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Green Chemistry / Green Chemistry / BiomimicryBiomimicry
[email protected] Dorfman
Fire retardantsSynthetic fabrics
Adhesives, paints, solvents, and coatings
Plastics and synthetic rubber
Detergents and cleaning chemicals
Electronics chemicals
Fuels
Common synthetic chemical-based products:
Agricultural insecticides and fertilizers
Artificial flavors and fragrances
Personal care productsPharmaceuticals
Meat processing hormones and antibiotics
There’s no such thing...There’s no such thing...
as a FREE LUNCHas a FREE LUNCH
Products do not come to the home or market without a “price”:
• Energy requirementsEnergy requirements
• Material inputs Material inputs
• Exposure to potentially toxic or Exposure to potentially toxic or hazardous substances…hazardous substances…
……at any point along the at any point along the Commercial Chemical ChainCommercial Chemical Chain
The Commercial Chemical ChainThe Commercial Chemical Chain
A Man-Made A Man-Made
Largely Linear Phenomenon Largely Linear Phenomenon
in a Cyclic Natural Worldin a Cyclic Natural World
Raw Material Extraction
• Crude oil
• Coal• Metals
• Minerals
Refining / Purification
• Gaseous fuels• Jet fuel• Gasoline• Home heating oil• Diesel
• Tar• BTX• Ethylene• Metals• Minerals
Synthesis / Formulation• Fabrics
• Pharmaceuticals
• Solvents
• Coatings
• Plastics
• Pesticides
• Fertilizers
• etc.
Generic Chemical Synthesis
Compound “A” Compound “B”
Product “C” By-products
Reaction Vessel
This is just to cover
Some products require Some products require multiple steps to get from raw multiple steps to get from raw
materials to final product. materials to final product.
Each step may release Each step may release potentially toxic or hazardous potentially toxic or hazardous
substances.substances.
Consumption / Utilization Consumption / Utilization of Final Productof Final Product
• Emergency ResponseEmergency Response• TransportationTransportation• EducationEducation• ElectronicsElectronics• MediaMedia• Arts/EntertainmentArts/Entertainment
• MedicineMedicine• FoodFood• ClothingClothing• ConstructionConstruction• MilitaryMilitary• SanitationSanitation
The next slide lists quantities of potentially The next slide lists quantities of potentially toxic and hazardous substances released to toxic and hazardous substances released to
the environment in a single year. the environment in a single year. They are limited to:They are limited to:
• Routine releases (excludes accidental releases),Routine releases (excludes accidental releases),
• The largest facilities in the USA,The largest facilities in the USA,
• 650 of the 100,000+ chemicals registered for 650 of the 100,000+ chemicals registered for commercial use,commercial use,
• Releases from manufacturing (excludes releases Releases from manufacturing (excludes releases from products inside homes, offices, or dumps).from products inside homes, offices, or dumps).
RELEASES TO THE ENVIRONMENT RELEASES TO THE ENVIRONMENT
• Air ------------------------- 105,000,000 kgAir ------------------------- 105,000,000 kg• Surface water ------------ 20,000,000 kgSurface water ------------ 20,000,000 kg• Underground ------------- 81,000,000 kgUnderground ------------- 81,000,000 kg• Hazardous Landfill ------ 2,000,000 kgHazardous Landfill ------ 2,000,000 kg• Non-Haz Landfill -------- 19,000,000 kgNon-Haz Landfill -------- 19,000,000 kg• ““Other” --------------------- 20,000,000 kgOther” --------------------- 20,000,000 kg(currently 1,234 former manufacturing or waste sites placed (currently 1,234 former manufacturing or waste sites placed
on the US “Superfund” list due to severe contamination)on the US “Superfund” list due to severe contamination)
Releases to:Releases to:
Product Use and DisposalProduct Use and Disposal100,000+ chemicals in commercial use.100,000+ chemicals in commercial use.
For 650 chemicals used in New Jersey:For 650 chemicals used in New Jersey:
• 575 million kgs/yr of bioaccumulators, 575 million kgs/yr of bioaccumulators, carcinogens, heavy metals, halo-organics carcinogens, heavy metals, halo-organics ozone depleters, are shipped in products.ozone depleters, are shipped in products.
• 741 million kgs/yr of all reported 741 million kgs/yr of all reported chemicals NOT intended as a product chemicals NOT intended as a product component end up in the final product.component end up in the final product.
Potential Environmental and Public Potential Environmental and Public Health Impacts from Exposure to Health Impacts from Exposure to
Commercial ChemicalsCommercial Chemicals
Single chemical health effects Single chemical health effects largely unknown.largely unknown.
Multiple chemical health effects Multiple chemical health effects almost entirely unknown.almost entirely unknown.
Emerging PictureEmerging Picture
Global impacts (ex. ozone hole, climate Global impacts (ex. ozone hole, climate change, worldwide Hg contamination).change, worldwide Hg contamination).
Indoor air more polluted than outdoor. Indoor air more polluted than outdoor.
Home chemicals found in U.S. streams.Home chemicals found in U.S. streams.
Hormonal disruption found in male Hormonal disruption found in male fish, polar bears, alligators, frogs, and fish, polar bears, alligators, frogs, and other wildlife species.other wildlife species.
Impacts on the Human Fetus?Impacts on the Human Fetus? Umbilical cord blood contains artificial musks, Umbilical cord blood contains artificial musks,
alkylphenols, bisphenol-A, brominated flame alkylphenols, bisphenol-A, brominated flame retardants, perfluorinated compounds, phthalates, retardants, perfluorinated compounds, phthalates, organochlorine pesticides and triclosan.organochlorine pesticides and triclosan.
100+ commercial chemicals in human breast milk 100+ commercial chemicals in human breast milk (too contaminated for sale as food in U.S.). (too contaminated for sale as food in U.S.).
Endocrine disruption at much lower levels than Endocrine disruption at much lower levels than previously considered safe.previously considered safe.
“[Man] can make something new which is better than anything in nature or naturally produced.” (Slosson, 1921)
This 1940’s Mobil gas ad (as well as the following 1920s quote) illustrate the perspective during most of the 20th century that petroleum and the chemical laboratory could improve the world… …how ironic that the ad shows the earth coated with oil.
……and into the and into the Nano-Bio-Technology AgeNano-Bio-Technology Age
As we step out of thePetro-Chem-Technology Age…
BEWARE!BEWARE!
Petro-Chem-Tech EraPetro-Chem-Tech Era::
• Tetra ethyl lead.Tetra ethyl lead.
• DDT, PCBs, CFCs.DDT, PCBs, CFCs.
• NOx, SOx, CO2.NOx, SOx, CO2.
• Di-Ethyl-Stilbestrol Di-Ethyl-Stilbestrol (DES).(DES).
• Endocrine disruptors.Endocrine disruptors.
Nano-Bio-Tech EraNano-Bio-Tech Era::• 2.5 micron particles cause 2.5 micron particles cause
health impact…health impact…
… … but nanoparticles are but nanoparticles are 1,000 times smaller.1,000 times smaller.
• Corn and edible fish Corn and edible fish genetically modified to genetically modified to produce pharmaceuticals.produce pharmaceuticals.
• ““Buckyballs” enter the Buckyballs” enter the brains of sportfish.brains of sportfish.
HAVE WE LEARNED ANY LESSONS?HAVE WE LEARNED ANY LESSONS?
If so, the following 12 If so, the following 12
““GREEN CHEMISTRY PRINCIPLESGREEN CHEMISTRY PRINCIPLES””
offer a means to enjoy offer a means to enjoy
the fruits of an industrial society the fruits of an industrial society
while reducing their impacts while reducing their impacts
on public and environmental healthon public and environmental health
Green Chemistry PrincipleGreen Chemistry Principle
1.1. Waste PreventionWaste Prevention::
It is better to prevent waste It is better to prevent waste than to treat or clean up waste than to treat or clean up waste after it has been created.after it has been created.
Green Chemistry PrincipleGreen Chemistry Principle
2.2. Atom EconomyAtom Economy::
Synthetic methods should be Synthetic methods should be designed to maximize the designed to maximize the incorporation of all [essential] incorporation of all [essential] materials used in the process materials used in the process into the final product.into the final product.
Green Chemistry PrincipleGreen Chemistry Principle
3.3. Less Hazardous Chemical Less Hazardous Chemical SynthesisSynthesis::
Wherever practicable, synthetic Wherever practicable, synthetic methods should be designed to use methods should be designed to use and generate substances that and generate substances that possess little or no toxicity to human possess little or no toxicity to human health and the environment.health and the environment.
Green Chemistry PrincipleGreen Chemistry Principle
4.4. Designing Safer ChemicalsDesigning Safer Chemicals::
Chemical products should be Chemical products should be designed to effect their desired designed to effect their desired function while minimizing their function while minimizing their toxicity.toxicity.
Green Chemistry PrincipleGreen Chemistry Principle
5.5. Safer Solvents and AuxiliariesSafer Solvents and Auxiliaries::
The use of auxiliary substances The use of auxiliary substances (e.g., solvents, separation agents, (e.g., solvents, separation agents, etc.) should be made unnecessary etc.) should be made unnecessary wherever possible and innocuous wherever possible and innocuous when used.when used.
Green Chemistry PrincipleGreen Chemistry Principle
6.6. Design for Energy EfficiencyDesign for Energy Efficiency::
Energy requirements of chemical Energy requirements of chemical processes should be recognized for processes should be recognized for their environmental and economic their environmental and economic impacts and should be minimized. If impacts and should be minimized. If possible, synthetic methods should possible, synthetic methods should be conducted at ambient be conducted at ambient temperature and pressure.temperature and pressure.
Green Chemistry PrincipleGreen Chemistry Principle
7.7. Use of Renewable FeedstocksUse of Renewable Feedstocks::
A raw material or feedstock A raw material or feedstock should be renewable rather than should be renewable rather than depleting whenever technically depleting whenever technically and economically practicable.and economically practicable.
Green Chemistry PrincipleGreen Chemistry Principle
8.8. Reduce DerivativesReduce Derivatives::
Unnecessary derivatization (use of Unnecessary derivatization (use of blocking groups, protection/ blocking groups, protection/ deprotection, temporary modification of deprotection, temporary modification of physical/chemical processes) should be physical/chemical processes) should be minimized or avoided if possible, minimized or avoided if possible, because such steps require additional because such steps require additional reagents and can generate waste.reagents and can generate waste.
Green Chemistry PrincipleGreen Chemistry Principle
9.9. CatalysisCatalysis::
Catalytic reagents (as Catalytic reagents (as selective as possible) are selective as possible) are superior to stoichiometric superior to stoichiometric reagents.reagents.
Green Chemistry PrincipleGreen Chemistry Principle
10.10. Design for DegradationDesign for Degradation::
Chemical products should be Chemical products should be designed so that at the end of designed so that at the end of their function they break down their function they break down into innocuous degradation into innocuous degradation products and do not persist in products and do not persist in the environment.the environment.
Green Chemistry PrincipleGreen Chemistry Principle
11.11. Real-time analysis for Real-time analysis for Pollution PreventionPollution Prevention::
Analytical methodologies need Analytical methodologies need to be further developed to to be further developed to allow for real-time, in-process allow for real-time, in-process monitoring and control prior to monitoring and control prior to the formation of hazardous the formation of hazardous substances.substances.
Green Chemistry PrincipleGreen Chemistry Principle
12.12. Inherently Safer Chemistry for Inherently Safer Chemistry for Accident PreventionAccident Prevention::
Substances and the form of a Substances and the form of a substance used in a chemical substance used in a chemical process should be chosen to process should be chosen to minimize the potential for chemical minimize the potential for chemical accidents, including releases, accidents, including releases, explosions, and fires.explosions, and fires.
The general public tends to assume that “chemicals” are man-made, and that nature is
something other than chemical.
This section is designed to show that the natural world is indeed a
chemical one.
The Rise ofThe Rise of Our ChemicalOur Chemical PlanetPlanet
The BIG BANG 14 Billion Years AgoThe BIG BANG 14 Billion Years Ago
ammoniaammoniacarbon dioxidecarbon dioxide
hydrogenhydrogennitrogennitrogen
phosphorousphosphoroussulfursulfur
oxygen oxygen ozone layer ozone layer water vaporwater vapor
mineralsmineralsamino acids amino acids heavy metalsheavy metalsradio nuclidesradio nuclides
Earth 4.5 –3 Billion Years Ago
Chemicals on the early Earth Chemicals on the early Earth interact spontaneously interact spontaneously inin reactions that reactions that take take
the path of least resistance, the path of least resistance, such as:such as:
Minerals dissolving in water.Minerals dissolving in water.
• Rust forming from iron.Rust forming from iron.
• Ozone created from lightning strikes.Ozone created from lightning strikes.
3 Billion to 350 Million Years Ago3 Billion to 350 Million Years Ago
• Living systems arise harnessing solar, Living systems arise harnessing solar, chemical, and thermal energy.chemical, and thermal energy.
• Complex chemical compounds (such as Complex chemical compounds (such as DNA, proteins, enzymes, etc.) are created, DNA, proteins, enzymes, etc.) are created,
• Complex compounds give rise to Complex compounds give rise to biological systems such as bacteria, blue-biological systems such as bacteria, blue-green algae, amphibians, and insects.green algae, amphibians, and insects.
350 Million to 10,000 Years Ago350 Million to 10,000 Years Ago
• Fibers (wood, cotton, silk, wool, etc)Fibers (wood, cotton, silk, wool, etc)
• Fragrances / Flavors / Dyes / Medicines Fragrances / Flavors / Dyes / Medicines (flowers, leaves, seeds, bark, insects)(flowers, leaves, seeds, bark, insects)
• Biological Toxins Biological Toxins (snakes, sea creatures, insects, plants)(snakes, sea creatures, insects, plants)
• Crude oil / coal / natural gasCrude oil / coal / natural gas
Bio- and inorganic-chemicals interact with each other, the environment, Bio- and inorganic-chemicals interact with each other, the environment, and living things in cycles such as the CARBON CYCLEand living things in cycles such as the CARBON CYCLE
……turning ashes turning ashes (burning wood)(burning wood)GLUCOSEGLUCOSE + + OXYGENOXYGEN COCO2 2 + Water + Heat+ Water + Heat
GLUCOSEGLUCOSE + + OXYGENOXYGEN COCO22 + Water + Sunlight + Water + Sunlight
back into trees back into trees (photosynthesis)(photosynthesis)
Biology accomplishes amazing Biology accomplishes amazing chemical feats, such as… chemical feats, such as…
Abalone ShellAbalone Shell
ChalkChalk
Both are made of Both are made of calcium carbonate, calcium carbonate, but Abalone is…but Abalone is…
• Twice as hard as high-tech ceramics.Twice as hard as high-tech ceramics.• Behaves like metal under stress.Behaves like metal under stress.
• CaCOCaCO33 hexagonal disks hexagonal disks
• Arranged in brick-wall motifArranged in brick-wall motif
• Protein “mortar” stretches, Protein “mortar” stretches, slides, or oozes upon stressslides, or oozes upon stress
Strength and Resilience of Strength and Resilience of “Nacre” due to:“Nacre” due to:
Nacre micrographNacre micrograph
How Abalone Do ItHow Abalone Do It
1.1. Marine water.Marine water.
2.2. ““Mortar” proteins self-Mortar” proteins self-assemble framework.assemble framework.
3.3. ““Wallpaper” proteins self-Wallpaper” proteins self-assemble on inner surfaces. assemble on inner surfaces.
4.4. Crystallization initiates “brick” Crystallization initiates “brick” formation from dissolved CaCOformation from dissolved CaCO33..
How Industry Makes CeramicsHow Industry Makes Ceramics
• BEAT…BEAT… clay to proper consistency.clay to proper consistency.
• BAKE…BAKE… at high temperatures (2000 - 3000 at high temperatures (2000 - 3000 OOf).f).
for prolonged periods (15 – 50 Hours).for prolonged periods (15 – 50 Hours).
(Ceramics Industry Major Contributor To Global Warming)(Ceramics Industry Major Contributor To Global Warming)
Mussel Byssus
Components and CharacteristicsComponents and Characteristics
• AdhesiveAdhesive: works underwater: works underwater
• DiscDisc: hard, resists cracks/stress: hard, resists cracks/stress
• ThreadThread: gradient, rigid to springy: gradient, rigid to springy
• SealantSealant: tough, biodegradable: tough, biodegradable
How a Mussel How a Mussel Makes its ByssusMakes its Byssus
Adhesive and Disc:Adhesive and Disc:1.1. Proteins SecretedProteins Secreted2.2. Fold, Twist, CrosslinkFold, Twist, Crosslink3.3. Creates hard foam structureCreates hard foam structure
Thread and Sealant
1.1. Hollow Tube Hollow Tube
2.2. Thread Thread - Strategic Protein Release- Strategic Protein Release- Cross-Link - Cross-Link - Springy-Rigid Gradient - Springy-Rigid Gradient
3.3. Sealant Sealant - Protein Release- Protein Release- Self-Assemble- Self-Assemble- Seal- Seal
Potential Industrial Applications
AdhesiveAdhesive: No-blister paint; underboat coat; medical suture: No-blister paint; underboat coat; medical suture
DiscDisc: dental surface, coating: dental surface, coating
ThreadThread: prostheses tendon: prostheses tendon
SealantSealant: slow-degrade: slow-degrade coat over fast-degrade material coat over fast-degrade material
HOW THE CHEMICAL INDUSTRY HOW THE CHEMICAL INDUSTRY MAKES ADHESIVES AND PLASTICSMAKES ADHESIVES AND PLASTICS
1.1. Reactive starting materials.Reactive starting materials.2.2. Potentially toxic “initiators”.Potentially toxic “initiators”.3.3. Potentially toxic additives for: Potentially toxic additives for:
Flexibility / StiffnessFlexibility / StiffnessStrength Strength
ColorColorStability, etcStability, etc..
Gecko feetGecko feet
Synthetic Gecko tape: Synthetic Gecko tape:
Polyimide nanofibersPolyimide nanofibers
Mimic to:Mimic to:
• Generate an electric current.
• Split water to produce hydrogen gas.
• Drive solar-based manufacturing.
• Create a switch for super fast computing.
PhotosynthesisPhotosynthesis
Energy from ATP plus enzyme NADPH is used to build sugar molecules from carbon dioxide.
• Photons split water into oxygen and hydrogen.
• Oxygen gas released from cell.• Hydrogen stored at H+ ion.• Light-induced electron flow
sets up charge separation.• Charge separation
shuttles H+ ionsinto cell.
• H+ build-updrives ATPsynthase.
Artificial photosynthetic system
Most Common Human Ways Most Common Human Ways of Generating Powerof Generating Power
• Burning fossil fuelsBurning fossil fuels
• Nuclear reactorsNuclear reactors
• Hydroelectric damsHydroelectric dams
Common Characteristics of Common Characteristics of Chemistry in NatureChemistry in Nature
• Self-assemblySelf-assembly
• Protein-mediatedProtein-mediated
• Water-basedWater-based
• Non toxic, renewable feedstocksNon toxic, renewable feedstocks
• Hierarchical “bottom-up” structuresHierarchical “bottom-up” structures
• Biodegradable end-products (cyclic)Biodegradable end-products (cyclic)
• Ambient temperatures and pressuresAmbient temperatures and pressures
VAST UNTAPPED POTENTIAL VAST UNTAPPED POTENTIAL
• 270,000 Species of Plants 270,000 Species of Plants
• 100,000 Fungi / Lichens 100,000 Fungi / Lichens
• 80,000 Protozoa / Algae 80,000 Protozoa / Algae
• 75,000 Spiders / Scorpions 75,000 Spiders / Scorpions
• 70,000 Mollusks70,000 Mollusks
0
10
Bill
ions
(not to scale)
Production
Population
Pollution
Quality ofLife
GLOBAL TRENDSGLOBAL TRENDSExtrapolating current Extrapolating current
technologies and technologies and practicespractices
0
10
Bill
ions
(not to scale)
Production
Population
Pollution
Quality of Life
Stone Age ImpactSpace Age Society…GLOBAL TRENDSUtilizing Green Chemistry
and Biomimicry (??)