rate strongly depended on the combined effect of the leaving group and the substituent. Among all compounds tested, the high ICL efficiency (30–43 %) and fast reaction rate were observed with compounds carrying a nitrophenyl group and acetate ( 2 a ), ether ( 2 b and 2 c) , or triphenylphosphonium salt ( 2 g ) as leaving groups. Most compounds with a 4-methoxybenzene group showed similar DNA ICL efficiency (≈30 %) with a slow DNA cross-linking reaction rate. Both cation trapping and free radical trapping adducts were detected in the photo activation process of these compounds, which provided direct evidence for the proposed mechanism. Heat stability study in combination with sequence study suggested that these photo-generated benzyl cations alkylate DNA at dG, dA, and dC sites.     

Blue organic electroluminescent devices based on a distyrylarylene derivative as emitting layer and a terbium complex as electron-transporting layer

With a blue distyrylarylene derivative, 4,4′-bis(2,2-di(2-methoxyphenyl)ethenyl)-1,1′-biphenyl (CBS) as emitting material, double-layer and triple-layer electroluminescent (EL) devices were fabricated. For the device using tris-(1-phenyl-3-methyl-4-isobutyryl-5-pyrozolone)-bis(triphenyl phosphine oxide) terbium (Tb(PMIP)₃(TPPO)₂) as the electron-transporting layer, blue EL emission with a maximum luminance of 253 cd/m² was achieved at 19 V. The difference of Tb(PMIP)₃(TPPO)₂ and tris(8-hydroxyquinolinate)aluminum (AlQ) as the electron-transporting materials in these devices were compared and discussed.     

N-Phenylation of N-Arylaminophthalimides with Triphenylbismuth and Cupric Acetate: A Convenient Synthesis of 1-Aryl-1- Phenylhydrazines

Synthesis of 1-aryl-1-phenylhydrazines (2) from N-aryl-N-phenylaminophthalimides (1) which were synthesized by the phenylation of 1 with triphenylbismuth and cupric acetate is described.     

Adapting (4,4) Networks through Substituent Effects and Conformationally Flexible 3,2’:6’,3”-Terpyridines

Coordination networks formed between Co(NCS)₂ and 4’-substituted-[1,1’-biphenyl]-4-yl-3,2’:6’,3”-terpyridines in which the 4’-group is Me (1), H (2), F (3), Cl (4) or Br (5) are reported. [Co(1)₂(NCS)₂]_n·4.5nCHCl₃, [Co(2)₂(NCS)₂]_n·4.3nCHCl₃, [Co(3)₂(NCS)₂]_n·4nCHCl₃, [Co(4)₂(NCS)₂]_n, and [Co(5)₂(NCS)₂]_n·nCHCl₃ are 2D-networks directed by 4-connecting cobalt nodes. Changes in the conformation of the 3,2’:6’,3”-tpy unit coupled with the different peripheral substituents lead to three structure types. In [Co(1)₂(NCS)₂]_n·4.5nCHCl₃, [Co(2)₂(NCS)₂]_n·4.3nCHCl₃, [Co(3)₂(NCS)₂]_n·4nCHCl₃, cone-like arrangements of [1,1’-biphenyl]-4-yl units pack through pyridine…arene π-stacking, whereas Cl…π interactions are dominant in the packing in [Co(4)₂(NCS)₂]_n. The introduction of the Br substituent in ligand 5 switches off both face-to-face π-stacking and halogen…π-interactions, and the packing interactions are more subtly controlled. Assemblies with organic linkers 1–3 are structurally similar and the lattice accommodates CHCl₃ molecules in distinct cavities; thermogravimetric analysis confirmed that half the solvent in [Co(3)₂(NCS)₂]_n·4nCHCl₃ can be reversibly removed.     

Synthesis,Neuroprotection, and Antioxidant Activity of 1,1′-Biphenylnitrones as α-Phenyl-N-tert-butylnitrone Analogues in In Vitro Ischemia Models

Herein, we report the neuroprotective and antioxidant activity of 1,1′-biphenyl nitrones (BPNs) 1–5 as α-phenyl-N-tert-butylnitrone analogues prepared from commercially available [1,1′-biphenyl]-4-carbaldehyde and [1,1′-biphenyl]-4,4′-dicarbaldehyde. The neuroprotection of BPNs 1-5 has been measured against oligomycin A/rotenone and in an oxygen–glucose deprivation in vitro ischemia model in human neuroblastoma SH-SY5Y cells. Our results indicate that BPNs 1–5 have better neuroprotective and antioxidant properties than α-phenyl-N-tert-butylnitrone (PBN), and they are quite similar to N-acetyl-L-cysteine (NAC), which is a well-known antioxidant agent. Among the nitrones studied, homo-bis-nitrone BPHBN5, bearing two N-tert-Bu radicals at the nitrone motif, has the best neuroprotective capacity (EC₅₀ = 13.16 ± 1.65 and 25.5 ± 3.93 μM, against the reduction in metabolic activity induced by respiratory chain blockers and oxygen–glucose deprivation in an in vitro ischemia model, respectively) as well as anti-necrotic, anti-apoptotic, and antioxidant activities (EC₅₀ = 11.2 ± 3.94 μM), which were measured by its capacity to reduce superoxide production in human neuroblastoma SH-SY5Y cell cultures, followed by mononitrone BPMN3, with one N-Bn radical, and BPMN2, with only one N-tert-Bu substituent. The antioxidant activity of BPNs 1-5 has also been analyzed for their capacity to scavenge hydroxyl free radicals (82% at 100 μM), lipoxygenase inhibition, and the inhibition of lipid peroxidation (68% at 100 μM). Results showed that although the number of nitrone groups improves the neuroprotection profile of these BPNs, the final effect is also dependent on the substitutent that is being incorporated. Thus, BPNs bearing N-tert-Bu and N-Bn groups show better neuroprotective and antioxidant properties than those substituted with Me. All these results led us to propose homo-bis-nitrone BPHBN5 as the most balanced and interesting nitrone based on its neuroprotective capacity in different neuronal models of oxidative stress and in vitro ischemia as well as its antioxidant activity.     

Fluorine cleavage of the light blue heteroleptic triplet emitter FIrpic

The lifetime stability of devices containing FIrpic as emitter has been a major concern for organic blue light emitting devices (OLEDs). To gain a deeper knowledge about the purity of FIrpic (bis[2-(4,6-difluorophenyl)pyridyl-N,C2′]iridium (III)) emitters and how the purity is influenced by sublimation steps, non-sublimated and sublimated FIrpic material was analyzed via liquid chromatography coupled with electron spray ionization mass spectrometry (LC/ESI/MS). Cleavage of an electron-withdrawing group from one of the ligands of the heteroleptic phosphorescent emitter could be identified in sublimated FIrpic material via LC/ESI/MS. A detailed chemical analysis using LC/ESI/MS was carried out for complete blue emitting devices of the following structure: indium-tin-oxide (ITO)/50 nm (α-4,4′-bis[(1-naphthyl)phenylamino]-1,1′-biphenyl) (α-NPD)/10 nm 4,4′,4″-tris(carbazol-9-yl)triphenylamine (TCTA)/100 nm TCTA:8% FIrpic/50 nm 1,1′-biphenyl-4′-oxy)-bis(8-hydroxy-2-methylquinolinato)-aluminum (BAlq)/1 nm LiF/100 nm Al. Two isomers of (FIrpic-1F) could be detected in an aged OLED. Changes in the ligand systems of FIrpic, especially the loss of fluorine during the deposition process can alter the emissive properties of the blue phosphorescent emitter. Beside isomer formation and chemical degradation of FIrpic, substantial degradation was observed for the hole transport material α-NPD in driven OLEDs.