Synthesis,Crystal Structure and Characterization of a New Hydrogen-bonded Organic Framework

The hydrogen-bonded organic framework(PFC-32), constructed by tetrahydroxyquinone(THQN)and diethylamine(DEA), was readily prepared via hydrothermal synthesis in DEF(N,N-diethylformamide).PFC-32 was characterized by PXRD, IR, UV-Vis, TGA and photoluminescence(PL). Single crystal analysis reveals that PFC-32 shows a three-dimensional(3 D) framework, where the THQN anions are coplanar and separated by DEA cations. PFC-32 displays intrinsic photoluminescence property owing to the alleviation of the aggregation-caused quenching(ACQ) effect caused by π-π stacking.     

DEA与SDS/n-C5H11OH/H2O微乳液的相互作用

以循环伏安法研究了N,N-二乙基苯胺（DEA）与十二烷基硫酸钠（SDS）/正戊醇（n-C5H11OH）/H2O体系O/W和W/O结构微乳液的相互作用.结果表明,DEA在SDS/n-C5H11OH/H2O体系微乳液中有两种定位方式:其一,DEA分子在微乳液液滴膜相中定位于表面活性剂和助表面活性剂的极性基团附近;其二,DEA分子在微乳液液滴膜相中定位于表面活性剂疏水基团一侧.两种定位的分布与微乳液的结构和组成相关.     

A general solution for the 2-pyridyl problem

Problem solved: an air-stable 2-pyridyl borane that can effectively couple to a wide range of aryl and heteroaryl halides and pseudohalides has evaded the synthesis community for decades. The discovery that Cu(DEA)(2) powerfully enables palladium-mediated cross-couplings with air-stable boronates 1 has finally provided a general solution to this problem. DEA=diethanolamine, DMF=N,N'-dimethylformamide, Tf=trifluoromethanesulfonyl.     

Diethylamine and triethylamine as sources of the dienophile component in the reverse azadiene synthesis with dimethylpyrimido[4,5-e]- and-[5,4-e]-1,2,4-triazinediones and 1,2,4,5-tetrazines

Diethylamine (DEA) and triethylamine (TEA) can function as sources for the two-carbon component in the reverse azadiene synthesis. Reaction of 5,7-dimethylpyrimido[4,5-e]-1,2,4-triazine-6,8-dione, 6,8-dimethylpyrimido-[5,4-e]-1,2,4-triazine-5,7-dione, or 1,2,4,5-tetrazine with an excess of DEA or TEA gives, respectively, the pyrido[2,3-d]pyrimidine-2,4-dione,pyrido[3,2-d]pyrimidine-2,4-dione, or pyridazine. The presence of an oxidant (atmospheric oxygen, MnO₂, or an electron-acceptor solvent) is required for the reaction to occur. Reaction of 5,7-dimethylpyrimido[4,5-e]-1,2,4-triazinedione with piperidine, morpholine, or under certain conditions DEA, results in opening of the triazine ring to give uracils with an amidine group in the 6-position.For preliminary communication, see [1, 2].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1545–1558, November, 1990.     

亲水性有机硅杂化防雾涂料的制备及性能

采用Sol-Gel技术制备了二乙醇胺/有机硅杂化涂料, 并用FTIR、UV-Vis、AFM、TGA及接触角等测试技术对涂料及其涂层进行了分析表征. 结果表明, 该杂化涂料具有良好的成膜性. 由于膜层中存在大量的亲水性羟基基团, 使膜层具有良好的亲水性能和防雾效果. 固化后的聚合物膜层中无机相形成了三维交联网络, 赋予了膜层优异的耐磨性和热稳定性.     

TS-1/H2O2体系催化二乙胺氧化竞争反应

系统研究了TS-1/H2O2催化二乙胺(DEA)氧化制备二乙基羟胺(DEHA)的反应规律,考察了DEA氧化及DEHA氧化反应之间的竞争关系.结果表明,H2O2以连续方式进料时,DEA转化率及H2O2有效利用率明显提高,而反应体系中DEA/H2O2的摩尔比对DEHA选择性的影响较大.TS-1既可催化DEA的氧化,又可催化...     

Fluorescence Quenching of Anthracene by N,N-Diethylaniline and Phenothiazine in CTAB/n-C5H11OH/H2O Microemulsion

Photoinduced electron transfer reactions of anthracene with N,N-diethylaniline (DEA) and phenothiazine (PTZ) occurred in the membrane phase of the CTAB (hexadecyltrimethylammonium bromide)/n-C₅H₁₁OH (1-pentanol)/H₂O micro-emulsion. DEA and PTZ exist in the membrane phase of the microemulsion because the presence of vitamin-C (Vc) can change the quenching constant. The change of the quenching constant for the DEA–anthracene system with the presence of Vc is more obvious than that for the PTZ–anthracene system. Thus, the DEA molecules are much closer to the polar head of the microemulsion than PTZ. Compared with DEA, the distribution of PTZ in the microemulsion tends to follow Poisson statistics.     

Dissociative electron attachment to CH2Cl2, CHCH3Cl2, and C(CH3)2Cl2

We perform theoretical studies of dissociative electron attachment (DEA) for the compounds CH(2-n)(CH(3))(n)Cl(2), n = 0, 1, 2, by combining the finite-element discrete model with the resonance R-matrix theory. An unexpectedly low DEA cross section for CH(2)Cl(2) is likely due to the relatively large resonance width for this compound that confirms experimental observations. However, there are some quantitative discrepancies with the experimental results. Since DEA cross sections are very sensitive to the resonance width, a slight adjustment of its value can significantly improve agreement between theory and experiment. Our calculation of the thermal rate coefficients show that there are some inconsistencies between beam and swarm measurements and between different swarm measurements of the rate coefficients for DEA to CH(2)Cl(2). Further experimental and theoretical studies are warranted.     

由苯-1,2,4-三羧酸-1,2-酐和二乙醇胺合成结构非对称超支化聚(酰胺-酯)

通过准发散法和一步法由苯 1 ,2 ,4 三羧酸 1 ,2 酐 (BTAA)和二乙醇胺 (DEA)合成了新型水溶性结构非对称超支化聚 (酰胺 酯 ) .聚合物的端基可通过BTAA与DEA的加料比来调节 .产物结构经FTIR ,1 H NMR和TGA进行了表征 .在一步法中 ,当BTAA于DEA的加料比大于 2 0 4时 ,反应体系不易凝胶 ,当加料比小于 2时 ,体系容易发生交联 .在准发散法中 ,不用中间分离过程 ,采用合成树状大分子发散法相同的加料方式 ,可得到大分子产物     

Simultaneous detection of monoethanolamine, diethanolamine, and triethanolamine by HPLC with a chemiluminescence reaction and online derivatization to tertiary amine.

In this paper we propose a new postcolumn detection method for compounds having primary, secondary, and tertiary amine moieties. The primary and secondary amine are delivatized by a reaction with epichlorohydrin having an epoxy moiety in a reaction coil to yield a tertiary amine with subsequent chemiluminescence detection using [Ru(bpy)3]3+. The liner values of the calibration curves of monoethanolamine (MEA), diethanolamine (DEA) and triethanolamine (TEA) were 0.02 - 1.0 nmol (r2 = 0.9986), 0.02 - 0.5 nmol (r2 = 0.9993) and 0.1 - 1.0 nmol (r2 = 0.9482), respectively. Also, the detection limits (S/N = 3) of MEA, DEA and TEA were 30, 25 and 40 pmol, respectively. The amount of DEA and TEA in shaving cream (60 microg/20 microL) were found to be 0.3 nmol and 14 nmol, respectively, by the proposed method.     

二乙胺导向合成SAPO-34及与其它模板剂的对比

以二乙胺 (DEA) 为模板剂, 合成了 SAPO-34 分子筛, 详细考察了磷酸用量、水用量以及硅源和铝源等因素的影响. 结果表明, 在 0.7 ≤ n(P2O5)/n(Al2O3) ≤ 1.2 及 25 ≤ n(H2O)/n(Al2O3) ≤ 100 范围内, 可以得到纯相 SAPO-34 分子筛, 铝源对所得样品的组成影响较大. 同时, 采用三乙胺 (TEA)、吗啉 (MOR) 以及二乙胺-三乙胺 (DEA-TEA) 混合模板剂合成了 SAPO-34, 通过 X 射线衍射、X 射线荧光分析、扫描电镜、热重和 29Si 固体核磁共振等手段对所得样品进行了表征. 结果显示, 不同模板剂促使硅进入 SAPO-34 骨架的能力顺序为 SAPO-34 (DEA) SAPO-34 (MOR) SAPO-34 (TEA); SAPO-34 骨架中所能容纳的最大 Si(4Al) 含量顺序为 SAPO-34 (DEA) ≈ SAPO-34 (MOR) SAPO-34 (TEA).     

Montmorillonite as an adsorbent for extraction and concentration of atrazine, propazine, deethylatrazine, deisopropylatrazine and hydroxyatrazine

Adsorption properties of the clay mineral montmorillonite in the potassium homoionic form (KMT) was investigated to achieve the extraction and concentration of the herbicides atrazine (AT) and propazine (PROP), as well as the main degradation products of atrazine, namely deethylatrazine (DEA), deisopropylatrazine (DIA) and hydroxyatrazine (ATOH). A batch approach was proposed, with recovery percentages for AT, PROP and DIA higher than 90% at concentrations of 0.50 and 2.50 μg L⁻¹. For DEA and ATOH, however, low recoveries were obtained. For DEA, this fact can be explained by its low K_d with KMT, contrary to ATOH, which interacts strongly with the mineral surface, hindering the complete desorption and hence, generating low recovery percentages. The influence of pH, ionic strength and humic acid was studied, and a comparison with the C₁₈ phase as SPE cartridges was carried out. Montmorillonite showed a similar performance to commercial cartridge for concentrations of AT, DEA and PROP, but better recoveries for DIA was obtained using the clay mineral. For ATOH the recovery was also higher on the clay mineral, although for this compound the most suitable SPE cartridge is constituted by cation exchange resin. After the concentration and elution steps, the 0.50 and 2.50 μg L⁻¹ gave chromatographic peak areas that could be easily quantified with an analytical curve obtained in the concentration range between 7.5 and 100 μg L⁻¹. The obtained concentration factors are suitable to allow the application of the method to the monitoring of triazine residues in drinking water.     

RAFT synthesis of amphiphilic (A‐ran‐B)‐b‐C diblock copolymers with tunable pH‐sensitivity

RAFT homopolymerization of 2‐(diisopropylamino)ethyl methacrylate (DPA) and 2‐(diethylamino)ethyl methacrylate (DEA) and their random copolymerization were investigated. The random copolymers of DPA‐ran‐DEA were synthesized and used as macro‐CTA to prepare poly(DPA‐ran‐DEA)‐b‐poly(N‐(2‐hydroxypropyl) methacrylamide) amphiphilic block copolymers. The ¹H NMR and GPC measurements confirmed the successful synthesis of these copolymers. The potentiometric titration results showed that the pK_b values of these copolymers were in the range of 6.7 ～ 7.7 and linearly varied with the DPA/DEA composition, regardless of the block length of HPMA. The pH‐induced micellization in PBS solution was verified by fluorescence spectroscopy. The dynamic light scattering evaluation showed that the hydrodynamic diameters of these micelles are between 37 ～ 43 nm © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 3740–3748, 2008     

Synthesis of highly isotactic poly(N,N‐diethylacrylamide) by anionic polymerization with grignard reagents and diethylzinc

N,N‐Dimethylacrylamide (DMA) and N,N‐diethylacrylamide (DEA) were polymerized with various Grignard reagents in tetrahydrofuran at −78 °C in the presence of diethylzinc (Et₂Zn). Highly isotactic poly(DEA) was produced in quantitative yield with tert‐butylmagnesium bromide and Et₂Zn, whereas atactic poly(DEA) was generated in the absence of Et₂Zn. No stereospecific polymerization of DMA proceeded with Grignard reagent in the presence of Et₂Zn. The highly isotactic poly(DEA) obtained was soluble in water and showed the characteristic coil–globule transition phenomenon. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 4677–4685, 2000     

Thermoresponsive N,N-dialkylacrylamide copolymer blends as DNA sieving matrices with a thermally tunable mesh size

In an earlier study we showed that a blend of thermoresponsive and nonthermoresponsive hydroxyalkylcelluloses could be used to create a thermally tunable polymer network for double-stranded (ds) DNA separation. Here, we show the generality of this approach using a family of polymers suited to a wider range of DNA separations: a blended mixture of N,N-dialkylacrylamide copolymers with different thermoresponsive behaviors. A mixture of 47% w/w N,N-diethylacrylamide (DEA)/53% w/w N,N-dimethylacrylamide (DMA) (DEA47; thermoresponsive, transition temperature = 55 degrees C in water) and 30% w/w DEA/70% w/w DMA (DEA30; nonthermoresponsive, transition temperature > 85 degrees C in water) copolymers in the ratio of 1:5 w/w DEA47:DEA30 was used to separate a dsDNA restriction digest (PhiX174-HaeIII). We investigated the effects of changing mesh size on dsDNA separation, as controlled by temperature. We observed good DNA separation performance with the copolymer blend at temperatures ranging from 25 degrees C to 48 degrees C. The separation selectivity was evaluated quantitatively for certain DNA fragment pairs as a function of temperature. The results were compared with those obtained with a control matrix consisting only of the nonthermoresponsive DEA30. Different DNA fragment pairs of various sizes show distinct temperature-dependent selectivities. Over the same temperature range, no significant temperature dependence of selectivity is observed for these DNA fragment pairs in the nonthermoresponsive control matrix. Overall, the results show similar trends in the temperature dependency of separation selectivity to what was previously observed in hydroxyalkylcellulose blends, for the same DNA fragment pairs. Finally, we showed that a ramped temperature scheme enables improved separation in the blended copolymer matrix for both small and large DNA fragments, simultaneously in a single capillary electrophoresis (CE) run.     

Cu(II) complexes of N,N-diethyl-2-picolinamine N-oxide

Cu(II) complexes have been prepared with N,N-diethyl-2-picolinamine N-oxide (DEA) employing the perchlorate, tetrafluoroborate, nitrate, chloride and bromide salts. A single unique solid was isolated for each Cu(II) salt with the following stoichiometries: Cu(DEA)₂X₂(XClO₄ and BF₄) and Cu(DEA)X₂(XNO₃, Cl and Br). Characterization has been accomplished primarily by IR, electronic and ESR spectral measurements of the solid state complexes. Significant, though not as great as with lighter ligands of the same series, changes occurred when spectral measurements of acetonitrile or nitromethane solutions were attempted. DEA was found to bind to Cu(II) exclusively as a bidentate ligand via the N-oxide oxygen and the amine nitrogen.     

Fluorescence Quenching of Anthracene by N,N-Diethylaniline in the Sodium Dodecyl Sulfate/Benzyl Alcohol/Water System

Photoinduced electron-transfer reaction of anthracene with N,N-diethylaniline (DEA) was studied in the SDS (sodium dodecyl sulfate)/BA (benzyl alcohol)/H₂O system. In an oil/water microemulsion, only the excited anthracene located at the interface can be quenched by DEA. In a water/oil microemulsion, this quenching reaction occurs in the BA continuous phase. Besides being the quencher of the excited anthracene, DEA could also change the system's structure.     

Reaction of iminopropadienones with amines--formation of zwitterionic intermediates, ketenes, and ketenimines

Five aryliminopropadienones 4a- d have been synthesized by flash vacuum thermolysis (FVT) by using two different precursors in each case. These compounds were deposited at 50 K at a pressure of ca. 10(-6) mbar together with three different nucleophiles, namely, trimethylamine (TMA), dimethylamine (DMA), and diethylamine (DEA), in order to study their reactions as neat solids during warm-up by FTIR spectroscopy. The reaction with TMA showed that a zwitterionic species (5 and/or 6) was formed in all the cases. With DMA and DEA, an alpha-oxoketenimine and/or an imidoylketene (7 and 8 or 9 and 10) was formed as the final product. In addition, several bands were observed, which can be assigned to zwitterionic intermediates (11 or 12). Optimized structures and vibrational spectra for all products were calculated at the B3LYP/6-31G(d) level of theory by using the polarizable continuum model (epsilon = 5).     

Phenol, chlorobenzene and chlorophenol isomers: resonant states and dissociative electron attachment

This paper reports a study of resonant dissociative electron attachment (DEA) to the phenol, chlorobenzene, p-, m-, and o-chlorophenol molecules. On the basis of spectroscopic and thermochemical approaches the resonant states of the molecular negative ions (NIs) and the structures of some dissociative decay products are assigned. In the electron energy range up to 3 eV, DEA processes are determined by the two 2[pi*]-shape resonances resulting mainly in formation of [M-H]- and/or Cl- ions. At higher electron energies the energy correlation between peaks in the negative ion effective yield curves and bands of UV spectra allowed identification of the core-excited resonances. The peculiarities of Cl- ion formation and the vibrational fine structure on the effective yield curves of the [M-H]- ions are discussed. The mass spectrometric procedures for measurement of relative cross sections for NI formation are described.