新型卟啉衍生物的合成与表征(英文)

以1-溴-2,3,4,6-O-乙酰-D-葡萄糖(1)或氯乙醇分别与5-(对-氨基苯基)-10,15,20-三苯基卟啉(2)反应,制备5-(对-(-D- 葡萄糖氨基苯基)-10,15,20-三苯基卟啉(3)或5-(对-羟乙基氨基苯基)-10,15,20-三苯基卟啉(4)．该方法的反应条件温和,合成路线短,纯化方法简单．     

Photoelectrical performance of nanocrystalline TiO2 film electrode sensitized by Ru(II)-bipyridine complexes

Two kinds of Ru(II)-bipyridine complexes,cis-di(thiocyanate)bis(2,2′-bipyridyl-4,4′-dicarboxylate) ruthenium(II) andcis-di(thiocyanate)bis(2, 2′-bipyridyl-3, 3′-dicarboxylate) ruthenium(II), were utilized as the sensitizers to the nanocrystalline TiO₂ film electrodes. Study shows that the two dyes have quite different sensitization properties due to the strong steric effect of carboxyl groups. In addition, the pretreatment to nanocrystalline TiO₂ film electrodes with TiCl₄ was investigated, which is an effective way to improve the photoelectric conversion performances of sensitized TiO₂ electrodes.     

Synthesis of a new type tetraamides bridged calix[4]arene

Two new tetraamides bridged calix[4]arenes were synthesized by the condensation reaction of 1,3-bis-chlorocarbonylmethyl p-tert-butylcalix[4]arene with 1,2-bis (2′-amino-2′-methylpropanamido) benzene or 1,2-bis (2′-amino-2′-methylpropanamido)-4,5-dichloro benzene, respectively. The new compounds were characterized by¹H-NMR, MS-FAB, and elemental analysis; macrocyclic polyamine. Foundation item: Supported by the National Science Foundation of China (20072029) Biography: Xiao Yuan-jing (1974-), male, Doctor, research direction: supramolecular chemistry.     

Synthesis of a symmetrical tetrasubstituted cucurbit[6]uril and its host-guest inclusion complex with 2,2′-bipyridine

Synthesis of a symmetrical tetrasubstituted cucurbit[6]uril has been achieved by using the diether of dimethylglycoluril (1) and the dimmer of glycoluril (2). The structure of the symmetrical tetramethylcucurbit[6]uril (TMeQ[6]) has been determined by single crystal X-ray diffraction, ^1H NMR spectroscopy and ESMS. The ^1H NMR spectra of 2,2‘-bipyridine added to TMeQ[6] reveal that the host-guest inclusion complex was easily formed.     

Synthesis and light-emitting properties of organic electroluminescent compounds and their metal complexes

Several organic electroluminescent (EL) compounds, 2,2‘-(1,4-phenylenedivinylene)bis-3,3-dimethyl-indolenine (1), 2,2‘-(1,4-phenylenedivinylene)bis-benzoxazole (2), 2,2‘-(1,4-phenylenedivinylene)bis-benzothiazole (3), 4,4‘-(1,4-phenylenedivinylene)bis-quinoline (4), 2,2‘-(1,4-phenylene divinylene)bis-quinoline (5), 2,2‘-(1,4-phenylenedivinylene)bis-1,3,3-trimethyl-indolenine dichlo ride (6), 2,2‘-(1,4-phenylene-divinylene)bis-1-hydro-3,3-dimethyl-indolenine dichloride (7), 2,2‘-(1,4-phenylenedivinylene)bis-8-acetoxy-quinoline (8), 2,2‘-(1,4-phenylenedivinylene)bis-8-hydroxyquinoline (9) and metal complexes of 9, Al(PHQ) (10) and Zn(PHQ) (11), have been synthesized and characterized. The crystal structure of 6 was determined. Light emitting properties of the prepared compounds have been investigated. 1 produces an orange-yellow emission (λmax=575nm). The cation, 6, gives a red emission (λmax=607nm), which is shifted 32 nm to the red compared to 1.8 produces a yellow emission (λmax=567nm). The metal complex 10 gives a red emission (λmax=610nm), which is a red shift of 43 nm compared to 8. The change in structure in the prepared compound caused a change in the electron distribution in the compounds, which induces a large wavelength shift of the emitted-light. Thermal analysis showed that the decomposition temperatures of the metal complexes (10, 11) were higher than those for the smaller organic molecular compounds (1-9). Therefore, metal complexes (10, 11) can be used as EL materials over a larger temperature range.     

一种新型卟啉席夫碱的合成

合成了一种未见报道的卟啉席夫碱5-(4-氨基苯基)-10,15,20-三苯基卟啉缩1-苯基-3-甲基-4-苯甲酰基-5-吡唑啉酮,并通过红外光谱、紫外-可见光谱、元素分析和质谱对目标产物进行了表征,并着重讨论了其紫外-可见光谱.     

Synthesis of calix[4]dithiacrown platinum complexes and their catalytic behavior in the hydrosilylation of olefins with triethoxysilane

5,11,17,23-Tetrakis-1′, 1′-dimethylethyl-25,27-dihydroxy-26,28-1″, 7″, 13″-trioxa-4″, 10″-dithiatridecylcene-calix[4]arene (calix[4]dithiacrown-5) and its O-methylated derivate (dimethylcalix[4]dithiacrown-5) were synthesized fromp-tert-butylcalix[4] arene via 1, 3-lower rim functionalization with chloroethyltosylate, followed by ring-closing condensation with β,β/t'-dimercaptoethyl ether in the presence of sodium ethoxide as a base in reflux ethanol under nitrogen atmosphere, followed by methylation with methyltosylate in the presence of NaH as a base in dioxane. It was found that they can coordinate with platinous chloride and the platinous complexes are efficient catalysts for the hydrosilylation of olefins with triethoxysilane. Foundation item: Supported by National Natural Science Foundation of China Biography: CHEN Yuan-yin (1936-), male, Professor.     

Studies on syntheses of biscrown ether compounds

Multi-ester type biscrown ether compound(I) was prepared by the reaction of 6-bromoacetacetic ester dibenzo-16-crown-5(7) with phenyl-methyl ether-2,6-diformic acid potassium salt in anhydrous DMF at refluxed temperature, and color biscrown ether compound(II) was prepared by the reaction of 4′-aminobenzo-15-crown-5(12) with 2,2′(O-formoyl naphthyl)ethyl ether (9) in anhydrous ethanol at 40 C under N₂. New compounds(I, II) were characterized by IR,¹H NMR, MS and elemental analysis. Supported by the National Natural Science Foundation of China Niu Changrong: born in December, 12, 1938, Professor     

Construct 2D nanostructure of co-adsorbed dipyridyl derivative by stabilization of hydrogen bond and long alkyl chains

The self-assembled structures of 4, 4‘‘-dionoyl-2,2‘‘-dipyridyl and its co-adsorption with stearic acid on highly oriented pyrolytic graphite (HOPG) have been studied by the scanning tunneling microscopy (STM). As a result, 4,4‘‘-dionoyl-2,2‘‘-dipyridyl forms a planar trans conformation in two cases, and through the co-adsorption with stearic acid, 4,4‘‘-dionoyl-2,2‘‘-dipyridyl and stearic acid form a well-ordered nanostructure.     

Bridging of Calixarenes with N, N＇-Bis（Chloroacetyl） Propylenediamine

A new bridging reagent, N, N‘-bis (chloroacetyl) propylenediamine was used to explore the relativeactivity and bridging pattern of p-ten-bury lcalix [4] arene, p-tert-butylcalix [6] arene and butylcalix [8] arene. It wasfound that the bridging reaction is selectively, at least, preferably at 1, 3-position for p-tert-butylcalix [4] arene and p-tert-butylcalix [6] arene, 1,5-position for p-tert-butylcalix [8] arene. Taking the yield of bridged calixarene as a compar-sion standard, the activity decreases with the increasing of the number of phenolic units in calixarene.     

Determination of some carbonyl carboxylic acids using chemiluminescent reaction of Ru(bipy)3 2+−Ce(IV)

A coupled chemiluminescence method for the determination of some carboxylic acids was developed, based on their enhancement the chemiluminescence light emission of the reaction of tirs (2,2′-bipyridine) ruthenium(II) and Ce(IV) in sulfuric acid medium. The conditions for their determination were optimized. The following detection limits were obtained: oxalic acid, 2.67×10⁻⁸ mol/L; propandioic acid, 1.20×10⁻⁶ mol/L; pyruvic acid, 1.35×10⁻⁸ mol/L; citric acid, 5.10×10⁻⁸ mol/L; barbituric acid, 2.48×10⁻⁷ mol/L. The proposed method was successfully applied to determination of oxalic acid. The coupled chemiluminescent reaction mechanism and rate equation are proposed. Foundation item: Supported by the National Natural Science Foundation of China and the Natural Science Foundation of Hubei Province Biography: HAN He-you (1962-), male, Associate professor, phD, graduate candidate     

Effect of iron deficiency on heterocyst differentiation and physiology of the filamentous cyanobacterium<Emphasis Type="Italic">Anabaena</Emphasis> sp. PCC 7120

The effect of iron deficiency on heterocyst differentiation and some physiological properties of the filamentous cyanobacteriumAnabaena sp. PCC 7120 was investigated. Under moderate iron limitation conditions, achieved by addition of iron chelator 2, 2′-Dipyridyl (<80 μmol/L) led to delayed heterocyst differentiation, no heterocyst differentiation was observed under severe iron limitation conditions, when the concentration of 2,2′-Dipyridyl in the medium was more than 100 μmol/L. it seemed that there are certain iron-regulated genes or operons whose function is to control heterocyst development. In addition, iron deficiency impaired the growth. Low iron cells had a decrease in the quantities of pigment content (chlorophyll and phycocyanin content), the whole cellin vivo absorbance spectra confirmed the decrease, the protein electrophoretic profiles revealed that iron-deficient cells had less protein bands, with the increase of 2,2′-Dipyridyl, the protein bands was more and more less. And differently, iron deficiency also caused an increase of ROS (Reactive Oxygen Species) and SOD activity, it suggests that iron deficiency led to oxidative stress, which generally occured under high-iron conditions. Foundation item: Supported by the National Natural Sciences Foundation of China (30070154), the Frontier Science Projects Programme of the Institute of Hydrobiology, the Chinese Academy of Sciences (220316), State Key Project on Cyanobacterial Bloom Control in Lake Danchi (K9905-35-01) Biography: Xu Wenllang (1974-), male, Ph. D. research direction: molecular genetics of eyanobacteria.     

Study on laccase-catalyzed oxidation of disubstituted ferrocene and π-arene-π-cyclopentadienyliron derivatives

It is studied that Rhus vernicifera laccase catalyzed oxidation of 26 disubstituted ferrocene and its metal complexes, π-arene-π-cyclopentadienyliron derivatives and metal meso-(tetra-4-sulfanatophenyl)porphyrin in the diethylene glycol monobutyl ether (DGBE)/phosphate buffer (V/V, 1/5). It is found that 1,1′-bishydroxylmethyl ferrocene etc 16 compounds are new substrates of laccase. The relation of structure and function of substrates is discussed. The affective factors of laccase-catalyzed oxidation of 1,1′-bishydroxyl-methyl ferrocene—pH, temperature, substrate concentration, laccase quantity and surfactant were investigated further. Foundation item: Supported by the National Natural Science Foundation of China (39170203) Biography: Ji Li-cai(1945-), male, professor, research direction: organic chemistry and biochemistry     

Inhibition of bromophenols against PTP1B and anti-hyperglycemic effect of <Emphasis Type="Italic">Rhodomela confervoides</Emphasis> extract in diabetic rats

Protein tyrosine phosphatase 1B （PTPIB） plays an important role as a negative regulator In insulin signaling pathways. PTPIB is an effective target for the treatment of type 2 diabetes mellitus. Four bromophenol derivatives from red algae Rhodomela confervoides, 2,2＇,3,3＇-tetrabromo-4,4＇,5,5＇-tetrahydroxydiphenyl methane （1）, 3-bormo-4,5-bis（2,3-dibromo-4,5-dihydroxybenzyl） pyrocatechol （2）, bis（2,3-dibromo-4,5-dihydroxybenzyl） ether （3） and 2,2＇,3-tribromo-3＇,4,4＇,5-tetrahydroxy-6＇-ethyloxymethyldiphenylmethane （4） showed significant inhibitory activity against PTPIB （IC50 were 2.4, 1.7, 1.5 and 0.84 μmol/L, respectively） as potential therapeutical agents for the treatment of type 2 diabetes mellitus. The anti-hyperglycemic effects of the ethanol extracts from If. confervoides on streptozotocin-induced diabetes （STZ-diabetes） in male Wistsr rats fed with high fat diet were investigated. The STZ-diabetic rats treated with medium-dose and high-dose alga extracts showed remarkable reductions in fasting blood glucose （FBG） as compared with the STZ-diabetic control. The results indicate that the in vivo anti-hyperglycemic activity of the R. confervoides extracts can be partially attributed to the inhibitory actions against PTPIB of the bromophenol derivatives and that may be of clinical Importance in improving the management of type 2 diabetes mellitus.     

Studies on the interaction of DNA and Ru (1,10-phenanthroline)2− (dipyrido[3,2−a:2′,3′−c]phenazine)2+

The interaction of Ru(phen)₂(dppz)²⁺(phen=1,10-phenanthroline,dppz=dipyrido[3,2−1:2′,3′−c]phenazine) and the calfthymus DNA were studied with fluorescence and ultraviolet visible absorption spectroscopy. The ultraviolet visible absorption spectrum of Ru(phen)₂(dppz)²⁺ calfthymus DNA, and their interaction demonstrated that Ru(phen)₂(dppz)²⁺ intercalated into the double helix of DNA via the ligand dppz. Fe(CN)₆ ⁴⁻ and NaCl can not quench the fluorescence of Ru(phen)₂(dppz)²⁺-DNA, which was in agreement with the intercalation mode. Foundation item: Supported by National Natural Science Foundation of China Biography: LING Lian-sheng (1972-), male, PhD, candidate.     

Preparation of (R)- and (S)-2-Allyl-1, 3, 2-dinaphtho (α, β) [d.f] dioxaborepin and their reactions with aldehydes

(R)- and(S)-2-Allyl-1,3,2-dinaphtho (α,β) [d.f] dioxaborepin ((R)-2 and(S)-2) have been first prepared by the reaction of(R)-(+)- or(S)-(−)-1, 1′-bi-2-naphthol and triallylborane in THF at room temperature, respectively.(S)-2 and(R)-2 are sensitive to moisture and oxygen in air and disproportionate easily to triallylborane and 1,1′-bi-2 naphthyl bis (1,1′-bi-2-naphtholborate) at ambient temperature. However, THF is a stabilizer for them. The reactions of(R)-2 or(S)-2 and some aliphetic or aromatic aldehydes in CH₂Cl₂ at −78°C for several hours afforded β-alkylenyl alcohols in up to 84.8%ee. Among them, optically active 1-(3, 5-dichlorophenyl)-3-butenol and 1-(2-methoxyphenyl)-3-butenol were first prepared Foundation item: Supported by the National Natural Science Foundation of China (29972033) Biography: Liu Dejun (1973), male, Ph. D, research direction: asymmetric synthesis     

Synthesis of Novel Covalent-linked Linear Porphyrin-Thiophene Copolymers

0　IntroductionTheconstructionofmacro molecularsystemcontainingmul tipleredoxcentersorphotosensitizersisanimportantsub jectinthedesignofmolecularelectronicdevices[1 ,2 ] .Forsuchobjectives,systematizationofdonor (redoxcenter) acceptortriadmoleculesintolargemolecularsystemsisoneofthemostfeasibleapproaches,becausetheexquisiteincorporationofthephotosensi tizersandsuitableelectrondonorsand /oracceptorsintoapoly mericchainisusefulforvariousmolecularsystembasedonphoto inducedelectrontransfer[3 ,4] …     

[2＋2]和[1＋1]型Schiff碱大环化合物的合成及表征

本文以2,2-二[5’-（2’-甲酰呋喃基）]丙烷（1）分别与N,N＇-（2．胺基苯基）-2,6-二甲酰亚胺吡啶（2）和N,N＇-（3-胺基苯基）-2,6-二甲酰亚胺吡啶（3）进行缩合,得到[2＋2]型Schiff碱大环化合物L＋-1和[1＋1]型Schiff碱大环化合物L2,并采用元素分析、1HNMR、IR和质谱手段对Schiff碱大环化合物L1和L2进行了表征。     

Studies on the synthesis and electron spectra of 2,6-bis (<Emphasis Type="Italic">p</Emphasis>-Aminophenyl) benzo [1,2-d; 5,4-d']bisoxazole

A novel method to synthesize 2,6-bis(p-aminophenyl)benzo[1,2-d;5,4-d′]bisoxazole using 1,2,3-trichlorobenzene as the starting material through nitration, substitution, hydrogenation, and condensation was reported. During the condensation, the influence of the amount of SnCl₂ on the yield of the product was studied. The electron spectra of the compound were discussed, the results showed that it is a fluorescence material with large Stokes shift. Foundation item: Supported by the High Technology Research and Development Program of China (2002AA305109) Biography: Chen Xiang qun (1969), female, Ph. D candidate, research direction: organic and polymer materials.