FromMembraneBiofoulingControltoAquaporinChannels

IsabelC.Escobar,PhDProfessorFPAT763D

Isabel.Escobar@uky.edu

ResearchfocusMy research focuses on developing and/or improving polymeric membrane materials through membrane materials development and post-synthesis modifications. Among my current projects are (1) low-fouling membranes; (2) anti-biofouling polypropylene feed spacers; (3) biofouling mechanisms; (4) low-fouling membranes using temperature-sensitive polymers activated using superparamagnetic iron nanoparticles; (5) polybenzoimidizole forward osmosis membranes; and (6) biomimetic membranes.

I have written over 50 manuscripts, have 1 licensed patent, and have over 100 presentations made at national and international conferences on membrane separations.

PhD in environmental engineering: Membrane separations

Chaired 3 membrane conferences AIChE Kunesh Award 2011 Board of Directors of NAMS

I am Associate Editor of EP&SE

With Professor Andrea Schaefer

Modern Applications inMembrane Science and

Technology

ACS SYMPOSIUM SERIES 1078

EDITED BYIsabel Escobar

and Bart Van der Bruggen

With Professor Bart Van der Bruggen

PointsofPrideI am Editor of the IDA Journal of Desalination & Water Reuse

Feed Permeate

Concentrate

¥  Allowformorechoicesoffeedwaters

•  Sea/BrackishWaterDesalinaGon,LowQualitySurfaceWater,Wastewater

¥  Higherpuritywatercanbeproducedtomeetincreasesinstringencyofwaterqualitystandards

¥  LessfootprintthantradiGonalwatertreatmentplants

WhyMembranes?

Membrane Process Application Guide .001 .01 .1 1.0 10 100 1,000

DissolvedOrganics

SandBacteria

Viruses

Salts Colloids

* MediaFiltraDon(sizeexclusion)

MicrofiltraDon(sizeexclusion)

UltrafiltraDon(sizeexclusion)

NanofiltraDon(sizeanddiffusion)

ReverseOsmosis(sizeanddiffusion)

* MediafiltraDon(notamembraneprocess)isshownforreferenceonly.

m m m m m m m

€

µ

*Electrodialysisremovesonlyionicspecies

€

µ

€

µ

€

µ

€

µ

€

µ

€

µ

CRaw

CConcentrate

CB

MembraneSeparaDons

Fouling

reversible irreversible

backslashTime

Flux

WhatisBiofouling?Biofoulingistheundesireddevelopmentofmicrobiallayersonthemembranesurfaceandthefeedspacer.Inbiofilms,organismssecreteextracellularpolymericsubstances(EPS),whichaidsintheiraUachmenttoasurfaceandresultsintheformaGonofamatrixofmicrobialorigin. Membrane Surface

MicrobialAUachment

MicrobialColonizaGon

EPS&MicrobialGrowth

0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0 10 20 30 40 50 60

FluxDeclin

e(%

)

Time(hr)

FluxDeclinevs.FiltraDonTime

HausmanR.,andI.C.Escobar(2013).JournalofAppliedPolymerScience,128(3):1706-1714.

Low-BiofoulingMembranesv Copper as Biocide:

v Disinfects water against microbial biofilms with effective dosages of a few tenths of 1 mg/L [1].

v Thought to be cytotoxic by causing changes in the plasma membrane permeability [2].

v  Generates reactive hydroxyl radicals, which can cause cellular damage imparted via oxidative stress [2].

v  It coordinates with proteins through thiol groups causing inhibition of the protein’s biological activity.

v  Silver is known biocide: v  Known to have strong

interactions with thiol groups, such as sulfydryl and –SH [3].

v  Silver attacks cytoplasmic proteins and DNA causing inactivation of enzymes [4].

v  Silver nanoparticles were chosen instead of chelating silver ions [5].

1. Kim et al (2002) Water Research, 36: 4433-4444. 2. Selvaraj, S. et al. (2009) Journal of Hazardous Materials, 166(2-3): p. 1403-1409. 3. Belly, R.T., Kydd, G.C., Silver resistance in microorganisms. Dev. Ind. Microbiol., 1982. 23: p. 567-577. 4. Pradeep, T. and Anshup (2009) Thin Solid Films, 517(24): p. 6441-6478. 5. Hausman R., and I.C. Escobar (2013). Journal of Applied Polymer Science, 128(3): 1706-1714.

Low-BiofoulingPolypropyleneFeedSpacersResults

sample of cells taken from modified

and copper charged PP sheets

after 48hrs

sample of cells taken from virgin PP sheets after

48hrs

Acknowledgements NSF SGER 0714539 & CBET 0754387 Patent US-2011-0120936-A1

Biofouling after 48 hours with

modified spacer

Initial biofouling

with traditional

spacer

Biofouling after 48 hours with virgin spacer

Waterpermeability

Low-BiofoulingMembranesAfter IDA and copper treatment the membranes changed from white to blue.

Acknowledgements Department of Interior – USBR NSF OISE 1264103 USAID

AsapuS.,S.Pant,C.L.Gruden,andI.C.Escobar(2014),Desalina6on,338:17-25.AsapuS.,S.Pant,P.Majid,I.C.Escobar,andC.Gruden(inpress2015),JournalofWaterReuseandDesalina6on,doi:10.2166/wrd.2015.001

ResponsiveMembranes

ResponsiveMembranes•  SDmuli-responsive

polymers•  Uniqueabilitytochangefroma

coiledtoglobularformaGoninthepresenceofasGmulus

•  SimuluscanbepH,temperature,ionicstrength,electricalandmagneGcfields:

(a)  NIPAAM hydrogel at room temperature (b) NIPAAM hydrogel at 34°C

(a) (b)

NIPAAMmembrane-coldcontactangle 47°

NIPAAMmembrane-hotcontactangle 56°Acknowledgements

NSF CBET 0610624 NSF GK-12 DGE-0742395

0.00#

1.00#

2.00#

3.00#

4.00#

5.00#

6.00#

7.00#

8.00#

0# 5# 10# 15# 20# 25# 30# 35# 40#

tempe

rature(adjus

ted(flu

x,(L/m

2hr(

time,(hr(

18%#CA+2%#NIPAAm#18%#CA#18%CA+2%NIPAAm4#average#flux##18%CA4#average#flux#

18%CA

18%CA+2%NIPAAm

SEMa=erfiltra6on

ChedeS.,andI.C.Escobar(2015).EnvironmentalProgress&SustainableEnergy,doi:10.1002/ep.12252.

ForAcDvaDon…•  Attaching carboxylated PNIPAAm (PNIPAAm-COOH) to amine group-

attached iron oxide magnetic nanoparticles using carbodiimide (EDC) chemistry

S

NHO

n

OH

O

+EDS

NHS

PNIPAAm-COOH PNIPAAm-NP

NP NH2

S

NHO

n

N

O

H

NP

Membrane placed at the center of the coil for RF heating

Radio frequency (RF) heating was achieved by sending current through coil. In present studies, current of 250 A and frequency 173 kHz was carried through a copper coil:

BiomimeDc&Bio-inspiredMembranes

5/13/14

1

!"#$%&'()**+,%-#"./01"23%45%%

67"/#7/%+#(%8/7,#4*4$3% !&-68%

Emerging membrane materials: from self-assembled

to biomimetic membranes!

%&(.+#7/(%9/:'0+#/1%+#(%;404)1%9+2/0"+*1%</#2/0=%

</#2/0%540%>/1+*"#+?4#%+#(%@+2/0%A/)1/=%!&-68%%

Journal of Membrane Science 454(2014)359–381

5/13/14

3

Journal of Membrane Science 454(2014)359–381

Journal of Membrane Science 454(2014)359–381

5/13/14

5

9

Apr. 19, 2005 — CORVALLIS, Ore. - Researchers from the College of

Forestry at Oregon State University have developed a new group of

adhesives that may revolutionize a large portion of the wood products

industry, and have important environmental and economic benefits.

Li observed mussels being pounded by ocean waves, and wondered

how they could cling so tenaciously to rocks by their thread-like

tentacles.

"I was amazed at the ability of these small mollusks to attach

themselves so strongly to rocks," said Li, who is an expert in wood

chemistry and adhesives in the OSU Department of Wood Science

and Engineering. "Thinking about it, I didn't know of any other type

of adhesive that could work this well in water and withstand so much

force."

Mussel-Inspired Surface Chemistry for

Multifunctional Coatings Haeshin Lee, Shara M. Dellatore, William M. Miller, Phillip B. Messersmith

Science 2007, 318, 426-430

Source:Klaus-V.Peinemann,KAUST

MembraneswithAquaporinChannels

How Nature does membranes … and far exceeds man-made performance

General cell wall structureSodium specific pump

Proton pumpsAquaporin water purifier

Nature is:• Incredibly diverse• Precisely selective• Very fast. Protein channels ~ 10^7

molec/s compared to transporters 10^2 molec/s.

• Aquaporin is 10,000 times faster than Haggen-Poiseuille flow prediction.

Protein Channels Basics

T.M. Devlin ‘Textbook of Biochemistry 6th ed’

Schematic representations explaining the mechanisms for blocking proton permeation in aquaporin.

Acknowledgements NSF 1308095

•  Combinetheultra-efficientfuncGoningofbiologicalmoleculeswiththeproducGvityofsyntheGcmembranes.

•  Aquaporins–Waterchannelproteins

presentincellmembranestoregulatetheflowofwaterinandoutofthecellwhileprevenGngthepassageofionsandothersolutes.

•  AddiGonofAqpZ;atypeofAquaporinsexpressedfromE.Coli,totheflatsheetpolymermembranestoimprovewaterfluxandrejecGonforwaterreuseanddesalinaGon.

MembraneswithAquaporinChannels•  PureWaterPermeability:

PBImembranefluxanalysis:Recoveryof61% PVA-alkyl-AqpZfluxanalysis:Recovery88%

0"

2"

4"

6"

8"

10"

0" 20" 40" 60" 80" 100" 120" 140"

Flux,"LM

H"

Time,"hrs"

Precompac<on"BSA"Lipase"NaCl"3.4"mM"NaCl"10"mM"NaCl"20"mM"NaCl"35"mM"NaCl"100"mM"CaCl2"3.4"mM"

0"

2"

4"

6"

8"

10"

0" 50" 100"

Flux,"LM

H""

Time,"hrs"

Precompac=on"BSA"Lipase"NaCl"3.4"mM"NaCl"10"mM"NaCl"20"mM"NaCl"35"mM"NaCl"100"mM"

•  SaltPermeability:

0"

10"

20"

30"

40"

50"

60"

70"

80"

90"

100"

0" 20" 40" 60" 80" 100" 120"

%"Rejec1o

n"

Feed"concentra1on"(mM)"

NaCl%filtra)on%rejec)on%Aqp"modified"membranes"unmodified"membranes"

0"

10"

20"

30"

40"

50"

60"

70"

80"

90"

100"

0" 20" 40" 60" 80" 100" 120"

%"Rejec1o

n"

Feed"concentra1on"(mM)"

CaCl2%filtra)on%rejec)on%

Aqp"modified"membranes"Unmodifed"membranes"

Wagh,P.,G.Parungao,R.E.ViolaandI.C.Escobar(2015).Separa6onandPurifica6onTechnology,156(2):754-765.

Scaled Processing •  Slot die extrusion - premetered casting •  Producing films typically above 15 µm from

solution and 20 nm from a suspension

a.

b. Picture of two slot die halves bottom) is a top view of the internal cavity.

Roll-to-roll Processing System

Heating control panel

Heated tank

Brake power supply

Roll-feed computer

LabVIEW monitoring station

Motor Brake Web speed control

Inspection system Inspection computer

with MATLAB

Inspection monitor

Power and thermocouple connections

Heated slot die

Heated platen

Scale up studies

0

2

4

6

8

10

0 4 8 12 16 20 24 28 32

perm

eabi

lity

time, hr

precompaction (lab scale) BSA filtration (lab scale)

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0 4 8 12 16 20

perm

eabi

lity

time, hr

precompaction (scale up)

lipase filtration (scale up)

BSA filtration

lipase filtration

BSA filtration

Lipase filtration

Lab scale 76.42% 68.06% Scale up 75.53% 78%

flux recovery after backwash

after BSA protein filtration followed by backwash

after lipase protein filtration followed by backwash

Lab scale Scale up

Acknowledgements NSF OISE 1264103 USAID

UsedforDifficultSeparaDons

HAB GROWTH

NUTRIENTS

GRAZING

WIND SPEED

WATER TEMPERATURE

LIGHT MICROCYSTIN PRODUCTION

Drinkingwater(provisional):1µg/LmicrocysGn-LR(WHO) 3µg/Lanatoxin-a(Australia)

TolerableDailyIntake(provisional):0.04µg/kg/day(WHO)

§ Highlywatersolubility§ StableinextremetemperaturesandpH§ NodegradaGonoftoxinaper15minutesofboiling

ToledoWaterCrisis,August2014

Source: Toledo Blade

Drinking water treatment system

Flocculation

ParDculate(cell)removalParDculate(cell)removal

Dissolved(toxin)removal:NotcompletelyeffecDve

Dissolved(toxin)removal:HelpfulbutmaynotbeeffecDveenough

To distribution system and

consumer tap

Source water with cyanoHAB

Toledo plant intake 3 miles offshore

Finished water

water

Flocculation

Treatment Process Concentration of MC-LR (ppb)

Ozonation 0.00

Biofiltration >5.00

Ozonation and Biofiltration 0.00

Ozonation, Biofiltration and Ultrafiltration 0.083

Biofiltration and Ultrafiltration 0.917

Nanofiltration 0.421

Ultrafiltration 2.552

Results

1

Evenasmembranetechnologiesmature,newinnovaGonsarebeingintroduced.Althoughmostofthesechangesareincremental,theyconGnuetoimprovereliability,reducecost,andmiGgateenvironmentalimpacts.

Conclusions

Acknowledgements•  NaGonalScienceFoundaGon•  DepartmentofInterior–USBureauofReclamaGon•  DepartmentofInterior–USGS•  USAID

hUp://www.engr.uky.edu/~iescobar/