In eg a ed Mas e in Chemical Enginee ing
Syn hesis o Pep ide-based Po ous Ma e ials
Mas e ’s Thesis
by
Seyedali Emami
Supe iso : P o . Adélio Mendes
Co-Supe iso : P o . Luis Gales
Depa men o Chemical Enginee ing
July 2013
"تر شوخ مدیدن قشع نخس زا دنامب راود دبنگ نیا در که یراگدای"
ظفاح
“I ha e ne e seen a mo e beau i ul eminde
Than he wo ds o lo e ha linge in his u ning dome”
-Ha ez (1325-1389 C.E.)
Syn hesis o Pep ide-based Po ous Ma e ials
i
Acknowledgmen s
I would like o hank my ad iso s P o . Adélio Mendes and P o . Luis Gales o hei in aluable suppo s
and encou agemen on his hesis. My special g a i ude goes o P o . Gales o his assis ance and
guidance du ing e e y single momen o he wo k, wi hou his endless suppo his esea ch would no
be a success.
I would also like o exp ess my special g a i ude o D . Filipe Paz o collec ing x- ay di ac ion da a and
sol ing he c ys al s uc u e o my sample a Eu opean Synch o on Radia ion Facili y (ESRF). Special
hanks o Joana Du ão o he g ea assis ance, guidance and aluable ime spen wi h me du ing
adso p ion measu emen o my samples.
I am e y indeb ed o Na ges and Reza, my lo ely sis e and he husband. I lo e you dea ly and I am
g a e ul o you wonde ul suppo . Reza’s in ini e suppo and guides du ing my s ay in Po o canno
be desc ibed in wo ds, hank you o being he e o me. I would also like o acknowledge my bes
iend, Behdad o his help and guidance o o ganizing my wo k, hank you so much.
Finally, I would no be who I am wi hou my pa en s lo e and suppo . My bigges hanks and lo e o
hem, which I uly belie e hey dese e mos o he c edi o his hesis.

Syn hesis o Pep ide-based Po ous Ma e ials
ii
Syn hesis o Pep ide-based Po ous Ma e ials
iii
Abs ac
Me al o ganic amewo ks a ac signi ican a en ion du ing he las decades, due o hei wide ange
applica ion in gas s o age, adso p ion, and d ug deli e y. In his wo k, we syn hesized wo new me al-
pep ide amewo ks (MPF) h ough assembling GlyAsp dipep ide wi h Zn(II) and Co(II) me al ions. The
s uc u es o Zn and Co po ous amewo ks exhibi ed wo-dimensional and h ee-dimensional
opologies, espec i ely. In ac , cobal -based amewo k is among he ew examples o epo ed MPFs,
which has a 3-D s uc u e. The mog a ime ic analysis o hese compounds showed he mal s abili y up
o 250 oC, which is a decen s abili y compa ed o ma e ials wi h simila s uc u e.
Keywo ds:
Me al-pep ide amewo k (MPF), Me al-o ganic amewo k (MOF), Po ous ma e ial, GlyAsp, CO2
Adso p ion.
Syn hesis o Pep ide-based Po ous Ma e ials
i
Syn hesis o Pep ide-based Po ous Ma e ials
Resumo
As es u u as de ma e iais híb idos me al-o gânico êm a aído uma a enção signi ica i a nas úl imas
décadas, de ido à sua ampla gama de aplicações que ão desde a concen ação/sepa ação de gases po
adso ção à u lização como eículos pa a anspo e de á macos. Nes e abalho, sin e izou-se duas
no as es u u as de me al-pep ídeo (MPF) a a és da combinação do dipép ido GlyAsp com Zn(II) e
Co(II). As es u u as exibem ipologias bidimensionais e idimensionais, espe i amen e. Na e dade, a
es u u a de base de cobal o é um dos poucos exemplos de MPFs epo ados, que em uma es u u a 3-
D. A análise e mog a imé ica des es compos os mos ou uma es abilidade é mica supe io à da maio
pa e dos ma e iais des a classe, e que se si ua acima dos 250 oC.
Syn hesis o Pep ide-based Po ous Ma e ials
xii

Syn hesis o Pep ide-based Po ous Ma e ials
xiii
Nomencla u e
Symbol
Desc ip ion
De aul Uni
ime
s
P
p essu e
ba
V
olume
cm3
m
mass
g
ρ
densi y
g.cm-1
Mw
molecula weigh
g.mol-1
n
mola numbe
mol
R
gas cons an
cm3.ba .K-1.mmol-1
nads
mola numbe adso bed
mmol
T
empe a u e
K
q
adso p ion up ake
mol.kg-1
Syn hesis o Pep ide-based Po ous Ma e ials
xi
Syn hesis o Pep ide-based Po ous Ma e ials
x
Ac onyms and Abb e ia ions
AA
Amino Acid
Ac
Ace yl
Ala
Alanine
A g
A ginine
Asp
Aspa ic acid
BDC
1,4-benzenedica boxylic acid
BDC-(OH)2
2,5-dihyd oxybenzenedica boxyla e
BPB
1,2-bis(4’-py azolyl)benzene
BPE
1,2-bis(4-py idyl)-e hane
BTC
1,3,5-benzen ica bozyla e
DMF
Dime hyl o mamide
DPNI
N,N’-di-(4-py idyl)-1,4,5,8-naph halene e aca boxydimiimide
DSCP
c,c, -P (NH3)2Cl2(OOCCH2CH2CO2H)2
EDS
Ene gy Dispe si e Spec ome y
Glu
Glu ama e
Gly
Glycine
HEPES
4-(2-hyd oxye hyl)-1-pipe azinee hanesul onic acid
HKUST
Hong Kong Uni e si y o Science and Technology
IBU
Ibup o en
INA
Isonico inic acid
IUPAC
In e na ional Union o Pu e and Applied Chemis y
MBioF
Me al-biomolecule F amewo k
MEA
Memb ane Elec ode Assembly
MIL
Ma e ials o Ins i u La oisie
MOF
Me al-o ganic F amewo k
MPF
Me al-pep ide F amewo k
NCP
Nanoscale Coo dina ion Polyme
NDC
2,6-naph halendica boxyla e
ORR
Oxygen Reduc ion Reac ion
Syn hesis o Pep ide-based Po ous Ma e ials
x i
PEM
P o on Exchange Memb ane
PSA
P essu e Swing Adso p ion
SBU
Seconda y Building Uni
SEM
Scanning Elec on Mic oscope
TEOS
Te ae hyl o hosilica e
TG
The mog a ime ic
TGA
The mog a ime ic Analysis
Th
Th eonine
TSA
The mal Swing Adso p ion
WDS
Wa eleng h Dispe si e Spec ome y
XRPD
X-Ray Powde Di ac ion
ZIF
Zeoli ic Imidazola e F amewo k
Syn hesis o Pep ide-based Po ous Ma e ials
x ii
Lis o Figu es
Figu e 1.1-The MOF-5 s uc u e shown as me al cen e clus e (ZnO4 e ahed a) joined by o ganic linke
(benzene dica boxyla e) o gi e an ex ended 3-D cubic amewo k. Yellow sphe e ep esen s he la ges
sphe e ha can occupy he po es wi hou coming wi hin he an de Waals size o he amewo k. ........ 2
Figu e 1.2- Examples o SBU om ca boxyla e MOFs. O, ed; N, g een; C, black. In o ganic uni s me al
oxygen polyhed al a e blue, and polygon de ined by ca boxyla e ca bon a oms (SBUs) a e ed. a)
T iangle ( h ee poin s o ex ension), b) Squa e paddle-wheel ( ou poin s o ex ension). .......................... 6
Figu e 1.3- Hyd ogen adso p ion iso he ms o MOF-5 p epa ed wi hou exposu e o ai . Da a we e
measu ed a 77 K by Je ey R. Long e al. and a e shown as excess ( illed ed squa es) and o al ( illed
blue iangles) up ake. Open ci cles indica es he olume ic capaci y o hyd ogen ( igh -hand scale).. ... 8
Figu e 1.4- Schema ic illus a ion o selec i e gas adso p ion in igid MOFs ( op: he molecula sie ing
e ec , bo om: he modynamic equilib ium e ec ). ................................................................................. 11
Figu e 1.5- CO2 and CH4 adso p ion iso he m o dehyd a ed MIL-53 a 304 K. ......................................... 12
Figu e 1.6-Schema ic ep esen a ion o a PEM uel cell consis ing o ca alys laye s, gas di usion
elec odes and p o on exchange memb ane. ............................................................................................ 14
Figu e 1.7- Pola iza ion cu es o PEM uel cell o H2/O2. S a e-o - he-a P -based ca hode (0.3 mgP cm-
2, g een squa es), Fe-based ca hode ca alys syn hesized using ZIF-8 (blue s a s) and Fe-based ca hode
ca alys syn hesized using high su ace a ea ca bon black ins ead o ZIF-8 ( ed ci cles). . ........................ 15
Figu e 1.8- Ibup o en deli e y o MIL-100 and MIL-101. .......................................................................... 17
Figu e 1.9- P % eleased p o ile o NCP-1, NCP-1’-a, and NCP-1’-b. ......................................................... 18
Figu e 2.1- P esen a ion o po en ial coo dina ion modes o he amino g oup o GlyGly dipep ide; a)
monoden a e mode, b) i e-membe ed chela e ing. ................................................................................ 23
Figu e 2.2- (a) S uc u e o [Cd(AlaTh )2].4H2O. (b) View along he c ys allog aphic b axis (blue ne wo ks
shows he hyd ogen bonds). ....................................................................................................................... 25
Figu e 2.3- (a) S uc u e o [Zn(GlyAla)2] abo e 298 K. (b) Rep esen a ion o 1-D po e along he c axis a
298K (a e sol en e acua ion). ................................................................................................................. 26
Figu e 2.4- (a) The mog a ime ic analysis o [Zn(GlyAla)2].(sol en ) (b) CO2 so p ion iso he ms o
[Zn(GlyAla)2] a 273 K. ................................................................................................................................. 27
Figu e 2.5- (a) Oc ahed al coo dina ion o he pep ide a ound Zn(II) ion o [Zn(GlyTh )2].MeOH. (b)
Space- illing ep esen a ion o [Zn(GlyTh )2], showing he 1-D po es along he a axis.. ............................ 27
Figu e 2.6- The mog a ime ic analysis o [Zn(GlyTh )2].MeOH.. ............................................................. 28

Syn hesis o Pep ide-based Po ous Ma e ials
x iii
Figu e 2.7- (a) Selec i e so p ion o CO2 (squa es) o e CH4 ( iangles) o [Zn(GlyTh )2].MeOH a 273 K.
(b) CO2 so p ion iso he ms o [Zn(GlyTh )2].MeOH a 273 K (squa es) and 298 K ( iangles). Filled and
emp y symbols showing he adso p ion and deso p ion, espec i ely. ..................................................... 29
Figu e 2.8- Rep esen a ion o he s uc u es o GlyGlyGly ( op) and AlaAlaAla (bo om) ipep ides. ..... 29
Figu e 2.9- (a) S uc u e o [Cd(GlyGlyGly)2].H2O, showing a 3-D coo dina ion o cadmium ions. (b) View
along he c axis, showing an 8-membe ed ings o med by linking wo Cd ions o wo ca boxyla e g oups.
. ................................................................................................................................................................... 30
Figu e 2.10- (a) S uc u e o [Cd(AlaAlaAla)2]. (b) View along he b axis, exhibi ing 1-D po es. ................ 31
Figu e 3.1- Schema ic ep esen a ion o base di usion me hod. .............................................................. 34
Figu e 3.2- S uc u e o GlyAsp c ys al, oxygen ( ed), ni ogen (ligh blue), ca bon (whi e), and hyd ogen
(ligh g ey). .................................................................................................................................................. 35
Figu e 3.3- Ene gy dispe si e spec ome y analysis o sample A. ............................................................ 36
Figu e 3.4- (a) Mic oscopic and (b) SEM images o [Zn(GlyAsp)].H2O. ....................................................... 37
Figu e 3.5- (a) Mic oscopic and (b) SEM images o [Co(GlyAsp)].H2O. ...................................................... 38
Figu e 3.6- Rep esen a ion o he s uc u e o GlyAsp............................................................................... 40
Figu e 3.7- Me al ions coo dina ion modes o [Zn(GlyAsp)] (le ) and [Co(GlyAsp)] ( igh ). .................... 41
Figu e 3.8- Rep esen a ion o Zn(II) ion coo dina ion in [Zn(GlyAsp)]. ...................................................... 41
Figu e 3.9- S uc u e o [Zn(GlyAsp)].H2O; (a) Polyhed al ep esen a ion, zinc (blue polyhed al),
hyd ogen (whi e), ca bon (g ey), oxygen ( ed), and ni ogen (ligh blue). (b) S ick ep esen a ion, Zn-N
bond (blue-ligh blue), Zn-O bond (blue- ed), and wa e molecules (yellow). ........................................... 42
Figu e 3.10- S uc u e o [Co(GlyAsp)].H2O; (a) Polyhed al ep esen a ion, cobal (pink polyhed al),
hyd ogen (whi e), ca bon (g ey), oxygen ( ed), and ni ogen (ligh blue). (b) S ick ep esen a ion, Co-N
bond (pink-ligh blue), Co-O bond (pink- ed), and wa e molecules (yellow). (c) Oc acoo dina ed Co(II)
ions in [Co(GlyAsp)].H2O complex. .............................................................................................................. 43
Figu e 3.11- The mog a ime ic analysis o [Zn(GlyAsp)].H2O (blue solid line). G een dashed line
indica es he de i a i e weigh loss ( igh -hand scale), and appa en weigh losses a e highligh ed wi h
ed boxes. .................................................................................................................................................... 44
Figu e 3.12- The mog a ime ic analysis o [Co(GlyAsp)].H2O (blue solid line). G een dashed line
indica es he de i a i e weigh loss ( igh -hand scale), and appa en weigh losses a e highligh ed wi h
ed boxes. .................................................................................................................................................... 45
Figu e 3.13- Schema ic ep esen a ion o olume ic adso p ion appa a us. ........................................... 47
Syn hesis o Pep ide-based Po ous Ma e ials
xix
Figu e 3.14- Schema ic ep esen a ion o cumula i e adso p ion da a collec ion o olume ic me hod.
.................................................................................................................................................................... 48
Figu e 3.15- CO2 adso p ion iso he m o [Co(GlyAsp)].H2O a 288 K. ........................................................ 50
Syn hesis o Pep ide-based Po ous Ma e ials
xx
Syn hesis o Pep ide-based Po ous Ma e ials
xxi
Lis o Tables
Table 3.1- Selec ed condi ions o he expe imen s done h ough sol o he mal syn hesis me hod. ........ 35
Table 3.2- C ys al da a and s uc u e e inemen o [Zn(GlyAsp)].H2O and [Co(GlyAsp)].H2O. ................ 39
Table 3.3- La ice shape and symme y ope a o s o [Zn(GlyAsp)].H2O and [Co(GlyAsp)].H2O. .............. 40
Table 3.4- CO2 amoun adso bed o [Co(GlyAsp)].H2O a 288 K. .............................................................. 49
Syn hesis o Pep ide-based Po ous Ma e ials
Me al-o ganic amewo k 6
collapse. This collapse, eleases he s o ed ene gy in he bubble wi h hea ing and cooling a e o >1010
Ks-1, empe a u es o app oxima ely 5000 K, and p essu es o app oxima ely 1000 ba [9].
1.2. MOF s uc u e
S uc u e o me al-o ganic amewo k can be classi ied by hei seconda y building uni s (SBUs). SBU
e e s o he geome y o he uni s de ined by he poin s o ex ension. Howe e , he o ganic linke plays
an impo an ole in he opology o MOF, bu SBUs dic a e he inal geome y o hese ma e ials. Figu e
1.2 exhibi s wo seconda y building uni s acco ding o hei ino ganic uni s[5]. A comple e e iew on he
seconda y building uni s acco ding o hei poin s o ex ension could be ound in e e ence [10].
Figu e 1.2- Examples o SBU om ca boxyla e MOFs. O, ed; N, g een; C, black. In o ganic uni s me al oxygen
polyhed al a e blue, and polygon de ined by ca boxyla e ca bon a oms (SBUs) a e ed. a) T iangle ( h ee poin s o
ex ension), b) Squa e paddle-wheel ( ou poin s o ex ension)[5].
In 2008, Collins and co-wo ke s p o en ha he geome y o he SBU is dependen on he cha ac e is ics
such as s uc u e o he ligand, ype o me al, me al o ligand a io, sol en , and he sou ce o anions o
balance he cha ge o he me al ion[11].
MOFs a e mos ly po ous; which means ha hey ha e oid spaces wi hin hei s uc u e. Acco ding o
IUPAC po es a e classi ied by hei size ange, which is mic opo es (<2 nm), mesopo es (2-50 nm), and
mac opo es (>50nm). Mesopo ous and mac opo ous a e a ac i e o ca alysis applica ions because o

Syn hesis o Pep ide-based Po ous Ma e ials
Me al-o ganic amewo k 7
hei la ge po es. Mic opo ous ma e ials can be good candida es o gas s o age and sepa a ion due o
he s ong in e ac ions be ween gas molecules and he po e walls[1].
Commonly he po es o MOFs a e illed wi h he sol en molecules, which mus be emo ed o mos
applica ions. One o he possible p oblems in emo al o gues molecule is s uc u al collapse.
Gene ally, in la ge po es he possibili y o collapse is highe .
1.3. MOF applica ions
Recen ly, me al-o ganic amewo ks ha e ecei ed much a en ion owing o hei wide ange o
applica ions. Being po ous makes hese ma e ials in e es ing in a eas such as hyd ogen s o age [12], gas
adso p ion and sepa a ion [13], ca alys [14], d ug s o age and deli e y [1], and elec ochemical [15].
1.3.1. Hyd ogen s o age
Du ing pas decades, esea ches ocused o ind sui able eplacemen o ossil uels. An al e na i e uel
o au omo i e anspo a ion wi h less ca bon emissions become a i s p io i y. Ba e y and uel cell
echnologies a e s ong candida es o eplace gasoline and diesel engines. In pa icula , hyd ogen is an
a ac i e ene gy ca ie because i is ca bon- ee and abundan ly a ailable om wa e . Hyd ogen mus
be comp essed o e y high p essu es o s o ed c yogenically (a low empe a u e) [16].
Ma e ials wi h la ge su ace a eas and low densi ies such as MOFs, po ous ca bons, zeoli es and o ganic
polyme s, a e a ac i e o hyd ogen s o age applica ions. Hyd ogen s o age capaci y in hese ma e ials
depends on hei su ace a ea and po e olume. The main limi a ion o MOFs usage in H2 s o age is he
weak an de Waals in e ac ion ene gy be ween H2 and he su ace o he ma e ial [12].
MOF-5
5
has been widely s udied since, and u ns ou o be he bes c yogenic s o age ma e ial cu en ly
known. In 2003, he ini ial H2 s o age da a we e epo ed o MOF-5 (4.5 w % a 77 K and 1 a m),
al hough i was ound la e ha he maximum H2 up ake a ies om 1.3 o 5.2 excess w % a 77 K
depending on he p epa a ion and handling condi ions. In 2010, Je ey R. Long e al. s udied 6
e e ences o MOF-5 p epa a ion and handling condi ions, and hey sugges ed a new condi ion wi h
be e hyd ogen up ake. They ha e minimized he exposu e o wa e and ai in hei syn hesis me hod,
by which hey ha e eached o one o he highes g a ime ic capaci y (7.1 excess w % a 77 K and 40
ba ) obse ed o a hyd ogen s o age ma e ial ope a ing a 77 K [17]. Figu e 1.3 shows he o al and
5
Zn4O(1,4-benzene dica boxyla e)3
Syn hesis o Pep ide-based Po ous Ma e ials
Me al-o ganic amewo k 8
excess up ake o hyd ogen o his ma e ial wi h e e ed syn hesis condi ions. In he same yea (2010),
Oma K. Fa ha e al. simula ed a new me al-o ganic amewo k wi h a s uc u e simila o MOF-5. The
simula ion esul s showed he highes excess H2 s o age capaci y so a o MOFs wi h 99.5 mg/g a 56
ba and 77 K (NU-100) in No hwes e n Uni e si y. A e eaching ha high s o age capaci y h ough
compu a ional design, hey syn hesized he ma e ial success ully.
Figu e 1.3- Hyd ogen adso p ion iso he ms o MOF-5 p epa ed wi hou exposu e o ai . Da a we e measu ed a
77 K by Je ey R. Long e al. and a e shown as excess ( illed ed squa es) and o al ( illed blue iangles) up ake.
Open ci cles indica es he olume ic capaci y o hyd ogen ( igh -hand scale). Rep in ed wi h pe mission om
[17].Copy igh 2007 Ame ican Chemical Socie y.
Excess up ake is he amoun o gas aken up in addi ion o wha would be p esen in he con aine wi h
a olume equal o he po e olume wi hin he sample. To al up ake is he amoun o gas con ained
wi hin he olume o he c ys als, wi h includes bo h su ace-abso bed molecules and p essu ized gas
wi hin he po es [17].
1.3.2. Ca alys
As men ioned be o e, one o he key ea u es o he MOFs is hei po osi y; his cha ac e is ic makes
me al-o ganic in e es ing in ca alys a ea. Zeoli es a e he mos comme cially impo an classes o
ca alys . MOFs ha e some o he ca aly ically ele an speci ica ions o zeoli es such as la ge in e nal
su ace a eas and uni o m po e and ca i y sizes. Fi s , compa ing o zeoli es, MOFs can be syn hesized in
much chemical a ie y because hey also con ain o ganic base. Second, s abili y (depends essen ially on
he ca ion coo dina ion) o MOFs is lowe han zeoli es, which makes hem weak ca alys s o eac ions
0
10
20
30
40
50
60
70
80
90
0
1
2
3
4
5
6
7
8
9
10
11
12
020 40 60 80 100 120 140 160 180
Volume ic Capaci y (g H2/L)
H2 Up ake (%w )
P (ba )
Syn hesis o Pep ide-based Po ous Ma e ials
Me al-o ganic amewo k 9
equi ing o cing condi ions. Thi d, pe sis ence o mic opo osi y a e sol en e acua ion is essen ial o
gas-phase ca alysis, bu some MOFs collapse when sol en is emo ed ( he la ge he po e, he mo e
likely he collapse). Howe e , o ca alysis o condensed-phase eac ions his ea u e is no essen ial
[14].
Po e sys em o he MOFs anges om ul amic opo ous o mesopo ous, which gi es hem a ema kable
oppo uni y o ca alysis. The a ie y choice o s uc u e, which acili a es po e-size enabili y, is a g ea
oppo uni y o designing MOFs wi h po e openings app op ia e o gene a ing size and shape
selec i i y. In addi ion o po e size, di e en po e opologies can be ound o MOFs. Fo example, he
po e s uc u e can be one-dimensional (1-D) wi h s aigh channels, 2-D, o 3-D [18].
In 2009, Da id Fa usseng and co-wo ke s e iewed he s a e o he a o ca aly ic MOFs, and hey
epo ed applica ion o me al-o ganic amewo ks in a eas such as Lewis acid ca alysis, B øns ed acid
ca alysis, base ca alysis, C-C bond o ma ion, polyme iza ion, e c.
Oma K. Fa ha e al. s udied me al-o ganic amewo ks applica ion as ca alys s. They epo ed MOF
usage in eac ions ca alyzed such as oxida ion o ole in, oxida ion o alkane, oxida ion o sul ide,
oxida ion o polyphenol, oxida ion o alcohol, educ ion o ni oa oma ic e c.[14] Fo example Y.Lu and
co-wo ke s examined he ca aly ic ac i i y o [Co(BPB)].3DMF
6
o oxida ion o cyclohexene by
employing e -bu yl hyd ope oxide as oxidan . They epo ed a as and mul iple u no e oxida ion o
cyclohexene in he p esence o men ioned MOF, whe eas no eac ion occu s in he absence o ca alys
unde he same condi ion [19].
1.3.3. Gas adso p ion and sepa a ion
Sepa a ion is a p ocess ha di ides a mix u e in o i s componen s, which is caused by a mass sepa a ing
agen called adso ben , o so ben . Adso p i e gas sepa a ion includes passing a gas mix u e h ough a
columns packed wi h so ben pa icles, o ixed-bed adso be s o yield a p oduc en iched in he mo e
weakly adso bed cons i uen . This is hen ollowed by deso p ion o he s ongly adso bed componen
so ha adso ben can be eused. Sepa a ion is he opposi e p ocess o mixing and no mally is no a
spon aneous p ocedu e. Selec i e adso p ion leads o sepa a ion[20].
6
Cobal (II) 1,2-bis(4’-py azolyl)benzene in dime hyl o mamide.
Syn hesis o Pep ide-based Po ous Ma e ials
Me al-o ganic amewo k 10
Adso p i e gas sepa a ion p ocesses can be di ided in o wo ypes: bulk sepa a ion (adso p ion o a
signi ican ac ion, 10% by weigh o mo e om a gas s eam) and pu i ica ion (less han 10%
7
by
weigh o a gas s eam is adso bed)[20]. High sepa a ion powe can be eached by con inuous con ac
and equilib a ion be ween he gas and adso ben , o his pu pose cyclic p ocess such as he mal swing
adso p ion (TSA) cycles, p essu e swing adso p ion (PSA) cycles a e a ailable[21].
E e y componen has i s own adso p ion capaci y as an adso ben . The di e ence be ween adso p ion
capaci ies is he ounda ion o gas sepa a ion in adso p i e sepa a ion. The pe o mance o any
adso p i e sepa a ion o pu i ica ion p ocess is di ec ly de e mined by he cha ac e is ics o he
adso ben s in bo h adso p ion equilib ium and kine ics. In addi ion o sui able mechanical p ope ies, a
p omising adso ben should ha e a o able adso p ion kine ics and egene abili y as well as good
adso p ion capaci y and selec i i y. To sa is y hese equi emen s, he adso ben should possess no
only easonably high su ace a ea, bu also ela i ely la ge po e sizes o po ous ma e ials o allow
adso ba e molecules o app oach he in e io su ace[21].
The e a e ou majo mechanisms o gas adso p i e sepa a ion by a po ous ma e ial which can be
eached by one o se e al o hese mechanisms[22][20]:
(1) Molecula sie ing e ec ; gas mix u e componen s a e ei he allowed o p e en ed om en e ing
o he po es o an adso ben , because o size and/o shape exclusion. The allowed componen s
a e subsequen ly adso bed while he p e en ed componen s don’ adso b.
(2) The modynamic equilib ium e ec ; because o di e en adso ba e su ace and/o adso ba e
packing in e ac ion, p e e en ial adso p ion o ce ain componen s o e o he s occu s on he
su ace o and adso ben .
(3) Kine ic e ec ; because o di e en di using a es, ce ain componen s en e he po es and
become adso bed as e han o he componen s.
(4) Quan um sie ing e ec ; because o quan um e ec , some ligh molecules ha e di e en
di using a es in na ow mic opo es, which allows such molecules o be sepa a ed.
7
Usually <2%
Syn hesis o Pep ide-based Po ous Ma e ials
Me al-o ganic amewo k 11
Figu e 1.4- Schema ic illus a ion o selec i e gas adso p ion in igid MOFs ( op: he molecula sie ing e ec ,
bo om: he modynamic equilib ium e ec )[21].
MOFs can be ca ego ized in o lexible and igid. Flexible MOFs ha e dynamic, “so ” amewo ks which
a e sensi i e o ex e nal s imuli, such as empe a u e, gues molecules, and p essu e, while igid MOFs
ha e ela i ely s able and obus po ous amewo ks wi h pe manen po osi y[23]. Me al-o ganic
amewo ks ea u es such as la ge su ace a ea, adjus able po e size and he mal s abili y, gi es hem a
decen oppo uni y o be used as adso ben s o gas sepa a ion. Resea ch on MOFs is in he ea ly s age,
and a ew numbe s o hem ha e been es ed o hei adso p ion p ope ies. The adso p ion selec i i y
in igid MOFs may be ela ed o he molecula sie ing e ec and/ o p e e en ial adso p ion based on
he di e en s eng hs o adso ben -adso ba e and adso ba e-adso ba e in e ac ion. Figu e 1.4,
p esen s a schema ic illus a ion o selec i e gas adso p ion in igid MOFs[21].

Syn hesis o Pep ide-based Po ous Ma e ials
Me al-o ganic amewo k 12
Adso p ion beha io o MIL-53 wi h chemical o mula o C (OH)(BDC), which is a lexible MOF, has been
s udied by Bou elly and co-wo ke s. As syn hesized MIL-53 has a molecule o wa e inside i s s uc u e,
dehyd a ion o his ma e ial can occu by hea ing i a empe a u e o 100 oC. Dehyd a ed MIL-53 shows
a ypical CH4 adso p ion beha io o a mic opo ous ma e ial, while he adso p ion o CO2 e eals wo
s eps (Figu e 1.5). The adso p ion o CO2 is highe han CH4, which is expec ed because CO2 has a
signi ican quad upole momen , whe eas CH4 is nonpola [24].
Figu e 1.5- CO2 and CH4 adso p ion iso he m o dehyd a ed MIL-53 a 304 K. Rep in ed wi h pe mission om
[24].Copy igh 2005 Ame ican Chemical Socie y.
In 2008, Youn-Sang Bae e al. syn hesized a MOF wi h o mula o Zn2 (NDC)2(DPNI)
8
by wo di e en
ou es: i s a 80oC o wo days wi h con en ional hea ing, and second a 120oC o 1 hou using
mic owa e hea ing. They epo ed a selec i i y o 30 o CO2 o e CH4 o he mic owa e sample, which
is among he highes selec i i ies epo ed o his sepa a ion[25].
8
NDC=2,6-naph halendica boxyla e
DPNI=N,N’-di-(4-py idyl)-1,4,5,8-naph halene e aca boxydimiimide
Syn hesis o Pep ide-based Po ous Ma e ials
Me al-o ganic amewo k 13
1.3.4. Elec ochemical
The elec ochemical applica ion o MOFs is qui e a new in es iga ion on his ype o ma e ials. Me al-
o ganic amewo ks may be used o ene gy s o age and con e sion. Fo ins ance, MOFs can be used o
supe capaci o s, echa geable ba e ies and uel cell. Elec ochemis y, is he s udy o chemical
eac ions, include elec on ans e , a he in e ace o elec ode and elec oly e. A chemical eac ion
ha in ol es elec on ans e be ween molecules is called oxida ion/ educ ion o “Redox” eac ion.
Me al ca ions a e edox sou ce inside he s uc u e o me al-o ganic amewo ks; hese ca ions can
p o ide a pa hway o elec ons. In addi ion, decen selec ing o o ganic linke may imp o e he cha ge
ans e inside he amewo k[15].
Two applica ions o MOFs in elec ochemical a ea a e b ie ly epo ed in his wo k; Li-ion ba e y and
P o on Exchange Memb ane (PEM) uel cell.
Li-ion ba e y:
One o he mos common echa geable ba e ies is li hium-ion (Li-ion) ba e y and i is widely used o
po able elec onics. Li hium in e cala ed/alloyed in he anode and du ing discha ge; Li is oxidized o
li hium ca ion (Li+) and ans e s o he ca hode.
Th ee a emp s ha e made o apply MOFs o posi i e elec ode in Li-ion ba e ies and only one o hem
was success ul. Zinc and Nickel based MOFs was used o achie e his goal, using o Ni-based
mic opo ous phospha e led o ans o ma ion o he solid in o a nanocomposi e elec ode made o Ni
nanopa icles and Li2O ma ix. The o he a emp wi h Zn-based MOF is also came up wi h he simila
esul o nickel based, in he p esence o Li ions Zn-based amewo k decomposed in o a zinc based
nanocomposi e ma ix con aining Li2O.
In con as , Fe ey e al. ealized ha s onge me al-oxygen bonds my lead o sui able s abili y;
he e o e, hey used me als such as C 3+ and Fe3+ wi h highe oxida ion s a e han Zn o Ni. The sui able
me al-o ganic amewo k was ounded o be MIL-53 (Fe). H2O, 15 % w ca bon was added o his
ma e ial o be used in he posi i e elec ode, while he nega i e elec ode was Li-me al.
Li0.6Fe(OH)0.8F0.2(BDC).H2O showed a maximum up ake o li hium upon discha ge while i was ully
e e sible o a leas 50 cycles [26][15].
Syn hesis o Pep ide-based Po ous Ma e ials
Me al-o ganic amewo k 14
PEM uel cell:
The need o swi ch om in e nal combus ion engines o a low emission engines was gained much
a en ion du ing pas decades, uel cells a e one o he main leade o his eplacemen . Fuel cells can
be cha ac e ized by he elec oly e o hem. E e y uel cell is consis ing o h ee pa s; Anode whe e uel
is oxidized in o elec ons and p o ons, Ca hode whe e oxygen is educed o oxide species, and
Elec oly e whe e oxide ion o p o ons (depending on he ype o elec oly e) a e combined wi h oxide
o p o ons o p oduce elec ici y powe and wa e .
Figu e 1.6-Schema ic ep esen a ion o a PEM uel cell consis ing o ca alys laye s, gas di usion elec odes and
p o on exchange memb ane.
PEM uel cell is among he low empe a u e ope a ing (50-100 oC) uel cell, i s elec oly e is a solid
polyme (such as Na ion). The hea o a PEM uel cell is i s memb ane elec ode assembly (MEA) wi h a
hickness o less han a ew hund ed mic ons. Liquid wa e should be p esen in he memb ane o
e ec i e p o on conduc ing, and his is why PEM uel cells should ope a e in low empe a u es. MEA
pe o mance depends on i s elec oca alys echnology. The ca alys s o m hin gas-po ous elec ode
laye s on ei he side o he memb ane[27].
Syn hesis o Pep ide-based Po ous Ma e ials
Me al-o ganic amewo k 15
Today, he mos amous and applicable ca alys used in MEA is pla inum-based ma e ials. One o he key
sou ces o ol age loss in H2/ai uel cells is he slow kine ics o he Oxygen Reduc ion Reac ion (ORR);
e en in he bes P -based ca alys , his p oblem aced. Finding an al e na i e o pla inum-based ca alys
is one o he majo esea ch a eas since pla inum is expensi e and i s a ailabili y is low. Sui able and low
cos al e na i e ca alys s o ORR may lead o dec ease he o e all cos o PEM uel cells.
MOFs ha e some ea u es such as a ailable me al ca ions in hei s uc u e, high mic opo e su ace a ea
and high olume ic densi y o me al-ion si es, which make hem sui able o be py olyzed, in o de o
syn hesize non-p ecious me al ca alys s o ORR[15].
Figu e 1.7- Pola iza ion cu es o PEM uel cell o H2/O2. S a e-o - he-a P -based ca hode (0.3 mgP cm-2, g een
squa es), Fe-based ca hode ca alys syn hesized using ZIF-8 (blue s a s) and Fe-based ca hode ca alys syn hesized
using high su ace a ea ca bon black ins ead o ZIF-8 ( ed ci cles). P ep in ed by pe mission om Macmillan
Publishe s L d: Na u e Communica ions [28], copy igh 2011.
In 2011, P oie i and co-wo ke s p oduced ORR-ca alys p ecu so by mixing zinc based ZIF-8 (ZnII
zeoli ic-imidazola e- amewo k) wi h e ous ace a e and 1,10-phenan h oline. ZIF-8 used o ha s udy
had chemical o mula o Zn(MeIm)2
9
and i s s uc u e exhibi s a nanopo e opology esul ing om
b idging he Zn(II) cen e s o ni ogen a oms o imidazola e ligands. A ca hode wi h bes elec oca alys
9
MeIm=2-me hylimidazola e
Syn hesis o Pep ide-based Po ous Ma e ials
Pep ide-based MBioFs 22
Table 2.1- Selec ed po en ial coo dina ion modes o me al ion in amino acids.
S uc u e
Coo dina ion mode
Main AAs chain/side chain
biden a e (µ2-N1O1:O2)
main chain
biden a e (µ2-O1:O2)
main chain
iden a e (µ3-N1O1:O1:O2)
main chain
monoden a e (µ1-O3O4)
side chain
biden a e (µ2-O3O4:O4)
side chain
monoden a e (µ1-O3)
side chain
biden a e (µ2-O3:O4)
side chain
iden a e (µ3-O3:O3O4:O4)
side chain

Syn hesis o Pep ide-based Po ous Ma e ials
Pep ide-based MBioFs 23
2.2. Dipep ide-based MBioFs
Dipep ides a e composed o wo amino acids linked by pep ide bond. Pep ide bond in a chemical bond
o med be ween wo molecules when he ca boxyl g oup o one molecule links o he amino g oup o
he o he molecule, which ollows by elease o wa e ( eac ion 2.1).
Reac ion 2.1
Bo h ca boxyl g oup and amino g oup o a pep ide can coo dina e me al ions ia di e en coo dina ion
modes. The amino g oup usually coo dina es o me al ions in a monoden a e o chela ing ashion( igu e
2.1) [2].
The i s dipep ide-based MBioF was epo ed in 1996 by Takayama e al. They used GlyGly dipep ide
wi h Zn(II) and Cd(II) me al sal s. These au ho s syn hesized h ee MBioFs by adjus ing he pH o 6 and 9.
A pH 6, hey ob ained 2-D amewo ks wi h o mula o [M(GlyGly)2].2H2O (whe e M is Zn(II) o Cd(II)).
Each oc ahed al me al ions o zinc o cadmium was linked o ou o he me al ions h ough GlyGly
ligands. Each GlyGly ligand b idges wo me al ions; a i e-membe ed chela e ing was o med be ween
he e minal amino g oup and he adjacen O, and a monoden a e mode h ough he e minal
ca boxyla e g oup. A pH 9, only Cd(II) amewo k o med, a no el 2-D MBioF o mula ed as
[Cd(GlyGly)2].H2O, which each oc ahed al cadmium ions was b idged o six o he Cd(II) ions by ou
GlyGly ligands. The e minal ca boxyla e g oup links o wo me al ions, and amino g oup b idges o
ano he Cd(II) ion in a monoden a e mode[32].
Figu e 2.1- P esen a ion o po en ial coo dina ion modes o he amino g oup o GlyGly dipep ide; a) monoden a e
mode, b) i e-membe ed chela e ing.
Syn hesis o Pep ide-based Po ous Ma e ials
Pep ide-based MBioFs 24
To da e, small numbe o dipep ide-based MBioFs has been epo ed. Some o hese amewo ks a e
summa ized in able 2.2. He e, in his wo k h ee o hese amewo ks ([Cd(AlaTh )2].4H2O,
[Zn(GlyAla)2].(sol en ), and [Zn(GlyTh )2].CH3OH) we e selec ed o discus in mo e de ails.
Table 2.2- A summa y o dipep ide-based me al-biomolecule amewo ks.
Dipep ide
Me al
ion(s)
MBioF(s) o mula
Re .
Cd(II),
Zn(II)
[Cd(GlyGly)2].2H2O,
[Zn(GlyGly)2].2H2O,
[Cd(GlyGly)2].H2O
[32]
Zn(II)
[Zn(GlyTh )2].CH3OH
[33]
Cd(II)
[Cd(AlaAla)]
[34]
Zn(II)
[Zn(GlyAla)2].(sol en )
[35]
Pb(II),
Cd(II)
[Pb(GlyGlu)(H2O)1/2].ClO4,
[Cd(GlyGlu)2].3H2O
[36]
Cd(II)
[Cd(AlaTh )2].4H2O
[34]
Syn hesis o Pep ide-based Po ous Ma e ials
Pep ide-based MBioFs 25
[Cd(AlaTh )2].4H2O[34]:
This amewo k was syn hesized a oom empe a u e using base di usion me hod wi h ul asound
assis an . A solu ion o 0.06 mmol o CdAc2 and 0.12 mmol o AlaTh in 2 mL o wa e was sonica ed o
5 min wi h gen le shaking a 150 w using ul asonic ba h. This solu ion was placed in a 5 mL glass ial,
which was in u n was placed in a 20 mL sc ew-capped ial. Two millili e s o 2% ie hylamine solu ion
was added o he 20 mL ial and sealed wi h cap. Needle c ys als wi h 60% yield (based on cadmium)
we e g own a e abou 3 weeks.
The c ys al o his amewo k was monoclinic wi h space g oup o C2. I s s uc u e exhibi ed a 2-D
opology in which ou pep ides we e linked oge he by ou cadmium ions ( igu e 2.2). As shown in
igu e 2.2a each oc ahed al Cd(II) ions a e linked o ano he ou me al ions h ough ou pep ide
ligands; wo o which h ough he C- e minus ca boxyla e g oup (monoden a e), and he emaining ou
ia wo di e en chela e ings h ough he N- e minus (NH2- and amide ca bonyl).
Figu e 2.2- (a) S uc u e o [Cd(AlaTh )2].4H2O. (b) View along he c ys allog aphic b axis (blue ne wo ks shows he
hyd ogen bonds).Rep in ed wi h pe mission om [34], Copy igh 2008 Ame ican Chemical Socie y.
[Zn(GlyAla)2].(sol en )[35]:
Sol o he mal me hod is used o syn hesize his amewo k. A solu ion o 0.5 mmol o GlyAla and 0.25
mmol o zinc ni a e hexahyd a e in a mix u e o 90% me hanol and 10% 1M aqueous NaOH, was hea ed
o 85 oC o 1 hou wi h hea ing a e o 2 oC.min-1 and cooling a e o 0.2 oC.min-1, esul ing c ys alline
p oduc wi h 75% yield.
The c ys al o his amewo k was o ho hombic belonging o he space g oup P21212. A 2-D s uc u e
was o med which, had a 1-D squa e-shaped po e along he c axis ( igu e 2.3b). In which, each
Syn hesis o Pep ide-based Po ous Ma e ials
Pep ide-based MBioFs 26
e ahed al zinc ions we e linked o ou o he me al ions h ough ou pep ide ligands; wo dipep ide
ligands we e coo dina ed by he C- e minal Ala ca boxyla e g oups (in monoden a e mode) and he
o he wo ia N- e minal Gly amine g oups (in monoden a e mode) ( igu e 2.3a).
Figu e 2.3- (a) S uc u e o [Zn(GlyAla)2] abo e 298 K. (b) Rep esen a ion o 1-D po e along he c axis a 298K (a e
sol en e acua ion). Rep in ed wi h pe mission om suppo ing online ma e ial o [35], Copy igh 2010, Ame ican
Associa ion o Ad ancemen o Science.
The sol en wi hin he s uc u e o his amewo k can be emo ed e e sibly o ob ain desol a ed
amewo k. Acco ding o he mog a ime ic analysis (TGA) o he [Zn(GlyAla)2]. (sol en ), he i s
weigh loss (15.4%) occu s in he empe a u e ange o 35-250 oC which, co esponds o sol en loss.
The nex weigh loss (64.5%) occu s in empe a u e ange o 250-700 oC which, ag ees wi h
decomposi ion o [Zn(GlyAla)2] o ZnO ( igu e 2.4a).
This amewo k shows a phenomenon called “b ea hing”. B ea hing phenomenon consis s o wo
successi e c ys al- o-c ys al ans o ma ions du ing adso p ion p ocess. In which, he po e olume o
lexible amewo k is changing om la ge po e s a e o na ow po e s a e, and back again o he la ge
po e s uc u e[37].
B ea hing phenomenon educed he po e olume o he desol a ed amewo k du ing CO2 adso p ion
by changing he ϕ o sion angle o he me hyl g oup o he Ala. The CO2 adso p ion iso he m o
desol a ed amewo k a 273 K indica es wo s eps, i s a p essu e ange o 0-2 ba showing an small
adso p ion (non-po ous s uc u e), and second a p essu e ange o 2-15 exhibi ing highe mass up ake
(po ous s uc u e) ( igu e 2.4b).
Syn hesis o Pep ide-based Po ous Ma e ials
Pep ide-based MBioFs 27
Figu e 2.4- (a) The mog a ime ic analysis o [Zn(GlyAla)2].(sol en ) (b) CO2 so p ion iso he ms o [Zn(GlyAla)2] a
273 K (closed and open symbols ep esen adso p ion and deso p ion, espec i ely). Rep in ed wi h pe mission
om [35], Copy igh 2010, Ame ican Associa ion o Ad ancemen o Science.
[Zn(GlyTh )2].CH3OH[33]:
This amewo k was syn hesized by he same g oup who p oduced he [Zn(GlyAla)2].(sol en ). The
syn hesis (sol o he mal me hod) p ocedu e is simila o ha MBioF wi h small change in he sol en . A
solu ion o 0.05 mmol o zinc ni a e hexahyd a e and 0.1 mmol o GlyTh in me hanol and 0.08 mmol o
NaOH (aq) 1M, was hea ed o 85oC wi h hea ing a e o 2 oC.min-1 and cooling a e o 0.5 oC.min-1,
esul ing in colo less c ys als wi h yield o 70%.
Figu e 2.5- (a) Oc ahed al coo dina ion o he pep ide a ound Zn(II) ion o [Zn(GlyTh )2].MeOH. (b) Space- illing
ep esen a ion o [Zn(GlyTh )2], showing he 1-D po es along he a axis. Rep in ed wi h pe mission om[33],
Copy igh 2012 Wiley-VCH Ve lag GmbH & Co. KGaA, Weinheim.

Syn hesis o Pep ide-based Po ous Ma e ials
Pep ide-based MBioFs 28
The c ys alline ma e ial o his amewo k had monoclinic s uc u e belonging o I2 space g oup. The
amewo k exhibi s 2-D s uc u e wi h 1-D po es along a axis ( igu e 2.5b). Each oc acoo dina ed Zn(II)
ions a e linked o ou dipep ides; wo pep ides ligands a e coo dina ed h ough he C- e minus Th
ca boxyla e g oup (in biden a e mode) , and he o he wo a e o ming a i e-membe ed chela e wi h
amine and oxo g oup ia N- e minus Gly esidue ( igu e 2.5a). This MBioF is soluble in wa e and non-
soluble is o ganic sol en s such as, e hanol, me hanol, and ace one.
Me hanol gues molecules can be e acua ed by hea ing he amewo k up o 100oc unde acuum
o e nigh . Acco ding o TGA o [Zn(GlyTh )2].MeOH, he i s weigh loss occu s a empe a u es below
50 oC which, co esponds o me hanol emo al. The s uc u e emains s able up o 250oC. The i s
decomposi ion o he amewo k akes place in empe a u e ange o 250-380oC, and he second
decomposi ion occu a ound 500oC, which co esponds, o he o ma ion o ZnO ( igu e 2.6).
Figu e 2.6- The mog a ime ic analysis o [Zn(GlyTh )2].MeOH. Rep in ed wi h pe mission om[33], Copy igh
2012 Wiley-VCH Ve lag GmbH & Co. KGaA, Weinheim.
Syn hesis o Pep ide-based Po ous Ma e ials
Pep ide-based MBioFs 29
The adso p ion iso he m o his amewo k was i ed o BET heo y o ge he BET su ace a ea o 192
m2.g-1. The mos in e es ing poin o his amewo k is i s adso p ion selec i i y o CO2 o e CH4. Figu e
2.7a shows he p e e en ial CO2 o e CH4 adso p ion wi h single-componen sepa a ion a io o 14:1
(w %:w %) a 1 ba . The highes epo ed CO2:CH4 sepa a ion a io o MOFs is 24:1 o [Zn2(BPDC)2BPE]
a 298 K and 1 a m[38].
Figu e 2.7- (a) Selec i e so p ion o CO2 (squa es) o e CH4 ( iangles) o [Zn(GlyTh )2].MeOH a 273 K. (b) CO2
so p ion iso he ms o [Zn(GlyTh )2].MeOH a 273 K (squa es) and 298 K ( iangles). Filled and emp y symbols
showing he adso p ion and deso p ion, espec i ely. Rep in ed wi h pe mission om[33], Copy igh 2012 Wiley-
VCH Ve lag GmbH & Co. KGaA, Weinheim.
2.3. T ipep ide-based MBioFs
Up o da e, he e a e only wo epo ed ipep ide-based me al-o ganic amewo ks by Lee and co-
wo ke s on 2007. They assembled wo MBioFs wi h Cd(II) me al ions and AlaAlaAla and GlyGlyGly
ipep ides, s uc u es o hese wo ipep ides a e p esen ed in igu e 2.8.
Figu e 2.8- Rep esen a ion o he s uc u es o GlyGlyGly ( op) and AlaAlaAla (bo om) ipep ides.
Syn hesis o Pep ide-based Po ous Ma e ials
Pep ide-based MBioFs 30
[Cd(GlyGlyGly)2].H2O:
The syn hesis ou e o his amewo k is simila o ea lie epo ed syn hesis o [Cd(AlaTh )2].4H2O. A
solu ion o 0.05 mmol o CdAc2 and 0.10 mmol o GlyGlyGly in 2:2:3 mL o DMF, wa e , and e hanol,
espec i ely, was sonica ed o 5 min wi h gen le shaking a 150 w using ul asonic ba h. This solu ion
was placed in a 5 mL glass ial, which was in u n was placed in a 20 mL sc ew-capped ial. One millili e
o 2% ie hylamine in e hanol solu ion was added o he 20 mL ial and sealed wi h a cap. Needle
c ys als wi h 59% yield (based on cadmium) we e g own a e abou 3 mon hs.
The c ys alline amewo k o his MBioF was monoclinic belonging o he space g oup C2/c. Each
oc ahed al Cd(II) ion was linked o six pep ides o o m a 3-D complex ( igu e 2.9a); wo o which
h ough he N- e minus o wo pep ides (monoden a e), and ou ia he C- e minus ca boxyla es o
ou pep ides (monoden a e).
Figu e 2.9- (a) S uc u e o [Cd(GlyGlyGly)2].H2O, showing a 3-D coo dina ion o cadmium ions. (b) View along he c
axis, showing an 8-membe ed ings o med by linking wo Cd ions o wo ca boxyla e g oups. Rep in ed wi h
pe mission om [34], Copy igh 2008 Ame ican Chemical Socie y.
[Cd(AlaAlaAla)2]:
This amewo k was also assembled h ough he base di usion me hod wi h ul asound assis an
desc ibed o [Cd(AlaTh )2].4H2O and [Cd(GlyGlyGly)2].H2O. A solu ion o 0.15 mmol o CdAc2 and 0.15
mmol o GlyGlyGly in 10:10:5 mL o DMF, wa e , and e hanol, espec i ely, was sonica ed o 5 min wi h
gen le shaking a 150 w using ul asonic ba h. This solu ion was placed in a 20 mL glass ial, which was in
u n was placed in a 100 mL sc ew-capped ja . Ten millili e o 2% ie hylamine solu ion was added o
he 100 mL ja and sealed wi h a cap. Colo less anspa en needle c ys als wi h 43% yield we e g own
a e abou 3 weeks.
Syn hesis o Pep ide-based Po ous Ma e ials
Pep ide-based MBioFs 31
This amewo k c ys allized as monoclinic c ys als belonging o he chi al g oup space C2. The esul ing
amewo k had a 3-D opology wi h 1-D po es along i s b axis. Each Cd(II) ion was oc ahed ally
coo dina ed by ou ialanine pep ides; wo h ough he C- e minus ca boxyla e g oup o wo pep ides
(monoden a e), wo o he h ough he N- e minus amine g oup o wo pep ides, and inally he
emaining wo ia N- e minus amide ca bonyl g oup o he wo o he pep ides ( igu e 2.10a).
Figu e 2.10- (a) S uc u e o [Cd(AlaAlaAla)2]. (b) View along he b axis, exhibi ing 1-D po es. Rep in ed wi h
pe mission om [34], Copy igh 2008 Ame ican Chemical Socie y.
Syn hesis o Pep ide-based Po ous Ma e ials
Expe imen al p ocedu e and esul s 38
[Zn(GlyAsp)].H2O demons a e 1:1 s oichiome y o zinc and dipep ide in he amewo k. The e o e,
ano he way o syn hesis o his ma e ial is o use 1:1 s oichiome y o dipep ide and zinc sal . This new
syn hesis ou e can educe he amoun o dipep ide used and hus educing he inal cos o amewo k
assembly o 1.
3.1.2. Syn hesis o [Co(GlyAsp)].H2O
We used a simila sol o he mal syn hesis me hod o assemble cobal -based pep ide amewo k. Thus
ins ead o zinc sal , cobal ni a e sal is used o syn hesis o MPF [Co(GlyAsp)].H2O (2).
A 20 mL scin illa ion ial was cha ged wi h GlyAsp (0.1 mmol, ≥99.0% om Ald ich) and cobal (II) ni a e
hexahyd a e (0.05mmol, 98% om Sigma-Ald ich) in a wa e /me hanol mix u e (1.9/1.9 mL
espec i ely). The ollowing s eps ca ied ou o p epa e he solu ion:
1. 0.0145 g (equal o 0.05 mmol) o cobal ni a e sal was ca e ully weigh ed and cha ged o lask.
2. 0.0190 g (equal o 0.01 mmol) o GlyAsp was added o scin illa ion ial.
3. 1.9 mL o me hanol and 1.9 mL o deionized wa e was added.
4. The solu ion was s i ed o app oxima ely 45 min. A anspa en (wi h pink colo ) and clea
solu ion had eached.
5. 1 M aqueous sodium hyd oxide was added o basi y he solu ion. The pH was adjus ed o 5.99
while s i ing.
6. The eagen s we e hea ed a 85 ⁰C o 15 hou s, and cooled down o oom empe a u e o 30
min ( he sample le in he o en o cool down o oom empe a u e o abou 5 hou s).
As shown in igu e 3.5a, needle shape c ys als we e g own in he edge o powde s o 2.
Figu e 3.5- (a) Mic oscopic and (b) SEM images o [Co(GlyAsp)].H2O.

Syn hesis o Pep ide-based Po ous Ma e ials
Expe imen al p ocedu e and esul s 39
Compa ing o 1, his amewo k has ad an ages such as, no undesi ed p ecipi a ion o cobal hyd oxide
du ing assembly, and highe c ys al yield (22.23% based on cobal ). In con as , al hough he amewo k
o 2 has 1:1 s oichiome y o dipep ide and Co bu he yield o c ys alliza ion was highly dec eased when
his s oichiome y was applied hus, 1:1 s oichiome y is no sui able o assembly o his amewo k.
3.2. X- ay di ac ion
X- ay di ac ion (XRD) is a me hod used o de e mining he s uc u e o a c ys al. When X- ay beams
in e ac wi h c ys alline subs ance, hey di ac and as a esul , a di ac ion pa e n is ob ained. E e y
c ys alline subs ance gi es a unique pa e n he e o e, XRD pa e n o a pu e subs ance is like a
inge p in o he subs ance. By measu ing he angle and in ensi y o di ac ed X- ay beams, he
s uc u e o c ys al can be sol ed.
Table 3.2 shows he c ys al da a and s uc u e e inemen o 1 and 2.
Table 3.2- C ys al da a and s uc u e e inemen o [Zn(GlyAsp)].H2O and [Co(GlyAsp)].H2O.
Me al-pep ide amewo k
[Zn(GlyAsp)].H2O
[Co(GlyAsp)].H2O
Empi ical o mula
C6H10N2O6Zn
C6H9N2O6Co
Fo mula weigh (g/mol)
271.54
264.09
Tempe a u e (K)
100
120
C ys al sys em
Monoclinic
O ho hombic
Space g oup
P21
P212121
a (Å)
4.807
6.086
b (Å)
9.472
8.954
c (Å)
9.701
16.757
α (o)
90
90
β (o)
95.76
90
γ (o)
90
90
Volume (Å3)
439.5
913.17
Z
2
4
ρcal (g/cm3)
2.0519
1.9135
R indexes14 (all da a)
R1=0.0676 , wR2=0.1694
R1=0.0693 , wR2=0.1687
14
R1=∑ΙIFoI-IFcII/∑IFoI and wR2= [w(Fo
2-Fc
2)2]/[w(Fo
2)2]1/2.
Syn hesis o Pep ide-based Po ous Ma e ials
Expe imen al p ocedu e and esul s 40
As epo ed in able 3.2, c ys als sys em o 1 and 2 a e monoclinic and o ho hombic, espec i ely. Bo h
o hese amewo ks ha e p imi i e (P) la ice cen e ing, in which la ice poin s a e only coo dina ed on
he cell co ne s. Space g oup desc ibes he symme y o a c ys al, and Z alue indica es he numbe o
he symme y ope a o s ( able 3.3).
Table 3.3- La ice shape and symme y ope a o s o [Zn(GlyAsp)].H2O and [Co(GlyAsp)].H2O.
Me al-pep ide amewo k
[Zn(GlyAsp)].H2O
[Co(GlyAsp)].H2O
C ys al sys em
Monoclinic
O ho hombic
La ice shape
Space g oup
P21
P212121
Symme y ope a o s
(x,y,z)
(-x,y+1/2,-z)
(x,y,z)
(1/2-x,-y,1/2+z)
(-x,1/2+y,1/2-z)
(1/2+x,1/2-y,-z)
3.3. S uc u e
He e we desc ibe he s uc u es and me al coo dina ion modes o 1 and 2. Bo h o hese amewo ks
we e assembled wi h GlyAsp dipep ide ligands. The s uc u e o GlyAsp illus a ed in igu e 3.6.
Figu e 3.6- Rep esen a ion o he s uc u e o GlyAsp.
Syn hesis o Pep ide-based Po ous Ma e ials
Expe imen al p ocedu e and esul s 41
As men ioned be o e, wo di e en me al sal s o zinc and cobal ni a es we e used o syn hesis o
hese amewo ks. Coo dina ion modes o Zn (II) and Cobal (II) me al ions in amewo ks 1 and 2 a e
p esen ed in igu e 3.7.
Figu e 3.7- Me al ions coo dina ion modes o [Zn(GlyAsp)] (le ) and [Co(GlyAsp)] ( igh ).
3.3.1. S uc u e o [Zn(GlyAsp)].H2O
As shown in igu e 3.7, ou Zn(II) me al ions a e linked o each GlyAsp dipep ide. Each pen ahed al Zn(II)
ions a e linked o ou o he me al ions by ou dipep ide ligands; one o ming a i e-membe ed chela e
wi h amine and oxo g oup h ough N- e minus Gly esidue, wo h ough C- e minus ca boxyla e g oup
o Asp α-ca bon (in biden a e mode), and inally one ia C- e minus ca boxyla e g oup o β-ca bon o
Asp esidue (monoden a e). The e o e, adap ing e aden a e coo dina ion mode o µ4-N1O1:O2:O3:O4
( igu e 3.8).
Figu e 3.8- Rep esen a ion o Zn(II) ion coo dina ion in [Zn(GlyAsp)].
Syn hesis o Pep ide-based Po ous Ma e ials
Expe imen al p ocedu e and esul s 42
The amewo k o 1 exhibi s 2-D opology wi h 1-D po es along he a axis. Figu e 3.9 illus a es he
ex ended s uc u e o 1, in which he sol en molecules (wa e ) a e placed in channels o he
amewo k. These sol en molecules can be emo ed by hea ing up o 100oC.
Figu e 3.9- S uc u e o [Zn(GlyAsp)].H2O; (a) Polyhed al ep esen a ion, zinc (blue polyhed al), hyd ogen (whi e),
ca bon (g ey), oxygen ( ed), and ni ogen (ligh blue). (b) S ick ep esen a ion, Zn-N bond (blue-ligh blue), Zn-O
bond (blue- ed), and wa e molecules (yellow).
3.3.2. S uc u e o [Co(GlyAsp)].H2O
Fi e cobal (II) me al ions a e coo dina ed wi h each GlyAsp dipep ide ( igu e 3.7). Each oc ahed al Co(II)
ions a e b idged o i e o he me al ions by i e dipep ide ligands; one o ming a i e-membe ed chela e
wi h amine and oxo g oup h ough N- e minus Gly esidue, ou ia C- e minus ca boxyla e g oup o Asp
α and β-ca bons (each wo in biden a e mode). As a esul , adap ing pen aden a e coo dina ion mode o
µ5-N1O1:O2:O3:O4:O5 ( igu e 3.10c).
Compound 2, shows h ee-dimensional po ous s uc u e, which has one-dimensional po es along a axis.
These po es a e illed wi h wa e gues molecule. As men ioned ea lie in chap e 2, me al-pep ide
amewo ks commonly ha e 1-D opology and a ew o hem showing 2-D s uc u e, 3-D opologies a e
sca ce.
Figu e 3.10 ep esen s he s uc u e o his amewo k in wo models o polyhed al and s icks. The i e-
membe ed chela e ing o med h ough he N- e minus o Gly is clea ly shown in he s ick model.
Syn hesis o Pep ide-based Po ous Ma e ials
Expe imen al p ocedu e and esul s 43
Figu e 3.10- S uc u e o [Co(GlyAsp)].H2O; (a) Polyhed al ep esen a ion, cobal (pink polyhed al), hyd ogen
(whi e), ca bon (g ey), oxygen ( ed), and ni ogen (ligh blue). (b) S ick ep esen a ion, Co-N bond (pink-ligh blue),
Co-O bond (pink- ed), and wa e molecules (yellow). (c) Oc acoo dina ed Co(II) ions in [Co(GlyAsp)].H2O complex.
3.4. The mog a ime ic analysis
The mog a ime ic analysis (TGA) is he analysis o weigh changes in ela ion o changes in
empe a u e. A plo o weigh loss e sus empe a u e exhibi s he composi ion changes in sample and
he mal s abili y o e e ed sample. Ano he cu e o de i a i e weigh loss (DTG) can be used o see
he poin a which weigh loss is mos appa en .
TGA o compounds 1 and 2 we e ca ied ou wi h NETZSCH TG 209 F1 ins umen in 30-650oC
empe a u e ange wi h hea ing a e o 5oC.min-1 and ai low a e o 50 mL.min-1. Sample size o 11 and
21 mg o amewo k 1 and 2 used o hese measu emen s.

Syn hesis o Pep ide-based Po ous Ma e ials
Expe imen al p ocedu e and esul s 44
3.4.1. The mog a ime ic analysis o [Zn(GlyAsp)].H2O
Figu e 3.11 displays he TGA o me al-pep ide amewo k o 1. The i s weigh loss, co esponded o he
emo al o wa e gues molecules, akes place a empe a u e below 100 oC. This 6.5% weigh loss is in
good ag eemen wi h 6.6% wa e molecule ac ion in he amewo k o compound 1. The amewo k
emains s able up o 250 oC whe e he second decomposi ion occu s. Finally, weigh loss o 69% a
empe a u e o 500oC, which lea es a inal esidue wi h mola weigh o 84.12 g.mol-1 associa ed wi h
he o ma ion o Zn(II) oxide
15
.
Figu e 3.11- The mog a ime ic analysis o [Zn(GlyAsp)].H2O (blue solid line). G een dashed line indica es he
de i a i e weigh loss ( igh -hand scale), and appa en weigh losses a e highligh ed wi h ed boxes.
3.4.2. The mog a ime ic analysis o [Co(GlyAsp)].H2O
This amewo k exhibi s di e en decomposi ion beha io compa ing o amewo k 1. As shown in
igu e 3.12, he i s decomposi ion occu s a empe a u e ange o 115-240 oC wi h 6.15% weigh loss
ha is associa ed o wa e emo al. Decomposi ion con inues up o 350oC whe e as weigh loss akes
place h ough 30oC empe a u e inc ease. The inal 69.89% weigh loss a e 380oC is in su icien
ag eemen wi h o ma ion o Co(II) oxide
16
.
15
ZnO=81.39 g.mol-1
16
CoO=74.93 g.mol-1 app oxima ely equal o 79.78 g.mol-1 ( esidue mola weigh )
-0.50
0.00
0.50
1.00
1.50
2.00
2.50
3.00
3.50
4.00
0
20
40
60
80
100
120
0 100 200 300 400 500 600 700
De i . Weigh loss (%/min)
Weigh loss (%)
Tempe a u e oC
TG
DTG
Syn hesis o Pep ide-based Po ous Ma e ials
Expe imen al p ocedu e and esul s 45
As men ioned in sec ion 3.2.2, po es o his amewo k a e illed wi h hese gues molecules he e o e;
be e adso p ion beha io can accomplish a e e acua ion by hea ing he amewo k o 2 up o 240oC.
Figu e 3.12- The mog a ime ic analysis o [Co(GlyAsp)].H2O (blue solid line). G een dashed line indica es he
de i a i e weigh loss ( igh -hand scale), and appa en weigh losses a e highligh ed wi h ed boxes.
3.5. Adso p ion
E e y so p ion p ocess is consis o wo componen s, so ba e and so ben . Fluid phase (so ba e) is
ans e ed o so bing agen (so ben ) which could be suspended in a essel o packed in a column[39].
Adso p ion, ion exchange, and ch oma og aphy a e so p ion ope a ions. In an adso p ion p ocess,
so ba e (gas/liquid) di uses o he su ace o a so ben (solid). Molecules, a oms, o ions o so ba e
bond wi h he su ace o he so ba e o a e held by weak in e molecula o ces o i . In gene al, he solid
ma e ial is e e ed o as adso ben , whe eas he adso bed solu es a e called adso ba e. Du ing
adso p ion, he adso ben become sa u a ed o nea ly sa u a ed wi h he molecules, a oms, o ions o
he adso ba e. The adso ben is egene a ed by deso p ion he so bed ma e ial, in o de o euse he
-1
1
3
5
7
9
11
13
0
20
40
60
80
100
120
0 100 200 300 400 500 600 700
De i . Weigh loss (%/min)
Weigh loss %
Tempe a u e (oC)
TG
DTG
Syn hesis o Pep ide-based Po ous Ma e ials
Expe imen al p ocedu e and esul s 46
adso ben . As men ioned be o e, adso p ion can be classi ied as pu i ica ion o bulk sepa a ion,
depending on he concen a ion in he eed luid o he componen s o be adso bed
17
[39].
Di e en ypes o o ces be ween adso ba e molecule and he molecules o he adso ben may
ca ego ize adso p ion in o physical adso p ion ( an de Waals adso p ion) and chemiso p ion (ac i a ed
adso p ion). Physical adso p ion om a gas happens when he in e molecula o ces o he gas a e
smalle han he in e molecula a ac i e o ces be ween molecules o adso ben and he gas. The
esul ing adso p ion is exo he mic and i is simila o condensa ion. Physical adso p ion begins as a
monolaye , becomes mul ilaye ed, and hen, i he po es a e close o he size o he molecules, capilla y
condensa ion occu s, he po es ill wi h adso ba e. Capaci y o a po ous adso ben depends on he po e
olume o i . Howe e , in case o ha ing gas o adso ba e and a empe a u e beyond i s c i ical
empe a u e, physical adso p ion is limi ed o a monolaye . In con as , chemiso p ion occu s when
adso ben and adso ba e o m a chemical bond wi h each o he . Chemiso p ion om a gas adso ba e
usually happens a empe a u es highe han 200 oC and may be slow and i e e sible [39].
3.5.1. Volume ic me hod o gas adso p ion
Du ing he adso p ion o gas in solid, he weigh o he solid inc eases and he p essu e o he gas
dec eases. The e o e, he amoun adso bed can be measu ed om mass o p essu e changes. When he
weigh change is used o measu emen , he echnique is e e ed o as g a ime ic adso p ion me hod.
Al e na i ely, measu emen based on he gas p essu e change is called olume ic adso p ion me hod.
In olume ic me hod, he olume o he sample equi ed o measu emen . The equilib ium adso p ion
iso he m is he plo o p essu e e sus amoun adso bed a a cons an empe a u e.
A schema ic ep esen a ion o olume ic appa a us used o his wo k is shown in igu e 3.13.
Commonly, olume ic appa a uses a e consis ing o wo sides, injec ion side and sample side. The
olumes o hese wo sides a e also equi ed o measu emen s.
Fo measu ing adso p ion a a ce ain p essu e and empe a u e wo s eps should ca ied ou . F is s ep
is o hold he gas inside he injec ion side while he al e (R2) be ween wo sides is closed. Second s ep
is ollowed by opening he R2 al e, and allowing he gas in o he sample side, whe e he adso p ion
akes place.
17
Bulk sepa a ion (adso p ion o 10 w % o mo e om adso ba e) and Pu i ica ion (> 2 w %)
Syn hesis o Pep ide-based Po ous Ma e ials
Expe imen al p ocedu e and esul s 47
Figu e 3.13- Schema ic ep esen a ion o olume ic adso p ion appa a us.
The ini ial p essu e inside injec ion and sample side is se o ze o h ough making acuum in he whole
appa a us. A e ollowing hose wo desc ibed s eps, he adso p ion da a o he i s p essu e poin
can be collec ed. Fo collec ing adso p ion da a o he second p essu e poin , he e a e wo possible
ou es. Fi s ou e is o epea he p ocedu e h ough making ano he acuum be ween each p essu e
poin . Al e na i ely, second ou e is o con inue he p ocedu e wi hou making acuum, which in his
case he inal equilib ium p essu e o p e ious poin is conside ed as he ini ial p essu e o he sample
side.
In his wo k, cumula i e measu emen (second ou e) is used o da a collec ion. Schema ic
ep esen a ion o cumula i e adso p ion measu emen used o wo p essu e poin s is shown on igu e
3.14. The ollowing calcula ion should be conside ed o measu ing he amoun adso bed o his
me hod.
Syn hesis o Pep ide-based Po ous Ma e ials
Re e ences 54
[14] K. A. S. JeongYong Lee, Oma K. Fa ha, John Robe s and S. T. N. and J. T. Hupp, “Me al–o ganic
amewo k ma e ials as ca alys s.pd ,” Chemical Socie y e iews, ol. 38, pp. 1450–1459, 2009.
[15] A. Mo ozan and F. Jaouen, “Me al o ganic amewo ks o elec ochemical applica ions,” Ene gy
& En i onmen al Science, ol. 5, no. 11, p. 9269, 2012.
[16] M. P. Suh, H. J. Pa k, T. K. P asad, and D.-W. Lim, “Hyd ogen s o age in me al-o ganic
amewo ks.,” Chemical e iews, ol. 112, no. 2. pp. 782–835, 08-Feb-2012.
[17] O. Zn, S. S. Kaye, A. Dailly, O. M. Yaghi, and J. R. Long, “Impac o P epa a ion and Handling on he
Hyd ogen S o age P ope ies o MOF-5,” J. Am. Chem. Soc, ol. 129, pp. 14176–14177, 2007.
[18] D. Fa usseng, S. Aguado, and C. Pinel, “Me al-o ganic amewo ks: oppo uni ies o ca alysis.,”
Angewand e Chemie (In e na ional ed. in English), ol. 48, no. 41, pp. 7502–13, Jan. 2009.
[19] Y. Lu, M. Tonigold, B. B edenkö e , D. Volkme , J. Hi zbleck, and G. Langs ein, “A Cobal (II)-
con aining Me al-O ganic F amewo k Showing Ca aly ic Ac i i y in Oxida ion Reac ions,”
Zei sch i ü ano ganische und allgemeine Chemie, ol. 634, no. 12–13, pp. 2411–2417, Oc .
2008.
[20] R. T. Yang, ADSORBENTS:FUNDAMENTALS AND APPLICATIONS. John Wiley & Sons, Inc., 2003.
[21] J.-R. Li, R. J. Kupple , and H.-C. Zhou, “Selec i e gas adso p ion and sepa a ion in me al-o ganic
amewo ks.,” Chemical Socie y e iews, ol. 38, no. 5, pp. 1477–504, May 2009.
[22] R. S aud and J. Kelle , Gas Adso p ion Equilib ia, Expe imen al Me hods and Adso p ion
Iso he ms. Sp inge Science+ Business Media, Inc., Bos on, 2005.
[23] D. B adshaw, J. B. Cla idge, E. J. Cussen, T. J. P io , and M. J. Rosseinsky, “Design, chi ali y, and
lexibili y in nanopo ous molecule-based ma e ials.,” Accoun s o chemical esea ch, ol. 38, no.
4, pp. 273–82, Ap . 2005.
[24] S. Bou elly, P. L. Llewellyn, C. Se e, F. Millange, T. Loiseau, and G. Fé ey, “Di e en adso p ion
beha io s o me hane and ca bon dioxide in he iso ypic nanopo ous me al e eph hala es MIL-
53 and MIL-47.,” Jou nal o he Ame ican Chemical Socie y, ol. 127, no. 39, pp. 13519–21, Oc .
2005.
[25] Y. Bae, K. L. Mul o , H. F os , P. Ryan, S. Punna hanam, L. J. B oadbel , J. T. Hupp, and R. Q.
Snu , “Sepa a ion o CO 2 om CH 4 Using Mixed-Ligand Me al-O ganic F amewo ks,” Langmui ,
no. 18, pp. 8592–8598, 2008.
[26] and J.-M. T. Ge a d Fe ey, F anck Millange, Ma hieu Mo c e e, Ch is ian Se e, Ma ie-Liesse
Double , Jean-Ma c G eneche, “Mixed-Valence Li/Fe-Based Me al–O ganic F amewo ks wi h
Bo h Re e sible Redox and So p ion P ope ies,” Angew. Chem. In . Ed., ol. 46, pp. 3259 –3263,
2007.
[27] G. Hooge s, FUEL CELL TECHNOLOGY HANDBOOK. CRC P ess LLC, 2003.

Syn hesis o Pep ide-based Po ous Ma e ials
Re e ences 55
[28] E. P oie i, F. Jaouen, M. Le è e, N. La ouche, J. Tian, J. He anz, and J.-P. Dodele , “I on-based
ca hode ca alys wi h enhanced powe densi y in polyme elec oly e memb ane uel cells.,”
Na u e communica ions, ol. 2, p. 416, Jan. 2011.
[29] P. Ho cajada, C. Se e, M. Valle -Regí, M. Sebban, F. Taulelle, and G. Fé ey, “Me al-o ganic
amewo ks as e icien ma e ials o d ug deli e y.,” Angewand e Chemie (In e na ional ed. in
English), ol. 45, no. 36. pp. 5974–8, 11-Sep-2006.
[30] W. J. Rie e , K. M. Po , K. M. L. Taylo , and W. Lin, “Nanoscale coo dina ion polyme s o
pla inum-based an icance d ug deli e y.,” Jou nal o he Ame ican Chemical Socie y, ol. 130,
no. 35, pp. 11584–5, Sep. 2008.
[31] M. Fleck and L. Boha ý, “Two no el glycine me al halogenides: ca ena-poly[[[diaquanickel(II)]-di-
mu-glycine] dib omide] and ca ena-poly[[[ e aaquamagnesium(II)]-mu-glycine] dichlo ide].,”
Ac a c ys allog aphica. Sec ion C, C ys al s uc u e communica ions, ol. 61, no. P 9, pp. m412–6,
Sep. 2005.
[32] Y. O. . Toshio Takayama, Shi abe Ohuchida, Yoshio Koike, Masanobu Wa anabe, Daisuke
Hashizume, “S uc u al Analysis o Cadmium–Glycylglycine Complexes S udied by X-Ray
Di ac ion and High Resolu ion _sup_113__sup_Cd and _sup_13__sup_C Solid S a e NMR,”
Bulle in o he Chemical Socie y o Japan, ol. 69, no. 6, p. 1579, 1996.
[33] C. Ma í-Gas aldo, J. E. Wa en, K. C. S ylianou, N. L. O. Flack, and M. J. Rosseinsky, “Enhanced
s abili y in igid pep ide-based po ous ma e ials.,” Angewand e Chemie (In e na ional ed. in
English), ol. 51, no. 44, pp. 11044–8, Oc . 2012.
[34] H.-Y. Lee, J. W. Kamp , K. S. Pa k, and E. N. G. Ma sh, “Co alen Me al−Pep ide F amewo k
Compounds Tha Ex end in One and Two Dimensions,” C ys al G ow h & Design, ol. 8, no. 1, pp.
296–303, Jan. 2008.
[35] J. Rabone, Y.-F. Yue, S. Y. Chong, K. C. S ylianou, J. Bacsa, D. B adshaw, G. R. Da ling, N. G. Be y,
Y. Z. Khimyak, a Y. Ganin, P. Wipe , J. B. Cla idge, and M. J. Rosseinsky, “An adap able pep ide-
based po ous ma e ial.,” Science (New Yo k, N.Y.), ol. 329, no. 5995, pp. 1053–7, Aug. 2010.
[36] R. Fe a i, S. Be ne, C. R. De Ba ba ı, and G. Mendoza-dı, “In e ac ion be ween Glyglu and Ca 2 ’ ,
Pb 2 ' , Cd 2 ' and Zn 2 ' in solid s a e and aqueous solu ion . C ys al s uc u es o poly [ aqua-1 , 2-
k-O-di [ lead ( gly- gluH )] bis ( pe chlo a e )] and poly [ bisglycylglu amic-cadmium ( II )
e ahyd a ,” Ino ganica Chimica Ac a, ol. 339, p. 193, 2002.
[37] D. Bousque , F. Coude , A. G. J. Fossa i, A. V Neima k, A. H. Fuchs, and A. Bou in, “Adso p ion
induced ansi ions in so po ous c ys als : An osmo ic po en ial app oach o mul is abili y and
in e media e s uc u es,” The Jou nal o Chemical Physics, ol. 174706, pp. 1–9, 2013.
[38] J. Zhang, H. Wu, T. J. Emge, and J. Li, “A lexible MMOF exhibi ing high selec i i y o CO(2) o e
N(2), CH(4) and o he small gases.,” Chemical communica ions (Camb idge, England), ol. 46, no.
48, p. 9152, Dec. 2010.
Syn hesis o Pep ide-based Po ous Ma e ials
Re e ences 56
[39] D. Seade and E. J. Henley, SEPARATION PROCESS PRINCIPLES, Second. John Wiley & Sons, Inc.,
2006.