1. Brno Panorama

2. Emerging Ubiquity of Green Chemistry in Analytical Chemistry (An Application of Green Theory in Analytical Chemistry)
Pavel PAZDERA
Centre for Syntheses at Sustainable Conditions and their Management, Department of Chemistry, Faculty of Science, Masaryk University, Kotlarska 2, CZ , Brno, Czech Republic

3. Excurcus - Introduction of Centre SSCM
Since 2006 Masaryk University, Gasmeter, Co. Brno, and Synthetic Manufactory Draslovka Co. Kolín have joined their human, equipment, cash flow and know – how potentials and have formed new Centre for Syntheses at Sustainable Conditions and their Management on financial support of Czech Republic government. Activities of the Centre are focused on an application of Green Chemistry and Cleaner Production principles in the chemistry research, development, technology, engineering and production.

4. Activities of Company Gasmeter – Water are oriented to technology, engineering and apparatus for cleaner and greener chemical production. Synthetic Manufactory Draslovka Co. Kolín is focused on production of chemical specialties and fine chemicals based on cyanide chemistry area. It is one of the biggest hydrogen cyanide producers in Europe.

5. Main purposes of the Centre
1/ Research, development and application of Green Chemistry methods, cleaner chemical syntheses, and technologies in area of fine chemicals and pharmaceuticals for industry,
2/ Conception, synthetic design and strategy for greener industrial syntheses,
3/ Education and preparation of human resources in this field,
4/ Cooperation with similar workplaces in European research area and other countries in the World,
5/ Publicity, promotion and popularization of objectives, results in searching of the new chemical synthesis and technologies in Green Chemistry and Sustainable Development in Czech Republic with the goal to integrate these in the scientific, exploratory and technological sphere in EU.

6. Approaches and applied methods
Approaches and applied methods * Sophisticated sustainable syntheses of organic specialties, namely in cyan and amine chemistry (pyridine, piperazine),
* One pot, Domino- and similar synthetic processes,
* Catalysis by supported d-metal complexes (C-C and C-N coupling reactions, reduction, oxidation, addition, elimination reactions etc.),
* Phase transfer catalysis (PTC) and inverse PTC by supported catalysts,
* Ultra-sonochemistry and microwave assisted syntheses,
* Mini-reactors for industrial continual low-tonnage syntheses of fine chemicals at non-classical conditions.

7. Applied results (since 2006) * 6 patents or patent applications
Staff * 2 professors
* 2 scientists with Ph. D. degree
* 10 workers with MSc. degree
* 2 workers with BSc. degree
Analytical equipment * Multinuclear NMR spectrometers (300, , 600 MHz)
* FTIR and RA spectrometer
* UV-VIS spectrophotometer
* MS incl. MALDI spectroscopy
* GC, GC-MS, HPLC
* X-RAY diffractometer
* electro-analytical equipment
Applied results (since 2006) * 6 patents or patent applications
* 3 pilot plant technologies
* 4 plant technologies
* Portable plastic pilot plant synthetic reactors – capacity ca 50 – 500 kg material
Annual budget
*300 000 € (60 % government grant)
*120 000 € full grant for MU

8. Emerging Ubiquity of Green Chemistry in Analytical Chemistry (An Application of Green Theory in Analytical Chemistry)
Sergio Frías-García, M. J. Sánchez, Miguel Á. Rodríguez-Delgado - ULL:
Solid phase microextraction

9. Background - Some current global trends: hyperbolic vs
Background - Some current global trends: hyperbolic vs. exponential dependence

10. - hyperbolic dependence declines to zero;
Discrepancy between hyperbolic end exponential dependences is very fatal:
- hyperbolic dependence declines to zero;
- exponential dependence increases to … a crash (moment is unknown)!!

11. For humankind => current and in perspective non-sustainable being with non-rational development and non-responsive growth in near time horizon.
The society built around the consumption, the „growth of growth" and non-controlled profits does not want to see these fatal current global trends.

12. The society built around the consumption, the „growth of growth" and non-controlled profits does not want to see these fatal current global trends

13. Solution of actual discrepancies - Sustainable Development
Sustainable Development (1987) is defined as: "Development that meets the needs of the present without compromising the ability of future generations to meet their own needs."
Sustainable Development for all might be a starting-point, solution and prevention for an ulterior being of human civilization. It might to optimize close relations between economy (production, consumption, growth), human society, and environment, respectively.

14. The emergence of Green Theory:
Green Theory for humankind development, incl. production, consumption, resources, growth, economy, society, and environment
The environmental issues are only one part of fatal current global trends of real world. Since 1990s the process from environmental issues to green theories and next to green practices – green sciences, technologies and engineering, is starting.
Green theory and practice is based on the sustainable development
(and reflexive modernization), ecological security, environmental justice/law, and cost-effective approaches exclusive an incommensurability between an individual and an integral.
Green Theory
ROBYN ECKERSLEY

15. From Green Theory to Green Chemistry
Since 1970 United States Environmental Protection Agency (EPA) operates.
In 1990 Pollution Prevention Act, US EPA’s Office of Pollution Prevention and Toxics (OPPT) began to explore the idea of developing new or improving existing chemical products and processes to make them less hazardous to human health and the environment.
In 1991, OPPT launched the model research grants program "Alternative Synthetic Pathways for Pollution Prevention". This program provided, for the first time, grants for research projects that included pollution prevention in the synthesis of chemicals. Since that time the Green Chemistry Program has built collaborations with many partners to promote pollution prevention through Green Chemistry. Partnering organizations represent academia, industry, banks, other government agencies, and non-governmental organizations.

16. Under the name Green Chemistry are realized corresponding activities first of all in countries except continental Europe. In European Union may be analogous activities presented under indication Sustainable Chemistry.
Two exclusive journals Green Chemistry (RSC since 1999) and ChemSusChem (Wiley Interscience since 2008) publish the most up-to-date results and solutions of Sustainable and Green Chemistry.

17. Green Chemistry is not:
„Greenpeace friendly chemistry“ ;
about an environmental chemical monitoring only;
fleeting trendy job.
Not to be green upon any terms!
The addition of the words „Green„ or „Sustainable“ to our vocabulary, to our reports, programs, and papers, to the names of our academic institutes and research programs, and to our community initiatives, is not sufficient to ensure that our chemistry becomes „Greener“ or „Sustainable“ – notabene!

18. Safer Reactions & Reagents
Green Chemistry is about chemicals, chemical products and their syntheses and technologies for Sustainable Development. And also about money (first of all for undertakings). Green Chemistry is about applied chemistry for an individual and an integral in the future.
Safer Reactions & Reagents
Catalysis
Solvent
Replacement
Separation
Processes
Green
Chemistry
Use of
Renewable
Feedstocks .
Energy
Efficiency
Waste
Minimisation
Process
Intensification

19. What for „Green“?
– Because it is green vegetation, green tree of a living, and green „GO!“ on semaphore signal, respectively. On the other hand, the Earth is blue globe (it tells us Czech Republic president Vaclav Klaus).

20. Goals and Principles of Green Chemistry
The essential keyword connected with 4 fundamental goals of Green Chemistry is the phrase „minimizing“:
waste and pollution minimizing,
efficient exploitation of material and energy resources ( i. e. minimizing of their depletion),
hazard minimizing,
and minimizing of costs as result of previous three.

21. Goals and Principles of Green Chemistry
The next keywords for the set of Green Chemistry goals are terms “efficiently”, “rationally”, “really”, and “preferably” because declared goals may be not achieved promptly and absolutely. It is no dogma!!!!!! As the first Paul Anastas and John C. Warner (Anastas and Warner Green Chemistry: Theory and Practice, Oxford University Press: New York. p. 30.) formulated and declared 12 principles of Green Chemistry. These are known and used generally since the time.

22. Re-formulated 12 Green Chemistry principles (P
Re-formulated 12 Green Chemistry principles (P. Pazdera in Handbook on Applications of Ultrasound - Sonochemistry for Sustainability (Dong Chen, Sanjay K. Sharma, Ackmez Mudhoo - Edits.), Chapter 1. Emerging Ubiquity of Green Chemistry in Engineering and Technology, CRC/Taylor & Francis 2011.)
A. Waste and pollution minimizing:
1. Prevention of waste formation is preferred before waste disposal. It is better to solve waste “at source” (=prevention) then “and of pipe” (= waste management and/ or treatment).
This principle should be applied generally in all humankind activities !!!

23. Re-formulated 12 Green Chemistry principles (P
Re-formulated 12 Green Chemistry principles (P. Pazdera in Handbook on Applications of Ultrasound - Sonochemistry for Sustainability (Dong Chen, Sanjay K. Sharma, Ackmez Mudhoo - Edits.), Chapter 1. Emerging Ubiquity of Green Chemistry in Engineering and Technology, CRC/Taylor & Francis 2011.)
B. Efficient exploitation of material and energy sources:
2. Syntheses, synthetic processes must by design with highest atom economy, i. e. with maximal incorporation of inputs into product;
3. Rational reduction for using of solvents and other auxiliaries is preferred before their recycling and/or regeneration;
4. Preference of catalytic reagents before stoichiometric;
5. Preference of (solid) supported catalysts before homogenous;
6. Multistep syntheses are preferable to realize as One-pot, ideally as more sophisticated Domino-syntheses;
7. Permanent and renewable material and energy resources should be practicable and applicable rather than non-renewable wherever it is acceptable technically and economically. Research, development and engineering of suitable technologies for renewable material and energy resources;
8. Rational reduction for using of a raw material or feedstock derivatives by reason of their protection, activation and other temporary modification;

24. Re-formulated 12 Green Chemistry principles (P
Re-formulated 12 Green Chemistry principles (P. Pazdera in Handbook on Applications of Ultrasound - Sonochemistry for Sustainability (Dong Chen, Sanjay K. Sharma, Ackmez Mudhoo - Edits.), Chapter 1. Emerging Ubiquity of Green Chemistry in Engineering and Technology, CRC/Taylor & Francis 2011.)
C. General hazard minimizing:
9. Synthetic processes, incoming and out-coming chemicals must be minimal general hazardous
(Note: haloalkanes, dichloromethane especially, will be since 2015 eliminated for massive using);
10. Life cycle assessment of chemical products must by effected
(Note for explanation: Life cycle of chemical product is time between prenatal period of chemical product formation, starting from environment, over time of its use and postmortem time of its safe incorporation into environment);
11. Developing and using of suitable precise analytical techniques and methods to allow for real-time, in-process monitoring and control prior to the formation of hazardous substances.
D. Minimizing of costs:
12. It will be resulted as rational and efficient using above presented principles.

25. Environmentally friendly sample-preparation techniques is long and includes the following more or less self-explanatory types:
• Solvent micro-extraction
- In-vial liquid–liquid extraction (in-vial LLE)
- Single-drop micro-extraction (SDME)
- Liquid-phase micro-extraction (LPME)
Liquid–liquid–liquid micro-extraction (LLLME)
• Sorption micro-extraction and liquid desorption
- Solid-phase extraction (SPE)
- In-tube solid-phase micro-extraction (in-tube SPME)
- Fiber-in-tube solid-phase extraction (fiber-in-tube SPE)
- Single short column (SSC)
- Solid-phase micro-extraction (SPME)

26. Environmentally friendly sample-preparation techniques is long and includes the following more or less self-explanatory types:
• Thermal desorption
- Solid-phase micro-extraction (SPME)
- Stir-bar-sorptive extraction (SBSE)
• Matrix solid-phase dispersion
Matrix solid-phase dispersion (MSPD)
• Enhanced fluid/solvent extraction
- Supercritical-fluid extraction (SFE)
- Pressurized-liquid extraction (PLE)
- Subcritical-water extraction (SWE)
- Microwave-assisted extraction (MAE)
Sonication-assisted solvent extraction (SASE)
• Thermal desorption from solids
- Direct thermal desorption (DTD)

27. Methods and approaches applicable for realization of Green Chemistry goals and for achievement of its principles in Synthetic Chemistry and Analytical Chemistry
Sophisticated approaches including regio- and stereoselective synthetic procedures (Note for explanation: A sophisticated approach to solving of problem we can characterize as trivial efficient solution of non-trivial complicated problem),
Goal for synthetic chemist and the necessary practice for analyst. Flow injection analysis and sequential injection analysis. Greening Signal Acquisition.

28. Methods and approaches applicable for realization of Green Chemistry goals and for achievement of its principles in Synthetic Chemistry and Analytical Chemistry
B. One-pot, Domino-reactions, and procedures saving chemicals
Hi-tech and dream for synthetic chemist. For analytical chemist for one-pot or Domino-derivatization of analyzed sample followed by molecular-analytical method; one-drop micro-extraction and similar (ultra)micro separations. High sensitive structural and molecular analytical method - Greening Signal Acquisition. Flow injection analysis and sequential injection analysis. Hydrophilic interaction liquid chromatography (HILIC).

29. Methods and approaches applicable for realization of Green Chemistry goals and for achievement of its principles in Synthetic Chemistry and Analytical Chemistry
C. Acid-base catalysis, catalysis by transitions metal and its complexes incl. nano-particles, and enzymatic catalysis,
D. Inter-phase catalysis, i. e. phase transfer catalysis – both “classic“ and inverse PTC, and micellar catalysis,
E. Synthetic applications of supported catalysts (mentioned above) and auxiliaries by reason of their easy separation, regeneration, and re-using, and next solid supported and combinatorial syntheses, application of quantum dots.
Derivatization of molecules and surfaces for next analytical using.

30. Methods and approaches applicable for realization of Green Chemistry goals and for achievement of its principles in Synthetic Chemistry and Analytical Chemistry
F. Syntheses realized under non-classic conditions:
Supercritical (sc) water, carbon dioxide (both considering the risk because of high pressure and temperature for water, especially) and next ionic liquids as solvents (with sense of their toxicity),
For analytical extraction, for separation processes and methods (UHPLC)
Microwaves (MW) as a low-energy and an efficient alternative to classic heating,
For mineralization of biological samples, for solution of minerals, stones, metals and their alloys.
Ultrasound (US) as a low-energy and an efficient alternative to classic stirring, shaking and heating, respectively,
For preparation of samples for analyses, for degasification of samples and equipment.

31. Methods and approaches applicable for realization of Green Chemistry goals and for achievement of its principles in Synthetic Chemistry and Analytical Chemistry
G. Combinations of presented above methods and approaches, which bear often very efficacious and surprising results especially thanks to their synergism.
Very effective for both synthetic and analytical chemists.

32. Conclusion
The goals, principles, methods and approaches of Green Chemistry are for synthetic and analytical chemistry similar or the same because chemistry is only the one.

33. Thank you for your attention and time
Viničné Šumice = the village, where vineyards whisper and my family lives