Response surface methodology for the optimization of the ultrasonic-assisted rhamnolipid treatment of oily sludge

This study investigates the recovery of oily sludge using ultrasound-assisted rhamnolipids and uses oil recovery yield as an evaluation index. The Box–Behnken response surface method was employed to investigate the individual and interactive effects of four different operating factors: frequency, dosage, liquid–solid ratio, and stirring speed. The model optimization results showed that the order of degree of influence of these four factors is frequency > liquid–solid ratio > dosage > stirring speed. The mathematical model predicted the highest oil recovery yield as 92.27%, which was highly accurate (in the 95% confidence interval) as from the experimental results, the highest oil recovery yield was 89.95% under optimal reaction conditions (frequency = 25.58 kHz, dosage = 150.45 mg/L, liquid–solid ratio = 4.1:1 mL/g, and stirring speed = 407 rpm). Thus, the deviation from the prediction model was only 2.32%, indicating that this method provides a theoretical basis for the treatment of oily sludge and can be implemented for practical application in Huaidong in the Xinjiang Province.     

高分子负载锰卟啉的合成及其催化烯烃环氧化反应研究

本文用羟基取代四苯基卟啉锰通过醚键与聚苯乙烯树脂键联，合成了一类高分子负载化锰卟啉化合物。经ＥＳＲ、ＩＲ、ＵＶ－ｖｉｓ散射光谱等测定证实其结构。本文同时考察了它们对烯烃环氧化反应的催化活性，结果表明，负载化金属卟啉在催化烯烃环氧化反应中能集均相和多相催化的优点于一体，不仅催化剂稳定性增强，而且易于分离和重复使用。     

Cation-controled formation of N,N′-dialkylimidazolium cadmium-thiocyanate complexes: synthesis and structural characterization

Three new N,N′-dialkylimidazolium salts of cadmium-thiocyanate, [EtMeIm]₂[Cd₂(SCN)₆] (2), [C₆H₄(CH₂ImMe)₂][Cd(SCN)₄] (3), [C₆Me₃(CH₂ImMe)₃][CdBr₃(SCN)](NO₃) (4) have been prepared, and their crystal structures have been determined by X-ray diffraction. Crystal data: 2, monoclinic, C2/c, a=18.349(4) Å, b=7.8667(18) Å, c=21.399(5) Å, β=110.346(4)°, V=2896.1(11) Å³, Z=4, and R1=0.0561; 3, monoclinic, C2/c, a=20.347(7) Å, b=14.029(5) Å, c=9.380(3) Å, β=112.034(6)°, V=2482.1(15) Å³, Z=4, and R1=0.0397; 4, hexagonal, P6₃, a=b=10.7634(8) Å, c=16.0315(17) Å, V=1608.4(2) Å³, Z=2, and R1=0.0569. Compound 2 consists of triply bridged infinite one-dimensional cadmium-thiocyanate chains, and two independent cadmium atoms are octahedrally coordinated in 2N4S and 4N2S geometry, respectively. In 3, the cadmium atom is octahedrally coordinated with two cis N-bonded monodentate NCS⁻ ligands and four bridging SCN⁻ in a S trans to S, and N trans to N coordination fashion, and thus form doubly bridged infinite one-dimensional chains. Whereas 4 is mononuclear, consisting of a discrete [C₆Me₃(CH₂ImMe)₃]³⁺ cation, a nitrate, and [CdBr₃(SCN)]⁻ ion, and each cadmium(II) ion is coordinated to three bromide and one nitrogen atom of SCN⁻ ion. The structures of these compounds are dictated by the imidazolium cations.     

{[Zn2(Bim)3(OH)(H2O)]·(DMF)(H2O)3}∞: A Two Dimensional Coordination Polymer with Layer Silicate‐like Structure

A layer silicate‐like zinc(II) benzimidazolate polymer {[Zn₂(Bim)₃(OH)(H₂O)]·(DMF)(H₂O)₃}_∞ ( 1 ) was synthesized at room temperature and characterized with X‐ray single‐crystallography: Monoclinic, space group C2/m (No.12), a = 10.423(3) Å, b = 17.416(6) Å, c = 16.583(5) Å, β = 92.698(4), V = 3006.8(17) ų.     

Terephthal­aldehyde bis­(thio­semi­carba­zone) bis­(di­methyl­form­amide) solvate

The thio­semicarbazone mol­ecule in C₁₀H₁₂N₆S₂·2C₃H₇NO has symmetry. The thio­semicarbazone moiety and the benzene ring are essentially coplanar, with mean and maximum deviations of 0.03 and 0.11 Å, respectively. The di­methyl­form­amide mol­ecules bridge the thio­semicarbazone moieties, forming two‐dimensional sheets through N—H?O hydrogen bonds.     

Electroluminescent copolymers based on dihexylfluorene and 2‐{2,6‐bis[2‐(4‐diphenylaminophenyl)vinyl]pyran‐4‐ylidene}malononitrile units

A series of statistical copolymers (poly[(9,9‐di‐n‐hexylfluorene)‐co‐2‐{2,6‐bis‐[2‐(4‐diphenylaminophenyl)vinyl]pyran‐4‐ylidene}malononitrile) were synthesized by the Suzuki coupling reaction. The copolymers showed absorption bands at 379 and 483–489 nm, which were attributed to the oligofluorene segments and the segments containing 2‐[2,6‐bis(2‐{4‐[(4‐bromophenyl)phenylamino]phenyl}vinyl)pyran‐4‐ylidene]malononitrile ( 3 ), respectively. The absorption band around 483–489 nm increased with the feed ratio of 3 . The photoluminescence (PL) spectra of the copolymers showed emission bands at 420 and 573–620 nm. As the feed ratio of 3 increased, the PL emission in the longer wavelength region redshifted, and the intensity increased as well. The electroluminescence (EL) spectrum of the copolymers showed a very weak emission at 420 nm. The PL and EL emission colors redshifted dramatically with the increase in the feed ratio of 3 . The highest occupied molecular orbital and lowest unoccupied molecular orbital levels of the model compound (2‐{2,6‐bis[2‐(4‐diphenylaminophenyl)vinyl]pyran‐4‐ylidene}malononitrile) were determined to be ?5.34 and ?3.14 eV, respectively. It was concluded that energy transfer took place from the oligofluorene blocks to the segments containing 3 and that direct charge trapping occurred in the segments containing 3 during the EL operation. The Commission Internationale de l'Eclairage (CIE) chromaticity coordinates of the copolymer (x = 0.63, y = 0.37) containing 10 mol % 3 were very close to those (x = 0.67, y = 0.33) for National Television System Committee (NTSC) red with a maximum photometric power efficiency of 0.27 cd/A. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3729–3737, 2006     

Chemical Transformations of (2,3,9,10-Tetramethyl-1,4,5,7,8,11,12,14-Octa-Azacyclotetradeca-1,3,8,10-Tetraenato)Cobalt(II)Perchlorate

The monomeric octa-aza bis-α-diimine macrocyclic complex [Co^II(C₁₀H₂₀N₈)(H²O)](ClO₄)₂ I, undergoes various reactions on the macrocyclic ligand. Reaction of complex I with triethylamine in double molar proportions, followed by slow aerial oxidation, produces a molecular dimeric complex [Co^II(C₁₀H₁₄N₈)]₂, III, and a novel Co(I) complex [Co^I(C₁₀H₁₉N₈)], IV. Complex III is a staggered cofacial dimer with a cobalt-cobalt bond length 2.86(1) Å. The macrocyclic ligand of the complex contains an a-diimine function in each five-membered chelate ring, and a three-atom N-C-N^? delocalized system in each six-membered chelate ring. Complex IV has the 5-5-6-6 chelate arrangement because one α-diimine moiety is rearranged to a syn-anti configuration. In the structure, the two fused six-membered chelate rings are fully conjugated and the two fused five-membered rings are saturated. However, when complex I reacts with excess triethylamine under the similar conditions, a dimeric complex of another type, [Co^II(C₁₀H_l6N₈)]₂, II, was generated, in which one N-N bond of the macrocyclic ligand is broken. Complex IV can be isolated also from the reaction of complex I with excess hydrazine, followed by slow aerial oxidation. When hydrazine in double molar proportions was used, complex [Co^I(C₁₀H₁₇N₈)(NHNH)] V, which contains a coordinated diazene ligand, was obtained. Only one six-membered chelate ring of complex V is deprotonated and oxidized to form a three-atom N-C-N^? delocalized system. The structures of octa-aza complexes I-V are determined by X-ray crystallography: I, orthorhombic, C mca, a = 11.646(4), b = 17.049(3), c = 10.706(3) Å, Z = 4, R = 0.045, R_w = 0.047, based on 1024 reflections with I > 2σ(I); II, monoclinic, P 2₁/c, a = 9.814(3), b = 22.583(6). c = 14.632(9) Å, β = 98.90(5)°, Z = 4, R = 0.085, R_w = 0.101, based on 2033 reflections with I > 2σ(I); III, tetragonal, P 4/nmm, a = 15.614(3), c = 6.498(2) Å, Z = 4, R = 0.081, R_w = 0.115, based on 340 reflections with I > 2σ(I); IV, orthorhombic, P bca, a = 8.484(1), b = 16.662(3), c = 18.760(2) Å, Z = 8, R = 0.029, R_w = 0.024, based on 1441 reflections with I > 2σ(I); V, monoclinic, P 2₁/m, a = 7.892(3), b = 11.713(6), c = 9.326(4) Å, β = 108.03(3), Z = 2, R = 0.047, R_w = 0.056, based on 948 reflections with I > 2σ(I).     

Synthesis, Characterization and Biological Activity of Diorganotin（IV） Complexes of N-（3,5-Dibromosalicylidene）-α-amino Acid

The diorganotin（Ⅳ） complexes of N-（3,5-dibromosalicylidene）-α-amino acid, R2Sn（2-O-3,5-Br2C6H2CH= NCHRCOO）（where R=H, Me, i-Pr, Bz; R＇=n-Bu, Cy）, were synthesized by the reactions of diorganotin dichlorides with in situ formed potassium salt of N-（3,5-dibromosalicylidene）-α-amino acid and characterized by elemental analysis, IR and NMR （^1H, ^13C and ^119Sn） spectra. The crystal structures of n-Bu2Sn（2-O-3,5-Br2C6H2CH= NCHRCOO）（R=i-Pr, Bz） and Cy2Sn（2-O-3,5-Br2C6H2CH=NCHRCOO）（R=Me, Bz） were determined by X-ray single crystal diffraction and showed that the tin atoms are in a distorted trigonal bipyramidal geometry to form five- and six-membered chelate rings with the tridentate ligand. Bioassay results indicated that the compounds possess better in vitro antitumour activity against three human tumour cell lines, HeLa, CoLo205 and MCF-7, than cis-platin and moderate anti-bacterial activity against two bacteria, E. coli and S. aureus.     

不对称诱导 Ⅱ.相转移催化下苯甲醛与氯仿、手性胺的反应

用溴化四正丁基铵作为相转移催化剂,苯甲醛、氯仿、α-苯基乙胺(la～c)和固体氢氧化钾在-5～0℃于无水乙腈中反应。反应产物2a～c经水解,氢解得到相应的光学活性苯甘氨酸(4a～c)。由1-苯基-2,2,2-三氯乙醇与1a反应也可制得2a,并对反应机理进行了讨论。     

柱前衍生-高效液相色谱分离测定及质谱鉴定脂肪胺

采用新型荧光衍生试剂2-(2-苯基-1-氢-菲[9,10-d]咪唑)-乙酸(PPIA)进行柱前衍生,经荧光检测实现了脂肪胺的高效液相色谱(HPLC)分离测定及柱后质谱鉴定。60℃下在乙腈溶剂中用N-乙基-N′-[(3-二甲氨基)丙基]碳二亚胺盐酸盐(EDC)做缩合剂,衍生反应15min可获得稳定的荧光产物。脂肪胺衍生物荧光检测波长为380nm(激发波长为260nm)。在EclipseXDB-C8色谱柱上,采用梯度洗脱对12种脂肪胺衍生物进行了优化分离,测定了造纸厂废水、大鼠端脑和酸奶中脂肪胺的含量。经柱后在线质谱大气压化学电离源(APCISource)正离子模式实现了各种脂肪胺衍生物的质谱鉴定,借助对活性中间体的质谱解析确定了衍生反应的反应机理。该方法具有良好的重现性和回收率,多数脂肪胺的线性回归系数大于0.9996;检出限为3.1~18fmol(S/N=3∶1)。