OFFICE OF NAVAL RESEARCH END-OF-THE-YEAR REPORT PUBLICATIONS/PATENTS/PRESENTATIONS/HONORS/STUDENTS REPORT. for GRANT: N

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1 FFIC F NAVAL RSARCH ND-F-TH-YAR RPRT PUBLICATINS/PATNTS/PRSNTATINS/HNRS/STUDNTS RPRT fr GRANT: N PR Number: 97PR3238- Funtinalized Nanprus Plymer Membranes with Well-Defined Pre Arhitetures via Lytrpi Liquid-Crystalline Mnmers Duglas L. Gin University f Califrnia, Berkeley Department f Chemistry Berkeley, CA VDHC QUALTJT INSPCTD S June 3,1997 Reprdutin in whle r in part is permitted fr any use f the United States Gvernment This dument has been apprved fr publi release and sale; its distributin is unlimited

2 Wl:.-i>. \irr iä?r.{:* ^ jbli rd't ' Withering dr: infletin ',' RPRT DCUMNTATIN PAG - Jen tr r.-l,',.vielen f rnfrrr.r.i..n ;,--,.. tuning ;h?-nu n»'.?dd. -tnd mu.'tinn,.r 1. AGNCvTjS NLY (ie^tbl^kj i 2. IMPRT ATS June 3, TITL AND SUBTITL Funtinalized Nanprus Plymer Membranes with Well- Frm Apprved MB N : :-.».,,.A.;.-. ;,-,J.;^"prV... JZf^S '' * nd "«Prts Jefferwn "" " - T-'SSj.Wav.tri-tn, PC 25J. 3. RPFT TYP AND DATS VRD" Y Reprt June 1/96- May 31/97 5. FUNDING NUMBRS Grant # N Si- ««i^'^^srsisssiii.. 5tr^ssts 6. AUTHR(S) Dr. Kenneth J. Wynne Duglas L. Gin 7. PRFRMING RGANIZATIN NAM(S) AND ADDRSS(S) Department f Chemistry University f Califrnia, Berkeley Berkeley, CA PRFRMING RGANIZATIN RPRT NUMBR SPNSRING/MNITRING AGNCY NAM(S) AND ADDRSS(S) ffie f Naval Researh Physial S&T Divisin, NR 331 Department f the Navy Arlingtn, VA I 1. SPNSRING/MNITRING AGNCY RPRT NUMBR 11. SUPPLMNTARY NTS 12a. DISTRIBUTIN /AVAILABILITY STATMNT " " " Reprdutin in whle r in part is permitted fr any purpse f the united States Gvernment. This dument has been apprved fr publi release and sale- its distributin is unlimited. 12b. DISTRIBUTIN D j 13. ABSTRACT simur*. 2 wrds) _J as building Mks rr" m s^sis.'s'slsssrjrs sr-sr«r er - ^«Stin«^? 'V* ^"^ *>**S<1 mesphase liquad-rystauise mnmer platfrms hava bean mtteslt S\ T lytrpi mndmain thin TilZ f ILl. headgrup f the mnmers. Highly riented, SSible V±a th^ pressing f the Squid ^T " 8? ^^ *" P lks-in the rsr^rsss«^ PrX r * P*"'^«*»««. whih 14. SUBJCT TRMS rdered nanprus membranes, lytrpi liquid-rystalline mnmers, phtplymerizatin, inverse hexagnal^nase plymerizable amphiphilps B pnase, 17. SCURITY CLASSIFICATIN F RPRT unlassified 754-' = SCURITY CLASSIFICATIN F THIS PAG Unlassified 19. SCURITY CLASSIFICATIN F ABSTRACT Unlassified 15. NUMBR F PAGS 16. PRIC D 2. LIMITATIN F ABSTRACT Unlimited Standar : rm 298 (Rev 2-39)

3 FFIC F NAVAL RSARCH PUBLICATINS/PATNTS/PRSNTATINS/HNRS/STUDNTS RPRT Y Reprt-Part II PR Number: Cntrat/Grant Number: Cntrat/Grant Title: Prinipal Investigatr: Mailing Address: Phne Number: Fax Number: -mail Address: http address 97PR3238- N Funtinalized Nanprus Plymer Membranes with Well- Defined Pre Arhitetures via Lytrpi Liquid-Crystalline Mnmers Duglas L. Gin Dept. f Chemistry, University f Califrnia, Berkeley, CA 9472 (51) (51) gin@hemgate.hem.berkeley.edu N/A (a) Number f papers submitted t referred jurnals but nt published: (b) Number f papers published in refereed jurnals () Number f bks r hapters submitted but nt yet published: (d) Number f bks r hapters published: (e) Number f printed reprts/nn-refereed papers: (f) Number f patents filed: (g) Number f patents granted: (h) Number f invited presentatins: (i) Number f submitted presentatins: (j) Hnrs/awards/prizes fr ntrat/grant emplyees: (k) Number f full time equivalent graduate students and pstdtral assiates supprted during this perid, under this R&T prjet number: 2 Graduate students: Pstdtral assiates 1 Female graduate students: Female pstdtral assiates: Minrity graduate students: Minrity pstdtral assiates: Asian graduate students: Asian pstdtral assiates: 1 (1) ther funding (see attahed list):

4 (j) Hnr/Awards Reeived: 1997 Researh Crpratin Cttrell Shlar 3M Untenured Faulty Award (2nd year) (1) ther Funding Reeived During This Perid: U.S. Dept. f nergy, Center fr Advaned Materials, Lawrene Berkeley Natinal Labratry- (n grant title); $58, this year; ttal amunt: $58, fr 1/97-1/97; unnneted t NR' grant. Center f xellene fr the Synthesis and Pressing f Advaned Materials, U.S. Dept f nergy (n grant title); $22,4 this year; ttal amunt $22,4 fr 1/97-1/97 Rayhem Crpratin; (unrestrited researh gift); $15, this year; ttal amunt: $3 fr 1/95-present; unnneted t NR grant. Junir Faulty Researh Grant, Cmmittee n Researh, U. C. Berkeley; "Syntheti Cmpsites with Tunable, Nanmeter-Sale Arhitetures: New Materials via Mnmer Self-Assembly " $3, this year; ttal amunt: $3 fr 7/96-6/97 ACS Petrleum Researh Fund; "Piezeletri Plymer Netwrks via Mnmer Self-Assembly" $1, fr 9/1/96-8/3/97; ttal amunt: $2, fr 9/1/96-8/3/98; unnneted t NR ' grant. 3M Crpratin; Untenured Faulty Grant (unrestrited researh gift); $15, this year- ttal amunt: $3, fr 4/1/96-present; unnneted t NR grant. Natinal Siene Fundatin; "Highly rdered Plymeri Materials via Mnmer Self- Assembly;" $64,2 fr 5/97-6/98; ttal amunt: $322,153 fr 6/15/96-5/31/; unnneted t NR grant. xxn duatinal Fund, unrestrited researh gift, $1, this year; ttal amunt: $1 fr 1/97-1/97; unnneted t NR grant. Researh Crpratin, Cttrell Shlarship; "Fluresent Chemsensrs fr the Detetin f Bilgially Ative Mleules via Mleular Imprinting," $5, this year; ttal amunt- $5, fr 5/97-5/99; unnneted t NR grant.

5 Y Reprt-Part n (a) Prinipal Investigatr: Duglas L. Gin (b) Phne Number: (51) () Cgnizant NR Prgram ffier: Dr. Kenneth J. Wynne (d) Prgram bjetive: Current plymer membrane manufaturing tehnlgies affrd extremely pr ntrl ver ritial strutural features suh as pre size, pre arhiteture, and pre density in the nanmeter size regime. In additin, urrent tehnlgies ffer few hemial alternatives t addressing the prblems f membrane fuling whih degrade membrane perfrmane with use. The bjetive f the urrent researh prjet is t develp a new lass f new highly rdered, plymeri materials ntaining unifrm pre sizes in the nanmeter range using plymerizable lytrpi (i.e., amphiphili) liquid rystals as building blks, in whih the arrangement, size, and hemial prperties f the pres may be tailred n the mleular level. Speifially, ur bjetive is t develp rsslinkable lytrpi liquid-rystalline mnmers that spntaneusly frm the inverse hexagnal phase in the presene f water and an be pht-plymerized with retentin f the verall mirstruture (see view graphs enlsed). The result wuld be rbust, rsslinked plymer netwrks with tunable, aligned, nanmeter-sale hannels f extremely unifrm size. (e) Signifiant Results and Prgress: In the five mnth perid between the terminatin f ur first NR grant (frm whih seed mney was btained t initially develp this membrane prjet) and the date f this reprt (ne mnth int the urrent grant), signifiant prgress has been made in pre size ntrl and fabriatin f the nanprus netwrks int usable membrane films. Samples f these films have been submitted fr study. Previusly, we reprted demnstratin f basi prf f nept fr this prjet. Tw nvel amphiphili mnmers were synthesized that adpt the inverse hexagnal phase and an be phtplymerized with retentin f the hexagnal hannel arhiteture (Sheme 1). Preliminary experiments als shwed that the hannels in LC phases f mnmer 1 an be hmetrpially aligned in thin films using simple tehniques. ver the past five mnths, we have managed t systematially alter the interhannel spaing (and impliitly, the hannels diameter) f these nanprus netwrks by exhanging the sdium unterin f the mnmers with transitinmetal and lanthanide ins. Fr example, the Ni(II), C(II), Ce(III), and u(hi) analgs f 1 all exhibit the inverse hexagnal LC phase, but with varying interhannel spaings in the A range. Phtplymerizatin f the LC phases f these mnmers result in retentin f the phase arhiteture and dimensins. The signifiane f this wrk is that a simple methd an be used t ntrl pre size in these nanprus materials. The ptial and magneti prperties f the transitin-metals and lanthanide ins are apparently als inrprated int the resulting plymers, thus affrding the ptential mre advaned membrane appliatins. Transitin-metal and lanthanide exhange in mnmer 1 in general alter the pressability f the resulting LC phase. Fr exampe, the Ni(II) and C(II) analgs f 1 are muh less visus and pasty at ambient temperature than the sdium salt. They als an be pressed t give

6 hmetrpially aligned films at muh lwer temperatures. Plymer netwrks made with the C(II) salt an be hmetrpially aligned s well that plymerized films > 6 im thik are ptially transparent, yet are brwn-lred and display the harateristi X-ray diffratin prfile f a hexagnal phase, nsistent with a mndmain sample. Plymer films f 1 and its C(II) analg (apprximately m in diameter) have just been submitted t Prf. B. Freeman at NCSU fr quantitative determinatin f water uptake. (Preliminary experiments by the Freeman lab have demnstrated that earlier samples f plymerized 1 absrb water). Samples have als been submitted fr BT gas absrptin measurements in rder t determine surfae area.

7 Desriptin f nlsed View Graphs and Slides View Graph # 1: This view graph presents an verview f the ratinale and amplishments f ur membranes researh prgram ver the past 5 mnths, frm the terminatin f ur last NR grant (frm whih seed mney was used t develp the membranes prjet) t ne mnth after the start f the urrent grant. We have managed t nt nly prvide prf f nept fr the nvel apprah f nstruting rdered nanprus membranes using plymerizable amphiphili LCs as building blks, but we have als demnstrated ntrl ver pre dimensins and marspi sample alignment utilizing hanges in mleular struture. Samples f aligned nanprus films are urrently under evaluatin by llabratrs. View Graph # 2: This view graph shws x-ray diffratin evidene fr the inverse hexagnal struture fr ne f primary mnmer platfrms, whih ntains lng aqueus hannels in a lse-paked hexagnal arrangment. X-ray diffratin prvides unequival nfirmatin fr this nanarhiteture, sine LC phases with ther gemetries have harateristially different X-ray diffratin peaks. The graph shws that the LC mnmer phase with the mpsitin speified abve has an interhannel spaing f apprximately 4 nm (i.e., di/s 3 ) at ambient temperature. After ne hur f phtplymerizatin with 365 nm light (18 iw/m2) at ambient temperature, the resulting insluble, rsslinked film exhibits the same harateristi X- ray diffratin prfile, exept that the unit ell dimensins have dereased slightly as wuld be expeted upn rsslinking. View Graph # 3 This view graph prvides X-ray diffratin data shwing hw the interpre spaing f the nanprus netwrks an be hanged upn exhange f the sdium atin n the headgrup with varius transitin-metal and lanthanide atins. Althugh nt all transitin-metal r lanthanide atin derivatives f 1 an frm the inverse hexagnal phase at the system mpsitin speified, ne basi trend an be inferred frm the small number f derivatives we have synthesized s far: Mre psitively harged metal ins tend t derease the interpre distane by drawing the anini headgrups lser tgether. Phtgraphi Slide: This slide (shuld yu hse t use it) shws what thin, plymerized and riented films f mnmer 1 and its C(II) analg lk like. Please nte the transpareny and unifrmity f the samples and the fat that these films an be made in fairly large sizes. The film thikness f the tw fims shwn are apprximately 3 nm fr the lrless sdium salt (1) film and 6 ixm fr the C(H) salt film.

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Document And Report Documentation Page Submitted edoc_ 'uaiwixll r'u.iu V xvpuii ifj-tmeniann iage Submitted as ed 1.. '...X,> https://trstiiit.dti.mil/passgi/ed/ed_press_sf298.pl -/ Dument And Reprt Dumentatin Page Submitted ed_17573268 as Reprt Dumentatin