Studies on Properties of p—Nitrophenylazo Calix[4]arene Derivatives

The p-nitrophenylazo calix[4] arene derivatives la-ld with nonlinear optical(NLO)properties were prepared by the diazo-coupling reaction of calix[4]arene with p-nitrophenyl diazonium.The diazotization reaction of p-nltroaniline was caried out with isoamyl nitrite as a source of nitrous acid in EtONa/EtOH under refluxing conditon.X-Ray crystallographic analysis and ^1H NMR sptectra reveal that they exist as cone conformation in crystal state or in soution.HRS measurements at 1064 nm in THF indicate that p-nitrophenylazo calix[4]arenes have higher hyperpolarizability βz values than the corresponding reference compound 4-(4-nitrophenylazo)-2,6-dimethyl-phenol,without red shift of the charge transfer band.The tetrakis p-nitropheylazo calix[4]arene(2)with longer alkyl chains can form monolayer aht the air/water interface.     

Amplified Electrochemical Immunoassay Using HRP Labeled Protein as an Inhibitor to Silver Deposition in the Presence of H2O2

A novel electrochemical immunosensor with amplification effect based on the enzyme inhibition of silver deposition was proposed. In this method, the capture antibody was first immobilized onto a gold electrode via a self-assembled layer. After a sandwich immunoreaction, HRP labeled antibody was bound to the gold electrode. The HRP on the electrode inhibited silver deposition when the electrode was incubated in hydroquinone-H2O2 solution and silver ion solution. The linear sweep voltammetry was chosen to detect the deposited silver and the result showed that the peak current was linearly proportional to the content of IgG in the range of 50 to 2500 ng/mL with a detection limit of 35 ng/mL.     

Synthesis and Complexation Properties of Novel Chiral Calix[4]-1,3-aza-crown and Calix[4]arene Hydrazone Derivative

<正>Refluxing calix[4]-1,3-substituted benzaldehyde derivative(4) with glycine hydrazide derivative,we obtained a novel calix[4]arene hydrazone derivative(5) via"1+2"condensation in a yield of 78%.In the reaction of compound 4 with L-leucine hydrazide derivative at room temperature,lariat calix[4]-1,3-aza-crown(6) with chiral amino acid group as branched chain was synthesized via"1+1"addition in a yield of 70%.The preliminary extraction experiments suggested that hosting compounds 5 and 6 possessed good complexation abilities forα-amino acids.     

Synthesis and Crystal Structure of a Novel Calix [8] arene Ester Derivative

The synthesis and crystal structure of a novel calix[8] arene ester are reported herein. The calix [8] arene ester derivative has been characterized by IR,NMR and X-ray crystal analysis. The X-ray structure analysis revealed that the 8 phenolic hydroxy groups of the calix [8] arene have been substituted by 4 diethyl dibromomalonate molecules with each two adjacent hydroxy oxygen atoms attached to a bridge diethyl malonate.     

Aminolysis reaction of calix [ 4 ] arene esters and crystal structures and conformational behaviors of calix[4]arene amides

We first make use of aminolysis of calix[4]arene esters to synthesize calix[4]arene amides. When the two ethyl esters of the calix[4]arene esters are aminolysized, the 1, 3-amide derivative is formed selectively. The crystal structures of the calix-[4]arene with two butyl amide (3b) and four butyl amide moieties (4b) were determined. The intermolecular hydrogen bonds make 4b form two-dimensional net work insolid state. The 1H NMR spectra prove that 3b is of a pinched cone conformation, while 4b and tetraheptylamide-calix[4]arene (6b) take fast interconversion between two C2v isomers in solution and appear an apparent cone conformation at room temperature. As decreasing temperature, the interconversion rate decreases gradually and, finally, the interconversion process is frozen at Tc = -10℃, which makes both conformations of 4b and 6b the pinched cone structures. The hydrogen bond improves the interconversion barrier, and the large different values of the potential barrier between 6b and 4b (or 6b) may     

Controlled solvothermal synthesis of PbS quasi-nanorods by calix[4]arene

A new idea of the nanorods preparation and a novel application of calixarenes are presented. Calix[4]arene was introduced into solvothermal system to produce one-dimensional inorganic nanomaterial. The obtained product was characterized by XRD and TEM. Results of the XRD analysis showed that the product was pure cubic phase of PbS with high crystallinity. TEM images revealed that the diameter and length of the PbS nanorods were about 200 nm and up to 3.5 μm, respectively. Optical properties of the product were also studied. PL emission image showed that the product exhibited an emission peak at 308 nm in ultraviolet region showing a blue shift of 14 nm compared to the bulk material. The formation mechanism of PbS nanorods in the presence of calix[4]arene is discussed.     

银纳米颗粒的合成及用于抗癌药氟他胺的电化学检测（英文）

Ag nanoparticles were synthesized on the surface of a glassy carbon electrode modified with p‐tert‐butylcalix[4]arene and p‐tert‐butylcalix[6]arene by the deposition of Ag+ at an open circuit potential followed by the electrochemical reduction of the Ag+.The presence of the calixarene layer on the electrode surface controlled the particle size and prevented agglomeration.Cyclic voltam‐metry showed that the Ag nanoparticles on the modified glassy carbon electrode had good catalytic ability for the reduction of flutamide.The effects of calixarene concentration,potential applied for the reduction of Ag+,number of calixarene layers,and p H value on the electrocatalytic activity of the Ag nanoparticles were investigated.The modified electrode had a linear range in differential pulse voltammetry of 10-1000 μmol/L with a detection limit of 9.33 μmol/L for flutamide at an S/N = 3.The method was applied to the detection of flutamide in practical samples.     

Synthesis and nitration of calix[4] (aza)crowns

Calix[4] (aza) crowns containing amide groups 3a-d were synthesized by the reactions of calix[4]arene (1a) or p-tert-butylcalix[4]arene (1b) with N, N'-ethylenebis(2-chloroac-etamide) (2a) or N, N'-1,2-phenylenebis(2-chloroacetamide) (2b) by one step procedure in yields of 85-90% . Calix[4]-(aza) crowns 4a-b could be obtained by the reduction of 3a-b with LiAlH4 in yields of 51 and 67% , respectively. The nitration of 3a or 3c afforded new chromogenic calix[4]arenes 5a bearing two nitrophenol moieties and 5c bearing one nitro-phenol and one quinone moiety, respectively. The ipso-nitrations of 3b and 3d were also studied. Both gave the products containing one nitrophenol and one quinone moiety. Moreover, a very interesting calix[4]arene derivative 5d containing one cyclohexadienone moiety was also separated as the main product when 3d was ipso -nitrated.     

Interaction and Interfacial Molecular Recognition of Calix[4] arene Derivatives Bearing Nucleobases for Complementary Nucleoside

The p-tert-butyl calix[4] arene derivatives la with uracils and 1b with adenines at the lower rim were synthesized.The Interaction between 1a and 1b in CDCl3 solution was demonstrated by ^1H NMR spectra.The interfacial molecular recognitions of la and 1b for the complementary nucleosides in aqueous subphases were investigated by Langmuir-Blodgett technique.     

单氧代-二硒烷基-1, w-二氧取代杯[4]衍生物的合成,结构及萃取性能研究

Novel macrocyclic monooxa-diselkylene-1,ω-dioxy substituted calix[4]arene derivatives 1a-5a were synthesized by the reaction of calix[4]arene dibromides 1-5 with the disodium salt of bis（2-selenylethyl）ether in the yields between 28% and 64%. Their structures were characterized by proton and carbon NMR spectra. X-Ray structure analysis of la further confirmed the cone conformation of compounds 1a-5a. An interesting host-guest complex of la with dichloromethane via CH/π and C1/π interactions was elucidated. Extraction experiments showed that these novel monooxa-diselkylene-1,ω-dioxy substituted calix[4]arene derivatives 1a-5a had strong extraction ability towards mercury ion. The interaction of Hg^2＋with the calix ligand has also been investigated by 1^H NMR titration.     

Synthesis of fully lower‐rim,carbonate‐bridged calix[8]arenes and their curing behavior

Novel fully lower‐rim, carbonate‐bridged calix[8]arene derivatives were successfully synthesized in high yield by the condensation of p‐alkyl substituted calix[8]arenes with triphosgene. Different bases and catalysts were used for the preparation depending on the p‐alkyl substituted groups of the calix[8]arenes. The conformational features of the derivatives were examined by ¹H NMR analysis. Thermosetting formulations were prepared from a mixture of bisphenol A polycarbonate with calix[8]arene carbonate derivatives using sodium benzoate as a catalyst. Their crosslinking behaviors were studied using differential thermal/thermogravimetric analysis. No glass‐transition temperatures were observed after annealing at 280–300 °C. © 2001 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 1149–1155, 2001     

Synthesis of p‐tert‐Butyl‐calix[6] ‐biscrown‐3 via Intramolecular Ring‐closure of 1,4‐Bis (2‐(2‐chloroethoxy) ethoxy) ‐p‐tert‐butyl‐calix[6]arene

With a variation in reaction conditions, 1, 4‐bis (2‐(2‐chloroethoxy)ethoxy)‐calix[6]arene (3) and l,3,5‐tris(2‐(2‐chloroethoxy) ethoxy)‐calix [6] arene (4) or 4 and 4‐chloroethoxyethoxy‐calix[6]crown‐3 (5) were selectively synthesized from p‐tert‐butyl‐calix [6] arene and 2‐(2‐chloroethoxy)ethyltosylate. l,3–4,6‐p‐tert‐butylcalix[6]‐bis‐crown‐3 (6) with (u,u,u,d,d,d) conformation and 1,3–4,5‐p‐tert‐butylcalix[6]‐biscrown‐3 (7) with self‐anchored (u,u, u, u, u, d) conformation were synthesized through an intramolecularly ring‐closing condensation of 1, 4‐bis (2‐(2‐chloroethoxy)ethoxy)‐p‐tert‐butyl‐calix[6]arene (3) in 25% and 15% yield, respectively. Using 5 instead of 3, only 7 was obtained in 65% high yield. 6 and 7 show different complexation properties toward alkali metal and ammonium ions.     

Water‐Soluble Molecular Capsules: Self‐Assembly and Binding Properties

The self‐assembly and characterization of water‐soluble calix[4]arene‐based molecular capsules ( 1?2 ) is reported. The assemblies are the result of ionic interactions between negatively charged calix[4]arenes 1 a and 1 b , functionalized at the upper rim with amino acid moieties, and a positively charged tetraamidiniumcalix[4]arene 2 . The formation of the molecular capsules is studied by ¹H NMR spectroscopy, ESI mass spectrometry (ESI‐MS), and isothermal titration calorimetry (ITC). A molecular docking protocol was used to identify potential guest molecules for the self‐assembled capsule 1 a?2 . Experimental guest encapsulation studies indicate that capsule 1 a?2 is an effective host for both charged (N‐methylquinuclidinium cation) and neutral molecules (6‐amino‐2‐methylquinoline) in water.     

对叔丁基杯[10]冠醚的合成

首次合成一系列杯[10]冠醚。通过将对叔丁基杯[10]芳烃和乙二醇双对甲苯磺酸酯或多甘醇双对甲苯磺酸酯在K2CO3/甲苯或Cs2CO3/丙酮体系中反应,得到一系列杯[10]冠醚:1,2-杯[10]冠-4、1,3-杯[10]冠-2、1,2-,1,3-杯[10]冠-3、1,4-杯[10]冠-4、和1,6-杯[10]冠-4。     

Novel Cesium‐Selective Electrodes Based on Lipophilic 1,3‐Bisbridged Cofacial‐calix[6]crowns

Five bisbridged calix[6]crowns have been investigated as Cs⁺ ionophore in PVC membrane electrodes. As ionophores, three 1,3‐bisbridged calix[6]crown‐4‐ethers( I–III ), 1,3‐bisbridged calix[6]crown‐5‐ether( IV ), and 1,3‐bisbridged calix[6]crown‐6‐ether( V ) have been evaluated. The membranes all give good Nernstian response in the concentration range from 1×10^?7 to 1×10^?1 M of cesium ion. The best detection limits (?log aequation/tex2gif-inf-1.gif=7.08–7.36) are obtained for electrode membranes containing 1,3‐bisbridged cofacial‐calix[6]crown‐4‐ethers( I‐III ), and the values are the lowest compared with those reported previously. The highest selectivity coefficients [ 3.74(Cs/K), 2.63(Cs/Rb)] are obtained for the membrane of 1,3‐bisbridged calix[6]crown‐4‐ether( II ), and these values are also the highest compared with previous reports for Cs⁺‐ISEs. The highest selectivity towards cesium ion is attributed to the geometrically cofacial positions of two crown‐ethers in calix[6]crowns in order to provide the complex of cesium ion and eight oxygens of cofacial crowns.     

Calix[4]arene‐based Bis‐phosphonites,Bis‐phosphites,and Bis‐O‐acyl‐phosphites as Ligands in the Rhodium(I)‐catalyzed Hydroformylation of 1‐Octene

New calix[4]arene‐based bis‐phosphonites, bis‐phosphites and bis‐O‐acylphosphites were synthesized and characterized. Treatment of these P‐ligands with selected rhodium and platinum precursors led to mononuclear complexes that were satisfactorily characterized. The solid state structure of the dirhodium(I) complex 14 has been determined by X‐ray diffraction. The two rhodium centres are bridged by two chloro ligands; one rhodium atom is further coordinated by calix[4]arene phosphorus atoms and the other by cyclooctadiene. The new calix[4]arene P‐ligands were tested in the Rh(I) catalyzed hydroformylation of 1‐octene. All Rh(I) complexes catalyzed the reaction leading to high chemoselectivity with regard to the formation of aldehydes. Yields and n/iso‐selectivities depended on the reaction conditions. Average yields of 80 % and n/iso‐ratios of about 1.3 to 1.5 were observed. High yields of aldehydes can be achieved using the methoxy substituted P‐ligands at low Rh:ligand ratios.     

Linked Supramolecular Building Blocks for Enhanced Cluster Formation

Methylene‐bridged calix[4]arenes have emerged as extremely versatile ligand supports in the formation of new polymetallic clusters possessing fascinating magnetic properties. Metal ion binding rules established for this building block allow one to partially rationalise the complex assembly process. The ability to covalently link calix[4]arenes at the methylene bridge provides significantly improved control over the introduction of different metal centres to resulting cluster motifs. Clusters assembled from bis‐calix[4]arenes and transition metal ions or 3d‐4f combinations display characteristic features of the analogous calix[4]arene supported clusters, thereby demonstrating an enhanced and rational approach towards the targeted synthesis of complex and challenging structures.     

Synthesis and photochemical reaction of cyclic oligomers: Synthesis and photopolymerization of novel C‐methylcalix[4]resorcinarene and p‐alkylcalix[n]arene derivatives containing spiro ortho ether groups

New photoreactive calixarene derivatives containing spiro ortho ester groups (calixarenes 3a–3c ) were synthesized by the reaction of 2‐bromomethyl‐1,4,6‐trioxaspiro[4.4]nonane with 2,8,14,20‐tetramethyl‐4,6,10,12,16,18,22,24‐octakis(carboxymethoxy)calix[4]resorcinarene, 5,11,17,23,29,35‐hexamethyl‐37,38,39,40,41,42‐hexakis(carboxymethoxy)calix[6]arene, and 5,11,17,23,29,35,41,47‐octa‐tert‐butyl‐49,50,51,52, 53,54,55,56‐octakis‐(carboxymethoxy)calix[8]arene, which were prepared by the reaction of C‐methylcalix[4]resorcinarene, p‐methylcalix[6]arene, and p‐tert‐butylcalix[8]arene, respectively. The thermal stability of the obtained calixarene derivatives containing spiro ortho ester groups was examined with thermogravimetric analysis, and it was found that these calixarene derivatives had good thermal stability. The photoinitiated cationic polymerization of spiro ortho ester groups in calixarene derivatives 3a–3c was examined with certain photoacid generators in the film state. Interestingly enough, the reaction of calixarene derivatives did not proceed with only photoirradiation; however, the reaction proceeded smoothly when the photoirradiation was followed by heating. Furthermore, calixarene 3a , composed of a C‐methylcalix[4]resorcinarene structure, showed the highest photochemical reactivity in this reaction system. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 1293–1302, 2002     

Synthesis and Structure of Novel Double Flexible Spacer Bridged Biscalix[4]arenes

25, 25′, 27, 27′‐Bis(1,3‐dioxypropane)‐bis(5, 11, 17, 23‐tetra‐tert‐butylcalix[4]arene‐26,28‐diol) (4) and 25, 25′, 27, 27′‐bis(1, 4‐dioxybutane)‐bis (5, 11, 17, 23‐tetra‐tert‐butylcalix‐[4]arene‐26, 28‐diol) (5) were synthesized by the reaction of p‐tert‐butylcalix[4]arene (1) with preorganized 25, 27‐bis(3‐bromoproxyl)calix[4]arene‐26, 27‐diol (2) and 25, 27‐bis(3‐bromobutoxyl)calix[4]arene‐26, 27‐diol (3) in the presence of K₂CO₃ and KI. Compounds 4 and 5 were characterized with X‐ray analysis and the selectivity of 4 and 5 toward K⁺ over other alkali metal ions, alkaline metal ions as well as NH₄⁺ were investigated with an ion‐selective electrode.