Green Chemistry /

Biomimicry

Mark Dorfman
DorfmanScience@gmail.com

Common synthetic chemical-based products:

Fire retardants

Synthetic fabrics
Detergents and cleaning chemicals

Fuels

Adhesives, paints,
solvents, and coatings

Electronics
chemicals

Plastics and
synthetic rubber

Meat processing
hormones and
antibiotics
Agricultural insecticides and fertilizers

Personal care products

Pharmaceuticals
Artificial flavors and fragrances

Theres no such thing...

as a FREE LUNCH

Products do not come to the home

or market without a price:
Energy requirements
Material inputs
Exposure to potentially toxic or
hazardous substances
at any point along the Commercial Chemical Chain

The Commercial Chemical Chain

A Man-Made
Largely Linear Phenomenon
in 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

Plastics

Pharmaceuticals Pesticides
Solvents

Fertilizers

Coatings

etc.

Generic Chemical Synthesis

Reaction Vessel

Compound A

Compound B

This is just to cover

Product C

By-products

Some products require

multiple steps to get from raw
materials to final product.
Each step may release
potentially toxic or hazardous
substances.

Consumption / Utilization
of Final Product

Medicine
Food
Clothing
Construction
Military
Sanitation

Emergency Response
Transportation
Education
Electronics
Media
Arts/Entertainment

RELEASES TO THE ENVIRONMENT

The next slide lists quantities of potentially
toxic and hazardous substances released to
the environment in a single year.
They are limited to:
Routine releases (excludes accidental releases),
The largest facilities in the USA,
650 of the 100,000+ chemicals registered for
commercial use,
Releases from manufacturing (excludes releases
from products inside homes, offices, or dumps).

Releases to:
Air ------------------------- 105,000,000 kg
Surface water ------------ 20,000,000 kg
Underground ------------- 81,000,000 kg
Hazardous Landfill ------ 2,000,000 kg
Non-Haz Landfill -------- 19,000,000 kg
Other --------------------- 20,000,000 kg
(currently 1,234 former manufacturing or waste sites placed
on the US Superfund list due to severe contamination)

Product Use and Disposal

100,000+ chemicals in commercial use.

For 650 chemicals used in New Jersey:
575 million kgs/yr of bioaccumulators,

carcinogens, heavy metals, halo-organics

ozone depleters, are shipped in products.

741 million kgs/yr of all reported

chemicals NOT intended as a product

component end up in the final product.

Potential Environmental and Public

Health Impacts from Exposure to
Commercial Chemicals
Single chemical health effects

largely unknown.
Multiple chemical health effects

almost entirely unknown.

Emerging Picture
Global impacts (ex. ozone hole, climate

change, worldwide Hg contamination).

Indoor air more polluted than outdoor.
Home chemicals found in U.S. streams.
Hormonal disruption found in male

fish, polar bears, alligators, frogs, and

other wildlife species.

Impacts on the Human Fetus?

Umbilical cord blood contains artificial musks,
alkylphenols, bisphenol-A, brominated flame
retardants, perfluorinated compounds, phthalates,
organochlorine pesticides and triclosan.
100+ commercial chemicals in human breast milk
(too contaminated for sale as food in U.S.).
Endocrine disruption at much lower levels than
previously considered safe.

This 1940s
Mobil gas ad
(as well as the
[Man]
followingcan
make
1920s quote)
illustrate the
something
perspective
new
which
during most of
is
better
the 20th
than
century that
anything
in
petroleum and
the chemical
nature
or
laboratory
naturally
could improve
produced.
the world
(Slosson,
how ironic that
1921)
the ad shows
the earth
coated with oil.

As we step out of the

Petro-Chem-Technology Age

and into the

Nano-Bio-Technology Age

BEWARE!
Nano-Bio-Tech Era:
Petro-Chem-Tech Era:
Tetra ethyl lead.
DDT, PCBs, CFCs.
NOx, SOx, CO2.
Di-Ethyl-Stilbestrol
(DES).
Endocrine disruptors.

2.5 micron particles cause

health impact
but nanoparticles are
1,000 times smaller.
Corn and edible fish
genetically modified to
produce pharmaceuticals.
Buckyballs enter the
brains of sportfish.

HAVE WE LEARNED ANY LESSONS?

If so, the following 12
GREEN CHEMISTRY PRINCIPLES
offer a means to enjoy
the fruits of an industrial society
while reducing their impacts
on public and environmental health

Green Chemistry Principle

1. Waste Prevention:
It is better to prevent waste
than to treat or clean up waste
after it has been created.

Green Chemistry Principle

2. Atom Economy:
Synthetic methods should be
designed to maximize the
incorporation of all [essential]
materials used in the process
into the final product.

Green Chemistry Principle

3. Less Hazardous Chemical
Synthesis:
Wherever practicable, synthetic
methods should be designed to use
and generate substances that
possess little or no toxicity to human
health and the environment.

Green Chemistry Principle

4. Designing Safer Chemicals:
Chemical products should be
designed to effect their desired
function while minimizing their
toxicity.

Green Chemistry Principle

5. Safer Solvents and Auxiliaries :
The use of auxiliary substances
(e.g., solvents, separation agents,
etc.) should be made unnecessary
wherever possible and innocuous
when used.

Green Chemistry Principle

6. Design for Energy Efficiency:
Energy requirements of chemical
processes should be recognized for
their environmental and economic
impacts and should be minimized. If
possible, synthetic methods should
be conducted at ambient
temperature and pressure.

Green Chemistry Principle

7. Use of Renewable Feedstocks:
A raw material or feedstock
should be renewable rather than
depleting whenever technically
and economically practicable.

Green Chemistry Principle

8. Reduce Derivatives:
Unnecessary derivatization (use of
blocking groups, protection/
deprotection, temporary modification of
physical/chemical processes) should be
minimized or avoided if possible,
because such steps require additional
reagents and can generate waste.

Green Chemistry Principle

9. Catalysis:
Catalytic reagents (as
selective as possible) are
superior to stoichiometric
reagents.

Green Chemistry Principle

10. Design for Degradation:
Chemical products should be
designed so that at the end of
their function they break down
into innocuous degradation
products and do not persist in
the environment.

Green Chemistry Principle

11. Real-time analysis for
Pollution Prevention:
Analytical methodologies need
to be further developed to
allow for real-time, in-process
monitoring and control prior to
the formation of hazardous
substances.

Green Chemistry Principle

12. Inherently Safer Chemistry for
Accident Prevention:
Substances and the form of a
substance used in a chemical
process should be chosen to
minimize the potential for chemical
accidents, including releases,
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 of Our Chemical Planet

The BIG BANG 14 Billion Years Ago

ammonia
carbon dioxide
hydrogen
nitrogen
phosphorous
sulfur
oxygen
ozone layer
water vapor
minerals
amino acids
heavy metals
radio nuclides

Earth 4.5 3 Billion Years Ago

Chemicals on the early Earth

interact spontaneously
in reactions that take
the path of least resistance,
such as:
Minerals dissolving in water.
Rust forming from iron.
Ozone created from lightning strikes.

3 Billion to 350 Million Years Ago

Living systems arise harnessing solar,
chemical, and thermal energy.
Complex chemical compounds (such as
DNA, proteins, enzymes, etc.) are created,
Complex compounds give rise to
biological systems such as bacteria, bluegreen algae, amphibians, and insects.

350 Million to 10,000 Years Ago

Fibers (wood, cotton, silk, wool, etc)
Fragrances / Flavors / Dyes / Medicines
(flowers, leaves, seeds, bark, insects)
Biological Toxins
(snakes, sea creatures, insects, plants)
Crude oil / coal / natural gas

Bio- and inorganic-chemicals interact with each other, the environment,

and living things in cycles such as the CARBON CYCLE

turning ashes (burning wood)

GLUCOSE + OXYGEN

CO2 + Water + Heat

Biology accomplishes amazing

chemical feats, such as
GLUCOSE + OXYGEN

CO2 + Water + Sunlight

back into trees (photosynthesis)

Chalk

Abalone Shell

Both are made of

calcium carbonate,
but Abalone is

 Twice as hard as high-tech ceramics.

Behaves like metal under stress.

Strength and Resilience of

Nacre due to:
CaCO3 hexagonal disks
Arranged in brick-wall motif
Protein mortar stretches,
slides, or oozes upon stress

Nacre micrograph

How Abalone Do It

1. Marine water.
2. Mortar proteins selfassemble framework.
3. Wallpaper proteins selfassemble on inner surfaces.
4. Crystallization initiates brick
formation from dissolved CaCO3.

How Industry Makes Ceramics

BEAT clay to proper consistency.
BAKE at high temperatures (2000 - 3000 Of).
for prolonged periods (15 50 Hours).

(Ceramics Industry Major Contributor To Global Warming)

Mussel Byssus

Components and Characteristics

Adhesive: works underwater
Disc: hard, resists cracks/stress
Thread: gradient, rigid to springy
Sealant: tough, biodegradable

How a Mussel
Makes its Byssus

Adhesive and Disc:

1.
2.
3.

Proteins Secreted
Fold, Twist, Crosslink
Creates hard foam structure

Thread
and
Sealant

1. Hollow Tube
2. Thread
- Strategic Protein Release
- Cross-Link
- Springy-Rigid Gradient
3. Sealant
- Protein Release
- Self-Assemble
- Seal

Potential Industrial Applications

Adhesive: No-blister paint; underboat coat; medical suture
Disc: dental surface, coating
Thread: prostheses tendon
Sealant: slow-degrade coat over fast-degrade material

HOW THE CHEMICAL INDUSTRY

MAKES ADHESIVES AND PLASTICS
1. Reactive starting materials.
2. Potentially toxic initiators.
3. Potentially toxic additives for:
Flexibility / Stiffness
Strength
Color
Stability, etc.

Gecko

feet

Synthetic Gecko tape:

Polyimide nanofibers

Mimic Photosynthesis to:

Generate an electric current.
Split water to produce hydrogen gas.
Drive solar-based manufacturing.
Create a switch for super fast computing.

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+ ions
into cell.
H+ build-up
drives ATP
synthase.

Artificial photosynthetic system

Most Common Human Ways

of Generating Power

Burning fossil fuels

Nuclear reactors
Hydroelectric dams

Common Characteristics of
Chemistry in Nature

Self-assembly

Protein-mediated
Water-based
Non toxic, renewable feedstocks
Hierarchical bottom-up structures
Biodegradable end-products (cyclic)
Ambient temperatures and pressures

VAST UNTAPPED POTENTIAL

270,000 Species of Plants
100,000 Fungi / Lichens
80,000 Protozoa / Algae
75,000 Spiders / Scorpions
70,000 Mollusks

GLOBAL TRENDS
Extrapolating current
technologies and
practices

Space Age Society Stone Age Impact

GLOBAL TRENDS
Utilizing Green Chemistry
and Biomimicry (??)