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.

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.

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.

Nanocrystals for enhancement of oral bioavailability of poorly water-soluble drugs

Nanocrystals,a carrier-free colloidal delivery system in nano-sized range,is an interesting approach for poorly soluble drugs.Nanocrystals provide special features including enhancement of saturation solubility,dissolution velocity and adhesiveness to surface/cell membranes.Several strategies are applied for nanocrystals production including precipitation,milling,high pressure homogenization and combination methods such as Nano-Edge^(TM),SmartCrystal and Precipitation-lyophilization-homogenization(PLH)technology.For oral administration,many publications reported useful advantages of nanocrystals to improve in vivo performances i.e.pharmacokinetics,pharmacodynamics,safety and targeted delivery which were discussed in this review.Additionally,transformation of nanocrystals to final formulations and future trends of nanocrystals were also described.

Application of ion chromatography to the determination of water-soluble inorganic and organic ions in atmospheric aerosols

A simple, sensitive and convenient ion chromatography(IC) method was established for the simultaneous determination of twelve water-soluble inorganic anions(F -, Cl -, NO - 2, NO - 3, SO 2- 3, SO 2- 4, PO 3- 4), and fifteen water-soluble organic ions(formate, acetate, MSA, oxalate, malonate, succinate, phthalates, etc.) in atmospheric aerosols. The linear concentrations ranged from 0.005 μg/m 3 to 500 μg/m 3(r = 0.999—0.9999). The relative standard deviation(RSD) were 0.43%—2.00% and the detection limits were from 2.7 ng/m 3 to 88 ng/m 3. The proposed method was successfully applied to the simultaneous determination of those inorganic ions and organic ions in PM 2.5 of Beijing.

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.

Adverse effects of metal exposure on chemotaxis towards water-soluble attractants regulated mainly by ASE sensory neuron in nematode Caenorhabditis elegans

Chemotaxis to water-soluble attractants is mainly controlled by ASE sensory neuron whose specification is regulated by che-1 in Caenorhabditis elegans. Our data suggested that exposure to high concentrations of metals, such as Pb, Cu, Ag, and Cr, would result in severe defects of chemotaxis to water-soluble attractants of NaCl, cAMP, and biotin. Moreover, the morphology of ASE neuron structures as observed by relative fluorescent intensities and relative size of fluorescent puncta of cell bodies, relative lengths of sensory endings in ASE neurons, and the expression patterns of che-1 were obviously altered in metal exposed animals when they meanwhile exhibited obvious chemotaxis defects to water-soluble attractants. In addition, the dendrite morphology could be noticeably changed in animals exposed to 150 μmol/L of Pb, Cu, and Ag. Furthermore, we observed significant decreases of chemotaxis to water-soluble attractants in Pb exposed che-1 mutant at concentrations more than 2.5 μmol/L, and in Cu, Ag, and Cr exposed che-1 mutant at concentrations more than 50 μmol/L. Therefore, impairment of the ASE neuron structures and functions may largely contribute to the appearance of chemotaxis defects to water-soluble attractants in metal exposed nematodes.

On-line Measurement of Water-Soluble Ions in Ambient Particles

Combining the system of rapid collection of ambient particles and ion chromatography, the system of rapid collection of fine particles and ion chromatography （RCFP-IC） was established to automatically analyze on-line the concentrations of water-soluble ions in ambient particles. Here, the general scheme of RCFP-IC is described and its basic performance is tested. The detection limit of RCFP-IC for SO4^2-, NO3^-, NO2^-, Cl^- and F- is below 0.3μg m^-3. The collection efficiency of RCFP-IC increases rapidly with increasing sized particles. For particles larger than 300 nm, the collection efficiency approaches 100%. The precision of RCFP-IC is more than 90% over 28 repetitions. The response of RCFP-IC is very sensitive and no obvious cross-pollution is found during measurement. A comparison of RCFP-IC with an integrated filter measurement indicates that the measurement of RCFP-IC is comparable in both laboratory experiments and field observations. The results of the field experiment prove that RCFP-IC is an effective on-line monitoring system and is helpful in source apportionment and pollution episode monitoring.

Preparation of Ultrafine Water-soluble Polymers Nanofiber Mats via Electrospinning

A series of water-soluble polymers such as poly（ethylene oxide）（PEO）, polyacrylamide（PAM） and poly（vinyl pyrrilidone）（PVP） was successfully prepared via the electrospinning of their aqueous solutions without the use of a surfactant. The effects of solution properties on the electrospinning of PEO, PAM and PVP solutions were investigated. The viscosity of the solution, charge density carried by the jet, and the surface tension of the solution are the key factors that influence the morphology and diameter size of the fibers. The viscosity of the solution was measured on a modular compact rheometer. The morphology and the diameter size distribution of the fibers were observed under an environmental scanning electron microscope（ESEM）. The results show that the diameters of the nanofibers electro spun from the solutions of these water soluble polymers were uniform and less than 300 nm.

Effect of kaolin on tensile strength and humidity resistance of a water-soluble potassium carbonate sand core

Water soluble cores(WSCs) have been widely applied in manufacture of complex metal components with hollow configurations or internal channels. However, the WSCs without any additons have low tensile strength and low humidity resistance. The purpose of this study is to prepare a water-soluble potassium carbonate sand core with addition of kaolin by the hot-temping method. The effects of kaolin on tensile strength, humidity resistance, fracture mechanism, as well as the gas evolution and collapsibility of WSCs were investigated. Results show that both the crystal morphology and the fracture mechanism of the inorganic salt are changed under the participation of kaolin, contributing to the increase of the tensile strength and the humidity resistance of the core. With the addition of 3wt.% kaolin, the tensile strength could be increased by a factor of 2, reached 1.50 MPa and the hygroscopic rate could be decreased by 14%, achieved 0.559%(after stored for 8 h), respectively. As the addition amount of kaolin increases from 0wt.% to 3wt.%, the main fracture mechanism changes from a adhesive to a cohesive fracture mechanism. The water-soluble potassium carbonate core obtained has the low gas evolution and excellent collapsibility, which makes it suitable for casting low melting metal with complex cavities and crooked channels.

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 .

Phosphoryl choline-grafted water-soluble carbon nanotube

Water-soluble property is the precondition of biomedical evaluation and application of carbon nanotube （CNT）. Novel water- soluble CNT was synthesized in this letter by grafting phosphoryl choline （PC） onto multi-wall CNTs. Utilizing FTIR, XPS, TGA and TEM, the title CNTs were characterized and it was found that the target products could facilely dissolve in water. 2007 Tao Zhang. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights reserved.

Study on Dyeing Performance of Cationic Water-soluble Sulphur Black on Silk

A novel polyquaternaryammonium cationic sulphur black dye was synthesized and its dyeing behavior on silk was studied. The dye exhibited excellent dyeing fixation of up to 98.2 %, as well as excellent dyeing fastness on silk.

Preparation of fructone catalyzed by water-soluble Brφnsted acid ionic liquids

Fructone （2-methyl-2-ethylacetoacetate-1, 3-dioxolane）, a flavouring material, has been synthesized from ethyl acetoacetate and glycol using five water-soluble Brφnsted acid ionic liquids as catalysts for the first time. The used Brφnsted acid ionic liquids include [Hmim]Tfa, [Hmim]Tsa, [Hmim]BF4, [Bmim]HSO4, [Bmim]H2P04, and [Hmim]BF4 showed the highest catalytic activity for the preparation of fructone. After reaction, the product could be isolated from the reaction system automatically, and the ionic liquid could be directly reused without dehydration.

Alginate encapsulated mesoporous silica nanospheres as a sustained drug delivery system for the poorly water-soluble drug indomethacin

We applied a combination of inorganic mesoporous silica material,frequently used as drug carriers,and a natural organic polymer alginate(ALG),to establish a sustained drug delivery system for the poorly water-soluble drug Indomethacin(IND).Mesoporous silica nanospheres(MSNs)were synthesized using an organic template method and then functionalized with aminopropyl groups through postsynthesis.After drug loading into the pores of aninopropyl functionalized MSNs(AP-MSNs),IND loaded AP-MSNs(IND-AP-MSNs)were encapsulated by ALG through the ionic interaction.The effects of surface chemical groups and ALG layer on IND release were systematically studied using scanning electron microscopy(SEM),transmission electron microscopy(TEM),nitrogen adsorption,zetapotential analysis and TGA analysis.The surface structure and surface charge changes of the ALG encapsulated AP-MSNs(ALG-AP-MSNs)were also investigated.The results showed that sustained release of IND from the designed drug delivery system was mainly due to the blockage effect from the coated ALG.We believe that this combination will help designing oral sustained drug delivery systems for poorly water-soluble drugs.

Inquiry of Water-Soluble Polysaccharide Extraction Conditions from Grapefruit Skin

Water-soluble polysaccharide was isolated from grapefruit with the method of water-dissolving and ethanol-precipitating. By single factor test and orthogonal experimental method, the extraction conditions of the water-soluble polysaccharide were investigated, which contained liquid-solid ratio, temperature, time and pH. The results showed that pH was the most important factor of polysaccharide extraction, followed by temperature. The optimized extraction technology conditions were obtained. The liquid-solid ratio was 1:40, temperature was 90?C, time was 2.0 h, and pH was 2. The highest extraction rate of crude polysaccharide was 8.30%.

Synthesis and Cytotoxic Activity of Novel Water-soluble Prodrugs of Combretastatin A-4

Novel water-soluble prodrugs of combretastatin A-4 （5-8） were synthesized and evaluated for their in vitro cytotoxicity against lung carcinoma A549. Compound 5, bearing phosphoryl choline （PC） moiety, showed 90% inhibition at 32 ktg/mL concentration after 24 h. The findings showed the PC derivative would be a promising candidate for the development of new water-soluble prodrug of cytotoxic combretastatin A-4,

Diurnal variations of water-soluble ions in PM_(2.5)in Shanghai

Thirty-six daily time interval PM2.5 samples were collected in different seasonal dates in urban Shanghai, and the concentrations of four anions （Cl- , NO3-, SO4^2-, C2O4^2-） and five cations （NH＋, Na＋, K＋, Ca2＋, Mg2＋） were analyzed with ion chromatography. Sulfate, nitrate and ammonium were found to be the dominant species, accounting for about 80% of the total ions. The daily nitrate to sulfate mass ratio ranged from 0.31 to 0.82, indicating that coal combustion was still the main pollution source in Shanghai. The equivalent ratio of ammonium to stun of nitrate and sulfate showed fixed diurnal variation pattern in all the sampling days with higher values in the nighttime, suggesting that fine particles in the night were more neutralized. The oxalate to sulfate ratio was lower in the winter sampling days than that in hotter summer and autumn sampling days. Oxalate was significantly correlated with sulfate in winter sampling days, but not in the summer and autumn, suggesting that the formation mechanism of oxalate and sulfate was similar in winter, however different in hot days.

Designandconstructionof athree-dimensionalelectrodewith biomass-derived carbon current collector andwater-soluble binder for high-sulfur-loading lithium-sulfur batteries

Lithium-sulfur batteries attract lots of attention due to their high specific capacity,low cost,and environmental friendliness.However,the low sulfur utilization and short cycle life extremely hinder their application.Herein,we design and fabricate a three-dimensional electrode by a simple filtration method to achieve a high-sulfur loading.Biomass porous carbon is employed as a current collector,which not only enhances the electronic transport but also effectively limits the volume expansion of the active material.Meanwhile,an optimized carboxymethyl cellulose binder is chosen.The chemical bonding restricts the shuttle effect,leading to improved electrochemical performance.Under the ultrahigh sulfur load of 28mg/cm2,the high capacity of 18mAh/cm2 is still maintained,and stable cycling performance is obtained.This study demonstrates a viable strategy to develop promising lithium-sulfur batteries with a three-dimensional electrode,which promotes sulfur loading and electrochemical performance.

Phase Transfer Catalyzed Synthesis and Antibacterial Activity of Water-soluble S-Triazolo[3,4-b][1,3,4]thiadiazoles Containing Piperazine Group

6/3-（4-Chlorophenyl）-s-triazolo[3, 4-b][1, 3, 4]thiadiazoles （2,a-e） and （Sa-e） were synthesized respectively by intermolecular cyclization of 5-aryl / 4-chlorophenyl-4-amino-3- mercapto-1, 2, 4-triazoles （la-e） and （4） with 4-chlorobenzoic acid / aryl acids, which were condensed with piperazine under phase transfer catalyst TBAB to yield the corresponding free bases of monopiperazine derivatives and followed to form water-soluble salts （3a-e） and （6a-e） with hydrochloric acid in good yields. The in vitro biological results showed that piperazine group conjugated with the above fused heterocycles played an important role in antibacterial activity. The structures of novel compounds were confirmed by IR, ＇H NMR, MS and elemental analysis.