Presentation on theme: "CALIXARENE RECEPTORS FOR RADIOWASTE PARTITION, CHEMOSENSORS, DRUG DESIGN HANNOVER MESSE-2007 16-20 April, 2007 Hannover Iurii MATVIEIEV +38 044 551-1628."— Presentation transcript:
CALIXARENE RECEPTORS FOR RADIOWASTE PARTITION, CHEMOSENSORS, DRUG DESIGN HANNOVER MESSE April, 2007 Hannover Iurii MATVIEIEV National Academy of Sciences of Ukraine Institute of Organic Chemistry Kiev
C.D.Gutsche. Org. Synth., Coll. Vol. 1993, 8, 75 Calixarenes are available macrocycles Upper rim modification Lower rim modification 2
CALIXARENE EXTRACTANTS FOR RADIOWASTE PARTITION CALIXARENE BASED CHEMOSENSORS CALIXARENES FOR DRUG DESIGN
RADIOWASTE PARTITION Problem Description & Market Need Efficient reprocessing of wastes arising from nuclear power remains one of the most complicated problems of radiochemical industry. Long-lived radionuclides, especially actinides, are the most hazardous components of the high level waste (HLW) of nuclear power stations. Their separation from the total waste mass and disposal should enable significantly to raise the ecological safety and efficiency of nuclear fuel cycle. A combined approach to HLW reprocessing, i.e. the recovery of several radionuclide groups immediately in one cycle, seems to be promising.
RADIOWASTE PARTITION RADIOWASTE PARTITION Brief technology description The HLW partitioning problem can be solved by the extraction technology with the use of organophosphorus extractants recovering TRU, technetium and platinides. The widely used extractants like trialkylphosphine oxide possess low efficiency and insufficient selectivity. We propose a new class of perspective extractants on the base of calixarenes functionalized with phosphine oxide, carbamoylphosphine oxide or diphosphine dioxide groups. In such compounds the binding groups may be best located around a metal cation, increasing the extraction efficiency and selectivity to a great extent. Extraction and stripping of radionuclides of the real High Level Waste
RADIOWASTE PARTITION RADIOWASTE PARTITION Extraction of radionuclides (% of initial) by CIP-67 from the Real High Level Waste E1 E2 Real HLW 0,04 M CIP-67 2% n-octanol NBTF Solvent EXTRACT, radionuclides, 100% E3 E4 Am – 47 Cm – 27 Eu – 20 Ce – 70 gross – 28 Eu < 0,1 Ce – 12 gross – 0,14 Extractant CIP-67
RADIOWASTE PARTITION RADIOWASTE PARTITION Advantages Calixarene alkylphosphine oxides, carbamoylphosphine oxides or diphosphine dioxides extract simultaneously actinides, lanthanides, technetium and palladium from real HLW hundred times more efficient than the industrial extractants. In three contacts almoust 100% of gross - activity, more than 98 % of Tc and Pd were recovered from real HLW.
RADIOWASTE PARTITION RADIOWASTE PARTITION Stage of development The Institute of Organic Chemistry of the National Academy of Sciences of Ukraine is enable to product the calixarene extractants in kilo scale quantities The testing of the calixarene extractants has being successfully performed with the real HLW on the MAYAK plant by specialists of the Khlopin Radium Institute (St.-Petersburg, Russia)
RADIOWASTE PARTITION RADIOWASTE PARTITION Opportunities We offer: Calixarene alkylphosphine oxides, carbamoylphosphine oxides or diphosphine dioxides for radiowaste partition (Institute of Organic Chemistry NASU, Kiev, Ukraine the extraction technology with the use of organophosphorus extractants recovering TRU, technetium and platinides (Khlopin Radium Institute, St. Petersburg, Russia www………) Targeted Market Segment Any Atomic Power Station Radiochemical Enterprizes
CALIXARENE BASED CHEMOSENSORS Easy to use Easy to use Flexible in application Flexible in application High sensitivity High sensitivity Multi-purpose Multi-purpose
CHEMOSENSORS CHEMOSENSORS Problem Description & Market Need Calixarene based Electronic Nose was developed for monitoring of organic compounds in environment. Application of traditional methods for monitoring of hazardous substances in variable environment (air, water, waste, etc.) is not often effective and has a range of drawbacks, mainly complicity and long-term exposure. The main problem in developing of sensor systems is to supply them with the exceptional selectivity towards a different analytes.
CHEMOSENSORS CHEMOSENSORS Basic operation principles -Array of quartz crystal resonators are covered with calixarenecontaining receptors which have different sensitivity towards different volatile organic molecules. -Due to adsorption of analyte molecules onto sensitive surfaces of sensors frequency of quartz resonators is reducing. This frequency shift is considered as a sensor response. -Obtained array of sensors responses to pulse of analyte vapor is used for teaching system and after that – for recognition of chemical image of analyte by means of special mathematical apparatus for statistical treatment.
CHEMOSENSORS CHEMOSENSORS Schematic view of ELECTRONIC NOSE 1.8-element Teflon gas cell 2.QCM-sensor array 3.air pump 4. filter-desiccant 5.two-positioned gas flow control valve 6.syringe–filler 7. analyte vapor 8. analyte container 9.analyte probe 10.end injection sensor
CHEMOSENSORS CHEMOSENSORS Stage of development The series of calixarene based receptors of ions and neutral molecules were synthesized in the Institute of Organic Chemistry NASU (www.ioch.kiev.ua/calix) The sensitive calixarene based polymer films were prepared in the Institute of Macromolecular Chemistry NASU The chemosensor pilot model ELECTRONIC NOSE is constructed in the Institute of Semiconductor Physics NASU (www.isp.kiev.ua)
CHEMOSENSORS CHEMOSENSORS Opportunities We offer the ELECTRONIC NOSE for: Targeted Market Segment monitoring of hazardous pollutants in environment; quality control in food industry and agriculture; quality control of perfumes and beverages.
CALIXARENES FOR DRUG DESIGN Calixarenes substituted with different pharmacophoric groups have shown multifarious biological activity. Highly diverse biomedical applications of these molecules now include antiviral, anti-thrombotic activities, enzyme blocking and protein complexation. Calixarenes are promising scaffolds for design of inhibitors containing of bioisosteric groups – the medicine-relevant molecules.
DRUG DESIGN The calixarene-methylene-bis-phosphonic acid is one of the most efficient substance among the alkaline phosphatase inhibitors described in the literature.
DRUG DESIGN Calixarenesulfonylamidine is a single inhibitor of Mg2+, ATP- dependent calcium pump of the myometrial plasma membrane. Calixarene-phosphonic acids are times more efficient than ouabaine in suppressing activity of the sodium pump.
DRUG DESIGN DRUG DESIGN Stage of development A series of calixarene based alkaline phosphatase inhibitors and Ca2+ exchange regulators were synthesized in the Institute of Organic Chemistry NASU (www.ioch.kiev.ua/calix). The high phosphatase inhibition activity and Ca2+ exchange regulation properties of the calixarenes were studied in the Institute of Bioorganic & Petrochemistry NASU (www ………………….) and in the Institute of Biochemistry NASU (www ……………..) Org. Lett., Vol. 8, No. 4, 2006, p ; Tetrahedron Letters 46 (2005) 7459–7462
DRUG DESIGN DRUG DESIGN Opportunitie s We offer: Design of new biologically active compounds by means of attaching of pharmacophoric groups to the calixarene platform. Targeted Market Segment Bio-medicine Industry Pharmacology
Contact information Iurii MATVIEIEV Institute of Organic Chemistry National Academy of Sciences of Ukraine Kiev