Adsorption of phenolic compounds from aqueous solutions by aminated hypercrosslinked polymers

Two novel polymers （NJ-1 and N J-2） were synthesized by chemically modified a hypercrosslinked polymer NJ-0 with dimethylamine and trimethylamine, respectively. The comparison of the adsorption properties of the three polymers toward phenol, resorcin and phloroglucin was made. The study focused on the static equilibrium adsorption behaviors and the adsorption thermodynamics. Freundlich equation was found to fit the adsorption results well. The effect of amino groups introduced onto the surface of the resin and the structure of phenolic compounds on the adsorption were also studied. The hydrogen-bonding interaction and electrostatic interaction could happen between the amino groups and the adsorbates. The adsorption impetus increased as quantity of hydroxyl groups increased, but the adsorption capacity decreased due to the drop of the matching degree of the aperture of resins and the diameter of adsorbate molecules.

Cluster-based Magnetic Porous Coordination Polymers

The creation of a porous magnet is a long-sought academic goal since magnetism and porosity are hostile to one another. While long-range magnetic ordering needs spin carriers of short separation through short bridges, porosity relies on the use of extended connecting ligands. Here, we will give a survey of the cluster-based magnetic porous coordination polymers, i.e., 0-D MPCPs, according to their functional subunits： （1） nanoporous spin crossover materials with single metal nodes; （2） metal-radical approach with rigid organic radical ligands and single metal nodes; （C） PCPs with rigid organic ligands and metal oligomer nodes; （D） PCPs with metal complex linkers and polymetal cluster nodes; （E） PCPs with organo-polymetal cluster linkers and single metal nodes. The assembly from clusters can provide a reasonable route to resolve the hostility between magnetism and porosity. This assembly’s merits are obvious： the pore benefits from the big cluster according to ＂Scale Chemistry＂, and the functional framework inherits interesting physical properties from the clusters with a large ground spin S.

Syntheses, Structures, and Properties of Five Coordination Polymers Involving Phthalic Acid

Five new coordination polymers Cu（phen）（H2O）（phth）·CH3OH（1）, [Cu（2,2′-bipy）（H2O）]（phth）·3.5H2O（2）, Zn（phen）（phth）（H2O）·1.125H2O（3） and [M（4,4′-bipy）（H2O）2]（phth）·2H2O[M=Zn（4）, Mn（5）]（H2phth=phthalic acid, bipy=bipyridine, phen=1,10-phenanthroline） have been synthesized from the amino acid derivatives（phthalyl-l- valine, H2L） and structurally characterized. H2L was hydrolyzed into phth2- group during the reaction, but the strucure feature was different from that of the complex directly synthesized from H2phth in the reported literature, revealing that H2L played an important role in composing the novel compounds. Compounds 1, 2 and 3 are all 1D chains, but the differences are that compound 1 is further hydrogen-bonded into 2D networks, and compound 2 is further extended into 3D supramolecular network through π-π stacking and hydrogen-bonding interactions. However, compound 3 is a 1D helix chain structure and further links into 2D networks through π-π stacking. Compounds 4 and 5 are isostructural and exhibit the same 2D layers, which are further connected by hydrogen-bonding interactions to form 3D supramolecular network. Antiferromagnetic superexchange was observed for compounds 1, 2 and 5.

Auxiliary Ligands Mediated One- and Two-dimensional Cd(Ⅱ) Coordination Polymers Incorporating Methyl-3- hydroxy-5-carboxy-2-Thiophenecarboxylate Ligand

Two N-donor ligands mediated Cd（Ⅱ） coordination polymers, namely,[Cd（L）（dmpz）2]n （1） and {[Cd（L）（atr）05（H20）]（H2O）}n （2） （H2L = methyl-3-hydroxy-5-carboxy-2-thiophenecarboxylate, dmpz = 3,5-dimethylpyrazole, and atr= 4-amino-l,2,4-triazole）, havebeen produced. Their structures were characterized by single-crystal X-ray diffraction analysis,elemental analyses and infrared spectra. Compound 1 possesses a one-dimensional （1D） chainstructure and is finally extended into a three-dimensional （3D） supramolecular architecturethough hydrogen bonding interactions. Compound 2 features a two-dimensional （2D） networkwith 4-connected sql topology based on dinuclear Cd（Ⅱ） clusters as nodes, which is alsoassembled into a 3D supramolecular architecture through hydrogen bonding interactions.Furthermore, compounds 1 and 2 exhibit high thermal stabilities and intense fluorescent emissionin the solid, and can be explored as potential luminescent materials.

Synthesis of PGMA Microspheres with Amino Groups for High-capacity Adsorption of Cr(VI) by Cerium Initiated Graft Polymerization

Abstract A novel polyglycidylmethacrylate （PGMA） microspheres with high adsorption capacity of Cr（VI） was prepared by cerium（IV） initiated graft polymerization of tentacle-type polymer chains with amino group on polymer microspheres with hydroxyl groups. The micron-sized PGMA microspheres were prepared by a dispersion polym erization method and subsequently modified by ring-opening reaction to introduce functional hydroxyl groups. The polymer microspheres were characterized by scanning electron microscopy （SEM） and Fourier transform infrared spectroscopy （FTIR）. The results indicated that the polymer microspheres had an average diameter of 5 m with uniform size distribution. The free amino group content was determined to be 5.13 mmol·g^-1 for g;PGMA-NH2 microspheres by potentiometric and conductometric titration methods. The Cr（VI） adsorption results indicated that the graft polymerization of tentacle-type polymer chains on the polymer microspheres could produce adsorbents with high adsorption capacity （500 mg-g-l）. The polymer microspheres with grafted tentacle polymer chains have potenial application in large-scale removal of Cr（VI） in aqueous solution.

Poly (N-Isopropyl Acrylamide-<i>Co</i>-Vanillin Acrylate) Dual Responsive Functional Copolymers for Grafting Biomolecules by Schiff’s Base Click Reaction

This article reports on the synthesis of acrylate monomer from renewable material. Vanillin was selected to be the start material to produce new monomer called vanillin acrylate and abbreviated by (VA). It has been successfully investigated by 1H, 13C NMR, IR and UV and all results were in logic state. The next step was to synthetize three different thermo-responsive functional copolymers by incorporation of three different molar ratios of vanillin acrylate (10, 20, 30 mol%) with N-Isopropylacrylamide via free radical polymerization by AIBN as initiator in solution. All copolymers were deduced by 1NMR and IR and all showed the presence of aldehyde group. The copolymer was used for grafting of tryptophan and β-alanine through the chemical link between amino group and the active aldehyde group by click reactions to form Schiff’s base imine compounds. Moreover, polymers were also elucidated by 1HNMR, IR and UV, Size Exclusion Chromatography (SEC) was used for the molecular weight determination, differential scanning calorimeter (DSC) for glass temperature of solid polymers, XRD for crystallinity. UV-vis Spectroscopy was used for the determination of phase separation or the lower critical solution temperature (Tc) of polymers solution not only in deionized water but in pH5 and pH11. The mount of conversation and linked amino acid was determined by UV-vis Spectroscopy.

THE ASYMMETRIC SYNTHESIS OF AMINO ACIDS UNDER POLYMER-SUPPORTED PHASE TRANSFER CATALYTIC CONDITION

The optical alpha-amino acids were synthesized under room temperature by alkylation of N-(diphenyl methylene) glycine t-butyl ester under polymer-supported phase transfer conditions using polymer-supported cinchonine (or quinine) alkaloids as chiral phase transfer catalysts and dichloromethane as solvent, followed by hydrolysis of the above intermediates introduced to the final products-optical alpha-amino acids. This is a new method for the asymmetric synthesis of alpha-amino acids. The influences of catalyst, temperature, substrates, and organic solvents on the chemical yield and optical purities of products were studied.

Two New Iron Coordination Polymers Based on Fe-pyta Chains Incorporating Pyridine-2,4,6-tricarboxylate

Reaction of FeCIz＇6H20, pyridine-2,4,6-tricarboxylic acid（H3pyta） and NaOH in the hydrothermal system at 185 ℃ resulted in the formation of 1D coordination polymer[Fe（Hpyta）（H2O）2]（1） based on Fe-Hpyta chains. When the abpt[abpt=-4-amino-3,5-bis（4-pyridyl）-l,2,4-triazole] ligand was employed in the reaction system, a 3D supramolecular porous network （H2bpt）[Fe（pyta）（H2O）2]·4H2O（2） was obtained. The framework was constructed with negative （Fe-pyta） chains and the positive H3bpt^＋ in situ, formed from the abpt reagent, to form 1D channels filled with guest water molecules via hydrogen-bonds. X-Ray diffraction crystal structure analysis shows that complex 1 crystallized in the monoclinic system, space group C2/c, a=1.1490（5） nm, b=0.9008（4） nm, c=1.0058（5） nm, B=107.254（9）°, V=0.9942（8） nm3, Z=4; and complex 2 crystallizes in the triclinic system, space group P1 with a=0.90392（11） nm, b=0.96027（11 ） nm, c=1.55540（18） nm, a=73.558（2）°,B= 86.126（2）°,r= 68.745（2）°, V=1.2059（2） nm^3 and Z=2.

A Zn(Ⅱ) Coordination Polymer Based on a Flexible Symmetric Multicarboxylate Ligand

A novel coordination polymer, namely [Zn2（CAPA）（DMA）（H2O）]2n·n（H2O）（1,H4CAPA = 5-（bis（4-carboxybenzyl） amino） isophthalic acid, DMA = N,N-dimethylacetamide） has been synthesized through a solvothermal method and characterized by single-crystal X-ray diffraction, elemental analysis, infrared spectra, and thermogravimetric analyses. The crystal structure is of monoclinic, space group P21/n with a = 8.0585（5）, b = 18.9733（10）, c = 20.2044（14） A^°3, β = 101.144（7）°, V = 3030.9（3） ？~3, C56H54Zn4N4O21, Mr = 1378.58, Z = 2）. The compound forms a three-dimensional（3D） supramolecular framework by linking adjacent layers via hydrogen bonds and π···π interactions. It is interesting that the crystal structure is much related to the flexibility and configuration of the ligand. In addition, the thermal stability and luminescence properties for the compound have also been investigated.

The Paramagnetic 2D Chiral-porous Polymer of L-Phenylalanine and Manganese

Mn(L-Phe)2稨2O]n (Phe=phenylalanine) with a single stranded coordination poly- mer has been synthesized by self-assembly of manganese salt and phenylalanine and characterized by X-ray single-crystal diffraction method. The complex crystallizes in the orthorhombic, space group P212121 with a = 6.0911(1), b = 10.3642(1), c = 30.4321(7) ? V = 1921.16(6) ?, Z = 4, Dc = 1.387 g/cm3, C18H22N2O5Mn, Mr = 401.32, F(000) = 836 and m(MoKa) = 0.717 mm-1. The final R = 0.0614 and wR = 0.1412 for 2291 observed reflections with I > 2s(I). The magnetic behavior study shows that there exist super-exchange antiferromagnetic interactions between the magnetic centers through the effective exchange pathway of the carboxylate group.

Synthesis and Crystal Structure of a Cu(Ⅱ) Coordination Polymer: [Cu(L)(1,10-phen)]_n

A new complex [Cu（L）（1,10-phen）]n （1, L = N-3-pyridine sulfonyl amino acid） has been synthesized and characterized by IR, elemental analysis and X-ray diffraction analysis, and its crystal belongs to monoclinic, space group P2Jc with a = 11.481 （2）, b = 1 8.094（4）, c = 8.5198（17） ]°, β= 102.26（3）°, V = 1729.5（6） ,/k3, Z = 4, Dc = 1.759 g/cm3, F（000） = 932, p = 1.422 mm-1, R = 0.0368 and wR = 0.0893. In 1, the Cu（ll） ion adopts a slightly distorted five-coordinated square pyramidal geometry. The L2- ligand adopts O of the carboxyl bridging adjacent Cu（Ⅱ）units to form an infinite chain structure along the c axis. Also, π-π stacking interactions between the adjacent chains expanded the 1-D structures into a 3-D supramolecular structure.

Polymer Supported Synthesis of Multi-substituted Pyrimidine-4-one Derivatives via Pbf-activated Thiourea

Efficient polymer supported synthesis of multi-substituted pyrimidine-4-one derivatives was described. Target products were produced from fluorenylmethoxycarbonyl（Fmoc） protected β-amino acid loaded on hydro- xymethyl resin through deprotection, N-alkylation, guanidine formation, and cleavage of 2,2,4,6,7-pentamethyl dihy-drobenzofuran-sulfonyl（Pbf） by trifluoracetic acid（TFA） followed with cyclization. The procedure has the advantages of easy operation, mild reaction conditions, and forming multiple substituents.

Selective Recognition and Detection of L-Aspartic Acid by Molecularly Imprinted Polymer in Aqueous Solution

Molecularly imprinted polymers selective for L-aspartic acid (LAA) have been prepared using the carboxy-betaine polymer bearing zwitterionic centres along the backbone. LAA is well known to promote good me-tabolism, treat fatigue and depression along with its significance in accurate age estimation in the field of forensic science and is an important constituent of ‘aspartame’, the low calorie sweetener. In order to study the intermolecular interactions in the prepolymerization mixture between the monomer and the template (LAA)/non-template (DAA), a computational approach was developed. It was based on the binding energy of the complex between the template and functional monomer. The results demonstrate that electrostatic in-teractions primarily guide the imprinting protocol. The MIP was able to selectively and specifically take up LAA from aqueous solution, human blood serum and certain pharmaceutical samples quantitatively. Hence, a facile, specific and selective technique to detect the amino acid, LAA in the presence of various interfer-rants, in different kinds of matrices is presented.

Syntheses and Characterization of Two New Alkaline Earth Metal-organic Topological Frameworks with 3-Amino-1H-1,2,4-triazole-5-carboxylate

Two new alkaline earth metal coordination polymers constructed from the deriva-tive of 1,2,4-triazole are presented herein,namely,{[Sr（AmTAZAc）2（H2O）]}（1） and {[Ba（AmTAZAc）2（H2O）]}（2）（AmTAZAc = 3-amino-1H-1,2,4-triazole-5-carboxylate）,which have been synthesized by using the layering method and structurally characterized by elemental analysis,IR,and single-crystal X-ray diffraction.Complexes 1 and 2 are isostructural,and both crystallize in the orthorhombic system,space group Fdd2.X-ray structural analysis shows that 1 or 2 has an intriguing 3-D infinite network of（318.438.510） topology based on a 2-D sheet structure of（4,4） net.The result shows that noncovalent interactions play an important role in strengthening the whole structures of the compounds.

A New Two-dimensional Coordination Polymer Based on Trinuclear Manganese Clusters

A novel two-dimensional Mn（II） coordination polymer, [Mn3（L）R（cis-chdc）fftrans- chdc）]n （L = 2-amino-4-（1H-imidazo[4,5-J][1,10]phenanthrolin-2-yl）phenol and chdc = 1,4-cyclo- hexanedicarboxylate）, has been hydrothermally synthesized and characterized by elemental analysis, IR, TG PL and single-crystal X-ray diffraction. Crystallographic data for this compound： monoclinic space group P2/n with a = 11.0058（13）, b = 9.0179（11）, c = 28.431（3） A, β = 92.850（2）°, V = 2818.3（6） A3, Z = 2, C62Hs6Mn3N10O14, Mr = 1329.99, Dc = 1.567 g/cm3, F（000） = 1370, p（MoKa） = 0.742 mm-1, R = 0.0553 and wR = 0.1421. The chdc carboxylates bridge the Mn（II） atoms to form a trinuclear Mn（lI） cluster. The cis-chdc ligands are held together by the trinuclear Mn（II） clusters to result in a chain structure. Further, the trans-chdc ligands link adjacent chains to furnish a two-dimensional network. The π-π interactions between neighboring layers link the adjacent layers into a three-dimensional supramolecular architecture. Moreover, the N-H...O and O-H...O hydrogen bonds further stabilize the 3D supramolecular architecture.

多氨基协效的偕胺肟基吸附材料制备及其铀吸附性能

海水中的有机物易于与铀酰离子络合成稳定的化合物,从而影响铀吸附材料的吸附性能。本研究使用聚丙烯/聚乙烯无纺布(PP/PESNW)为基材,通过辐射诱导接枝聚合(RIGP)在基材表面引入甲基丙烯酸缩水甘油酯(GMA)单体后,分别与三亚乙基四胺(TETA)、四亚乙基五胺(TEPA)以及五乙烯基六胺(PEHA)进行开环反应引入氨基,与丙烯腈进行加成反应后,再进行胺肟化反应制备出具有多氨基协效官能团的偕胺肟基(AO)吸附材料P-TETA-AO、P-TEPA-AO、P-PEHA-AO。对制得的材料进行了结构表征、吸附性能探究以及吸附机理分析。实验结果表明:成功在基材表面修饰了3种不同链长功能高分子链,制备出目标偕胺肟基吸附材料;3种材料P-TETA-AO、P-TEPA-AO、P-PEHA-AO的铀吸附行为均符合准二级动力学模型以及Langmuir等温吸附模型;24 h内3种材料对铀的吸附容量分别为66.1 mg/g、63.22 mg/g、65.62 mg/g,在pH为5~9范围内表现出良好的吸附性能;5次吸附-解吸实验中材料的铀吸附率仅下降6%,解吸率维持在95%以上,具有良好的可再生性;模拟海水吸附实验中3种材料的铀去除率分别为72.94%、79.97%、87.78%,并且材料吸附性能随着接枝链的增长而上升;XPS结果表明,3种吸附材料在吸附铀的过程中,氨基与偕胺肟基均参与了与铀酰离子的配位,具有协效作用。

芳香性聚氨基酸破乳剂的制备及性能评价

以芳香族氨基酸苯丙氨酸为疏水单体、脂肪族氨基酸天冬氨酸为亲水单体,通过氨基酸N-羧基环内酸酐(NCA)单体的开环聚合(ROP),制备了一系列强极性、高芳香度的聚氨基酸类高分子破乳剂聚苯丙氨酸-聚天冬氨酸苄酯(PPA-b-PBAA),并对产物进行了结构表征和相对分子质量测定。采用瓶试法评价了PPA-b-PBAA的破乳性能,结果表明PPA-b-PBAA具有优秀的低温破乳效率,室温下2 min内能高效分离pH=6.0~11.0、含油量1.0%~10.0%(质量分数)的稀释沥青乳状液。其中,PPA-b-PBAA对1.0%(质量分数)的含油乳化废水的最佳脱水效率达到了99.98%,相应脱出水中残余油含量低至8.50 mg/L。破乳机理研究表明,PPA-b-PBAA加入油水乳状液后能快速迁移到达油水界面,通过与形成油水界面膜的沥青质、胶质相互作用,促使分散油滴絮凝聚并,实现油水分离。量子化学计算和弱相互作用分析表明,破乳剂PPA-b-PBAA分子与形成油水界面膜的主要成分沥青质之间产生的强相互作用有利于加速油水界面膜破裂和分散油滴聚并,是助推PPA-b-PBAA低温高效快速破乳脱水的关键。

Syntheses, Structures and Properties of Four Manganese Coordination Polymers Derived from 4-Amino-3,5- bis（imidazol-1 -ylmethyl）-1,2,4-triazole

The reaction of 4-amino-3,5-bis（imidazol-l-ylmethyl）-1,2,4-triazole （abit） and manganese（Ⅱ） salts yields four coordination polymers {[Mn（abit）3]（C104）z}n （1）, {[Mn（abit）3]（PF6）2},, （2）, [Mn（abit）（dca）2（H2O）2],, （3a） and [Mn（abit）（dca）2（H2O）2]n （3b）. Compounds 1 and 2 are one-dimensional triple-stranded chain. Compounds 3a and 3b are polymorphous and construct one-dimensional single chain. The conformational analysis is performed. The thermal properties have been investigated.

端氨基超支化聚合物及其季铵盐的制备与性能

以丙烯酸甲酯和二亚乙基三胺为原料,通过缩聚反应制备了一种水溶性端氨基超支化聚合物(HBP-NH2);并以2,3-环氧丙基三甲基氯化铵(EPTAC)为改性剂,在水溶液中继续与HBP-NH2反应,制备了端氨基超支化聚合物季铵盐(HBP-HTC)。分别采用红外光谱(FT-IR)、核磁共振(1H-NMR)和凝胶色谱(GPC)分析表征了产物的结构及分子量,同时研究了HBP-NH2和HBP-HTC的溶解性能、抗菌性能、紫外吸收性能及热性能等,为其在纺织加工中的应用提供依据。结果表明,HBP-NH2和HBP-HTC具有良好的抗菌性能和紫外吸收性能,同时在H2O,二甲基亚砜(DMSO),C2H5OH和CH3OH等极性溶剂中具有优异的溶解性能。

高分子硅烷偶联剂改性环氧树脂性能研究

采用侧链氨基硅油(AEAPS)和小分子偶联剂KH-560为原料合成了一系列氨基硅油高分子偶联剂(APCA)并用作双酚A型环氧树脂(EP)/4,4′-二氨基二苯基甲烷(DDM)体系的改性剂,系统研究了改性剂含量等对改性环氧固化物的冲击强度、拉伸强度、断裂伸长率、玻璃化转变温度(Tg)和断裂面形态等的影响。结果表明,APCA能明显提高固化体系的性能,其中环氧树脂经10份APCA-60改性后,与未改性环氧相比,抗冲强度提高了近一倍,断裂伸长率增加了94.55%,拉伸强度也提高了59.55%,而Tg也提高了5℃,达到了明显的增强增韧和提高耐热性等效果。