应用于纳米制造的新型电子束抗蚀剂Calixarene的工艺研究

为了满足电子束光刻(EBL)对高分辨率、性能优秀抗蚀剂的需求,研究了将Calixarene衍生物作为电子束抗蚀剂在胶液配制、电子束曝光及显影等工艺过程中的相关技术.其中电子束曝光实验在JEOL JBX-5000LS系统上进行.实验结果表明,在入射电子能量50 keV、束流50 pA的条件下,Calixarene可以方便地形成50 nm的单线、50nm等线宽与间距的图形结构.通过与常用电子束抗蚀剂的对比,总结了Calixarene在电子束光刻性能上的优缺点,并分析了其成因.作为一种新型的高分辨率电子束光刻抗蚀剂,Calixarene有望应用在纳米结构制造、纳米尺寸器件及电路的研制等领域.

High extraction ability of 1,3-dialkynyl calixarene towards mercury(Ⅱ) ion

The reaction of 1,3-dipropyn-2-yloxycalix[4]arene with mercury（U） acetate could give mercury-containing alkynyl calixarene polymer. The extraction behavior of 1,3-dipropyn-2-yl-oxycalix[4]arene towards mercury（Ⅱ） ion was examined. When the mole ratio of Hg^2＋/calixarene was 1：1, the extractive percent can reach to 99.1%, and the extraction capacity was up to 431 mg/g. It could also decrease the Hg^2＋ concentration from 5 to 0.85 mg/L, which was only 17% of the national standard of effluent and satisfied the national standard of drinking water. The extraction process included chemical reaction.

RING-OPENING POLYMERIZATION OF TRIMETHYLENE CARBONATE CATALYZED BY NOVEL SINGLE COMPONENT RARE EARTH CALIXARENE COMPLEXES

In this paper,ring-opening polymerization of trimethylene carbonate(TMC)with rare earth(Nd,Y,La)ρ-tert- butylcalix[n]arene(n=4,6,and 8)complexes as catalysts has been studied.Poly(trimethylene carbonate)(PTMC)with M_v of 21,400 was produced by bulk polymerization under the conditions as follows:[TMC]_0/[Nd](molar ratio)=1000,80℃, 8 h.Mechanism study reveals that the polymerization proceeds via a coordination mechanism.

CATALYTIC ACTIVITIES OF RARE-EARTH CALIXARENE COMPLEXES IN POLYMER SYNTHESES

The studies of our group on the catalytic activities of rare earth calixarene complexes in polymer syntheses are reviewed. Rare earth calixarene complexes are effect catalysts for the polymerizations of butadiene, isoprene, ethylene, styrene, propylene oxide, styrene oxide, trimethylene carbonate and 2,2-dimethyl-trimethylene carbonate.

A New Type of Dibenzoyl Tartaric Acid Selective Electrode Based on Polymer Membrane Containing Calixarene Ionophore

A new type of di benzoyl tartaric acid selective electr ode has been developed. Three double\| arm calixarene derivatives were emp loyed as the neutral ionophores. The poly(vinyl chloride) membrane electrode containing an amide derivative of ca lixarene as the neutral carrier an d a dibutyl phthalate as the plastici zer exhibited the highest sensitivity for dibenzoyl tartaric acid. The slop e of linear portion was 27.8 mV per c oncertration decade. The electrode has a fast response and a long lifetime .

COVALENTLY ATTACHED MULTILAYER ULTRA-THIN FILMS FROM DIAZORESIN AND CALIXARENES

A kind of photosensitive ultra-thin film was fabricated from diazoresin (DR) and various calixarenes by using theself-assembly technique. Under UV irradiation both the ionic- and hydrogen bonds between the layers of the film will convert into covalent bonds. As a result, the stability of the film toward polar solvents increases dramatically.

Synthesis of Two Blue-light emitting Complexes with Schiff Base Calixarene as the Ligand

Two new blue luminescent zinc and beryllium complexes with Schiff base calixarene derivative as the ligand were prepared. Their luminescent properties were determined, which indicated that they had strong blue fluorescent properties. They also had good solubility and film formation. These new complexes can be used as blue organic electroluminescent materials (OELMs) in organic electroluminescent devices.

Hydrothermal Synthesis of [ Mn_5(H_2PO_4)_2(PO_4)_2(H_2O)_4]Templated by Calixarene Under Mild Conditions

The title compound [ Mn5 （ H2PO4 ）2 （ PO4 ）2 （ H20）4 ] was hydrothermally synthesized in the presence of calix[4]arene-p-tetrasulfonate. The title compound was structurally characterized by X-ray single crystal diffraction. It crystallizes in the monoclinic space group C2/c with α = 1.762 9（4） nm, b = 0.913 44（18） nm, c=0.94977（19） nm, β=96.52（3）°, V=1.5195（5） nm^3, Z=4 and R1=0.0283, and exhibits a three-dimensional framework and channel structure. It was proposed that calixarene can act as template during the formation of the title compound because calixarene can bind Mn^2＋ through second-sphere coordination.

New Chiral Calixarene Derivatives: Syntheses and Their Chiral Recognition Toward Amino Acids by UV-Vis Spectroscopy

Three novel types of chiral calixarene derivatives 5, 8, and 10 were designed and synthesized by introducing chiral units to parent calixarenes. Their chiralities were confirmed by rotational analysis. Chiral recognition properties of these host compounds towards L- and D-threonine were studied by UV-Vis spectroscopy. The results indicated that calixarene derivatives 5 and 8 exhibited good chiral recognition capabilities toward L- or D-threonine. Although calixarene derivative 10 had no evident chiral recognition ability, the supramolecules of calixarene derivative 10 with L- or D-threonine showed a hypochromic effect or hyperchromic effect respectively. Therefore, calixarene derivative 10 might serve as a good chiral UV-indicator.

The Synthesis of a New Type of Calixarene with Chiral Pendant

Two new chiral calixarenes were synthesized by condensing 1,3 bis chlorocarbomethyl calixarenes with (1S, 2S) 2 amino 1 (4 nitrophenyl) 1,3 propanediol, a by product from antibiotic industry , and were characterized by 1H NMR , MS FAB, and elemental analysis. The 1H NMR spectra show that those molecules assume a cone conformation in solution.

STUDIES ON CALIXARENES I THE CNDO／2 CALCULATION OF EQUILIBRIUM MOLECULAR GEOMETRY OF CALIX［4］ARENE I

The equilibrium molecular geometry of 25, 26, 27. 28-tetrahydroxycalix[4]arene in cone cowtrmation was calculated by a CNDO/2 method based on the standard geometrical models. The results are in good agreement with those obtained from X-ray analysis.

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

A new bridging reagent, N,N ′\|bis(chloroacetyl)propylenediamine was used to explore the relative activity and bridging pattern of p \|tert\|buty lcalix\arene, p \|tert\|buty lcalix\arene and butylcalix\arene. It was found that the bridging reaction is selectively, at least, preferably at 1,3\|position for p \|tert\|butylcalix\arene and p \|tert\|b utylcalix\arene, 1,5\|position for p \|tert \|butylcalix\arene. Taking the yield of bridged calixarene as a comparsion standard, the activity decreases with the increasing of the number of phenolic units in calixarene.

Study on the Surface Acoustic Wave Sensor with Self-Assembly Imprinted Film of Calixarene Derivatives to Detect Organophosphorus Compounds

The molecularly imprinted technology and the self-assembly technique were used together on the calixarene surface acoustic wave (SAW) chemical sensors to detect organophosphorus compounds. 25-(thioalkyl-alkoxy)-p-tertbutylcalix[4] arene with self-assembled monolayer character was the sensitive coating of the sensors. The sensors had a special response to organophosphorus compounds and the response frequency shift of this sensor to organophosphorus compounds in 0.1 mg/m3 was 350 Hz. The response frequency increased linearly with the increase of the concentration of DMMP in the range from 0.1 to 0.6 mg/m3. The possible explanation of the interaction between the coatings and organophosphorus compounds was discussed.

NOVEL WATER SOLUBLE HOST MOLECULE DERIVED FROM CALIXARENE

Reaction of p-t-butylcalix[6]arene with ethylene oxide gives a water soluble host compound with a hydrophobic cavity and it can include organic molecules and ions in aqueous solution.

Azocalixarenes: a scaffold of universal excipients with high efficiency

Excipients are important components of pharmaceutical preparations that affect their quality, safety, and efficacy. Macrocyclic receptors are a family of supramolecular excipients with several advantages, including molecular-level protection, small sizes,fast kinetics of host-guest recognition, and modular construction. With the continuous advances in the medical field, personalized and precision medicine requires the development of excipients with low dosages, integrated modifying effects, universality,and controlled release. To meet these requirements, we have developed a new family of macrocyclic excipients based on calixarenes by integrating their covalent(broad chemical design space) and noncovalent(wide range of substrates) advantages.Accordingly, azocalixarenes(Azo CAs) were designed, showing high binding affinities to a broad spectrum of active pharmaceutical ingredients(APIs), selectivity to interferents, and responsiveness to hypoxic microenvironments. Due to their highly efficient and controllable recognition, Azo CAs serve as low-dose excipients for 30 APIs. Molecular encapsulation by Azo CAs results in the integrated modification of the physicochemical properties of APIs, including solubility, stability, bioavailability,and biocompatibility. Moreover, Azo CAs can be reduced by azoreductases overexpressed in hypoxic microenvironments,leading to the controlled release of APIs. Collectively, Azo CA excipients have broad application prospects for a series of diseases such as enteritis, arthritis, stroke, cancer, bacterial infection and kidney injury, with diverse therapeutic modalities,including chemotherapy, photodynamic therapy, photothermal therapy, immunotherapy, boron neutron capture therapy, radiotherapy, fluorescence imaging, and their combinations.

Nucleotide Recognition by a Guanidinocalixarene Receptor in Aqueous Solution

Nucleotides participate in various physiological processes through their supramolecular interactions with biomolecules.Therefore,the molecular recognition of nucleotides became an important topic in supramolecular chemistry and exhibited many biomedical applications.Guanidinocalixarenes showed very strong binding affinities towards nucleotides,even reaching the nanomolar level.In this work,we systematically determined the binding constants between a typical guanidinocalixarene(guanidinium-modified calix[5]arene,GC5A)and various nucleotides and revealed the driving forces behind the molecular recognition using theoretical calculations.The electrostatic interactions and hydrogen bonding provided by the phosphate groups of the nucleotides dominated the binding between the nucleotides and GC5A.The lower rim alkyl chains and the skeleton of GC5A provide preorganized cavity and upper guanidinium groups.The difference in the type of nucleobase is also attributed to the different binding affinities.This work provides insight into the molecular recognition of nucleotides and facilitates the development of new supramolecular hosts for nucleotides and related biological applications.

Calixarenes enabling well-adjusted organic-inorganic interface for inverted organic solar cells with 18.25%efficiency and multifold improved photostability under max power point tracking

Compared with organic solar cells(OSCs) adopting conventional architecture,inverted OSCs have offered generally better stability,where Zn O is the most widely used electron transporting layer(ETL) material.For ZnO-based inverted OSCs,a welltuned interface of organic(active layer)-inorganic(Zn O film) with matched surface energy(γS) is critical for both high performance and high stability.In this work,two typical calixarenes,C4A and Bu C4A,were employed as the tuning agents to adjust this organic-inorganic interface for ZnO-based inverted OSCs.As a result,with PM6:L8-BO as the active layer,significantly promoted power conversion efficiencies(PCEs) from 17.14%(for ZnO) to 18.25%(for ZnO/C4A) and 17.80%(for ZnO/Bu C4A) were achieved.Photodynamic studies indicate that the enhanced performance is due to the faster charge extraction process,the suppressed recombination and more ideal internal electric field in ZnO/calixarene-based devices.In addition,wellmatched interface energy and more ordered molecular aggregation in active layer effectively improved photostability and thermal stability for ZnO/calixarene-based devices.These results indicate that calixarenes could act as effective modifying agents of ZnO to improve inverted OSCs’ performance and stability simultaneously,and likely also stimulate calixarenes’ and other macromolecules’ broader studies in other organic electronic devices.

Upper Rim Diester-bridged Calixarenes and Oligocalix-arenes: the Effects of the Length of Bridged Reagents on Their Distribution

A series of monobridged calixarenes 3a-f, cyclic biscalix arenes 4a-f, diametrically bridged at the upper rim with saturated aliphatic diester chains, have been synthesized. The results at dilute conditions show that the percentage of yields of mono , bis and oligo calixarenes are related to the length of the chains. With the shortening of the chains, the percentage of monocalixarenes decreased. All the calixarene moieties are in a cone conformation according to the AB quartet pattern of the methylene protons between the phenolic rings in the 1H NMR spectra.

Natural Silicate as a Solid Support for the Calix[4]Thiophosphorus Derivative for Removal Mercury (II), as Picrate from Water

Currently a technique widely used for gold extraction is mercury by amalgamation technique, the tailing produced pollutes water of all kinds, so it is necessary to develop a form of selective mitigation, for which it is necessary to use complexing agents based on calixarene functionalized with mercury sequestering agents. These are immobilized by adding supports based on natural silica to form polymers and make them insoluble in all types of solvents, so that they can be used as an extractor and at the same time regenerate to their original properties for continuous reuse.

Calixarene-integrated nano-drug delivery system for tumortargeted delivery and tracking of anti-cancer drugsin vivo

Nano-drug delivery systems(nanoDDS)have been extensively investigated clinically to improve the therapeutic effect of anticancer drugs.However,the complicated synthesis during the preparation as well as the potential drug leakage during transportation has greatly limited their general application.In this work,a calixarene-integrated nanoDDS(CanD)that achieves tumor-targeted delivery and tracking of anti-cancer drugs in vivo is presented.The hypoxia-responsive calixarene(SAC4A)exhibits high binding affinity to a series of anti-cancer drugs and rhodamine B(RhB)under normoxic condition while decreasing the binding affinity under hypoxic condition,which leads to the drug release and fluorescence recovery simultaneously.Furthermore,the hypoxia-responsiveness of SAC4A conveys CanD with tumor-targeting ability,resulting in the enrichment of the drug in tumors and enhancement in tumor suppression in mice.Moreover,CanD could become a general platform allowing the delivery of a wide scope of anti-cancer drugs that have strong host-guest interaction with SAC4A.