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The way of greening analytical chemistry
Mihkel Koel,Mihkel Koel, Mihkel KaljurandInstitute of Chemistry, Tallinn University
of TechnologyAkadeemia tee 15
Tallinn 12618, [email protected]
Position of analyst
An analytical measurement is the presentation of knowledge about the chemical system that can be transferred, interpreted and processed
Support synthetic chemist and chemical engineer in confirmation of the greenness of their products and processes
Develop the methods and perform the analyses according to green chemistry&engineering principles
Role in society
Participation in knowledge accumulation and theory formulationDevelopment of standards and specifications in cooperation with producers in industry and agriculture
Motivation of new technologies and logistic solutions
Justify the need for new laws and administrative prescriptions
Justify the environmentally friendliness of new methods, processes and products
2009 Greener Reaction Conditions Award
CEM Corporation
“Innovative Analyzer Tags Proteins for Fast, Accurate Results without Hazardous Chemicals or High Temperatures”
This is green analytical chemistry what they are doing !
Monitoring of pollutantsVery low concentration in environment (fish, aquatic and
terrestrial mammals and birds, milk and blood of humans as well as soils and sediments):
Persistent organic pollutants (POPs)polychlorinated biphenyls (PCBs)organochlorine pesticides (OCPs)
Highly toxic effects are proved. Regular monitoring programs existing
• Organohalogens in atmosphere• Destroing ozone layer. Use is banned
complex instrumental analysis providing extremely low limits of detection at currently acceptable international standards - high cost.
BioanalyticsResidues of pharmaceuticals
antibioticswide range of other bioactive compounds
Ungent need to estimate any impact and toxic effects on living organisms. Regular monitoring programs are needed.
• Biomarkers and GMO• Early diagnostic of illness• Accidental spreading of GMO-s
• Active research started
Process analytical chemistry
Effluent treatment and monitoring
ManufacturingHealth and safety monitoring
Raw materials quality control
Process control and monitoring
Product quality control
Analytical signals
The molecule is a source (carrier) of information, and the useof particular method (using proper instrumentation) is theprocedure to extract and present this information – ananalytical signal – in the precise, most selective andeconomical way.
Analytical methods are based on chemical reactions andelectrochemical processes as well as on interactions with allforms of energy, particularly radiation, giving unambiguoussignals directly from the place where something important fora chemist is taking place – be it in the bulk or surface, solid,liquid or gas
Analytical instrumentation
Sensitive to detect single moleculesSelective to identify single moleculeDifferentiate structures of molecules
(Flourescence) SpectroscopyElectrochemistry
Laboratory analytical chemistryField analytical chemistryProcess analytical chemistry (technology)
Analytical laboratory
Analytical chemistry is considered to be independent applied chemical discipline with a multidisciplinary nature.
The control and monitoring laboratories have huge number of sample to analyze →
analytical laboratory ≈ industry of fine chemicalsrelated E-factor (ratio of by-products to the desired products) for
them is 25 - 100
Productively Improvements
Green Chemistry Green Engineering
P - Prevent wastes I - Inherently non-hazardous and safe R - Renewable materials M - Minimize material diversity O - Omit derivatization steps P - Prevention instead of treatment D - Degradable chemical products R - Renewable material and energy inputs U - Use safe synthetic methods O - Output-led design C - Catalytic reagents V - Very simple T - Temperature, Pressure ambient E - Efficient use of mass, energy, space and time I - In-Process monitoring M - Meet the need V - Very few auxillary substances E - Easy to separate by design E - E-factor, maximize feed in product N - Networks for exchange of local mass and
energy L - Low toxicity of chemical products T - Test the life cycle of the design Y - Yes, it is safe S - Sustainability throughout product life cycle
S. Tang, R. Bourne, R.Smith, M.Poliakoff, The 24 Principles of Green Engineering and Green Chemistry: “IMPROVEMENTS PRODUCTIVELY”Green Chem., 2008, 10, 268–269
Green analytical chemistryAnalytical method needs solvents, reagents, energy, and it creates the waste.
The principles of green chemistry in design of new methods:prevention of waste (1);safer solvents and auxiliaries (5);design for energy efficiency (6);avoid chemical derivatives (8)safer chemistry to minimize the potential of chemical accidents (12).
The principles of green engineering in design of new instruments:• all inputs and outputs are inherently nonhazardous (1)• maximize mass, energy, space and time efficiency (4)• limit the underused and unnecessary materials and energy (8)• minimize material diversity (9)• design for commercial “afterlife“ (11)
Choice of analytical methods
Origin of the sample and aim of data obtained on this sample affects the choice of the analytical methodWide choice of preparation methods for sample pre-treatment and separation before the analysisWide choice of determination methods for detection and identification
important is the assessment:of methods about the safety and riskof instrumentation about the economy and efficiency
Availability of mathematical methods for planning of analytical procedures and data processing
Present challengesMicrosystems Remote (wireless) control and data acquisition and analysis
Miniaturization: lab-on-a-chip and total analysis systemsMicrofluidicsNew automated sampling strategies
New materials Polymers, composites, alloys, biomaterialsNanostructured materials, molecular imprinting
Sensors Calibration-free: all sensors equal / total sample conversionReal time: “instantaneous” response, no kinetic effectsBiosensors
Information Multiple, localized simultaneous measurements to give- Spectrum of information- Multidimensional presentation of information
Chemometrics and new data analysis techniques (multivariate calibration, QSPR)
Prevention of waste
Replace wet-chemistry in sample preparation and treatmentUse direct analysis techniques
SpectroscopySurface analysisLaser-spectroscopic techniques
Solventless techniquesDecrease sample volume needed
Use of laboratory-on-chip in analysisUtilization of immunoassays
Alternative solventsSupercritical fluids
Not widely spread, lack of standard proceduresTechnically complicated, needs careful control of extraction parametersPossible losses of analytes during the sample collection after the extraction Not fully studied of handling of liquid samples
Ionic liquidsFew data on toxicity (bioaccumulation, biodegradability)Few data on physical properties and not clear understanding of solvent/material properties with regards to the structural features of IL No official analytical methods where ionic liquids are involvedExpensive and not commercially available
Safer chemistryIntegration sample preparation and separationUse of environmentally friendly solventsand reagents
Avoid derivatization•Direct analysis of sample•Reduce need for derivatization with different dection methods and signal processing
Design for energy efficiency
Efficient sample treatmentUltrasonic irradiationMicrowavesPhotochemical activationMechanical activation
Automation and miniaturizationUse of hyphenated techniques
Simple and economical instrumentation
Development of instrumental methods to replace wet-chemistry methodsAutomation of analysis processesMiniaturization and hyphenation of techniquesLimit the underused and unnecessary materials and functions
Liquid Chromatography
Capillary Electrophoresis
Injected volume 1-100 µL 1-100 nL
Flow rate of liquid phase
1-10 mL/min 1-100 nL/min
Flow profile parabolic plug
Number of separated peaks
20-30 20-100
Analysis time 10-60 min 1-20 min
Separation high pressure electrical field, no back pressure
Solvents different solvents for the different columns
different solvents in the same column
Level of developments
mature technique young, developing fast
Chemometrics
chemometric principles and computer applications are included at all steps of the analytical process:
sampling theory and experimental design,optimization of analytical measurements and separation procedures, signal processing for improvement of signal-to-noise ratio and signal resolution, multivariate statistics and data analysis for extraction of useful information from large (multidimensional) data sets,intelligent laboratory systems and robotics.
Conclusions
Confirm that chemical products and processes are safe Ensure the safety of chemical processesUse economical and efficient instrumentation
Perform analysis in a green way - The waste prevention, economy and life cycle of analyzer must become a part of decision in choosing proper analytical method
Acknowledgements
Estonian Science Fundation – G7303
Chair of analytical chemistry, Tallinn University of Technology