Nanoscale
COMMUNICATION
Ci e his: Nanoscale, 2024, 16, 9742
Recei ed 21s Ma ch 2024,
Accep ed 29 h Ap il 2024
DOI: 10.1039/d4n 01261e
sc.li/nanoscale
Consecu i e one-po alkyne semihyd ogena ion/
alkene dioxygena ion eac ions by P (II)/Cu(II)
single-chain nanopa icles in g een sol en †
Jokin Pinacho-Olaci egui,
a,b
Es e Ve de-Ses o,
a,c
Daniel Ta on
b
and
José A. Pomposo *
a,c,d
He e obime allic P (II)/Cu(II) single-chain polyme nanopa icles
(SCNPs) we e sequen ially syn hesized om a polyme ic p ecu so
ea u ing bo h α-diazo-β-ke oes e and naked β-ke oes e unc-
ional g oups. Pho oac i a ed ca bene gene a ion a λ
exc
= 365 nm
om α-diazo-β-ke oes e moiei ies was igge ed o bonding P (II)
ions om dichlo o(1,5-cyclooc adiene)P (II) o he polyme ic p e-
cu so , whe eas Cu(II) ions we e subsequen ly inco po a ed ia Cu
(II)-(β-ke oes e )
2
complex o ma ion using Cu(II) ace a e. Bo h
in achain P (II) bonding and Cu(II) complexa ion we e ound o
con ibu e o he olding o he polyme ic p ecu so gene a ing P
(II)/Cu(II)-SCNPs as e idenced by in a ed spec oscopy, size exclu-
sion ch oma og aphy and dynamic ligh sca e ing. These he e o-
bime allic SCNPs p o ed highly efficien as so nanoca alys s o
he consecu i e one-po alkyne semihyd ogena ion/alkene dioxy-
gena ion eac ions a oom empe a u e in N-bu ylpy olidone, as
a non- oxic al e na i e sol en o N,N-dime hyl o mamide.
Me al–ligand coo dina ion allows in amolecula olding o
ligand-deco a ed disc e e syn he ic polyme chains o me allo-
olded single-chain polyme nanopa icles (SCNPs).
1
SCNPs
a e in a-chain c oss-linked single polyme chains wi h mani-
old p omising applica ions, mainly as ca alys s, nanosenso s
and d ug nanoca ie s.
2,3
In gene al, in amolecula olding o
he isola ed syn he ic chains gene a es locally compac zones
wi hin he SCNPs o efficien immobiliza ion o ca aly ic
ac i e species, luminopho es o d ugs.
4
To some ex en , he
in achain olding o disc e e syn he ic polyme chains o
SCNPs esembles he olding o ce ain p o eins o hei
p ecise unc ional con o ma ion (i.e., na i e s a e).
5
In pa icu-
la , me allo- olded SCNPs le e age he dual ole played by he
me al: as a olding elemen ia in a-chain me al–ligand
coo dina ion, and as an immobilized unc ional cen e o
subsequen ca alysis.
6
The numbe and ca aly ic applica ions
o me allo- olded SCNPs as enzyme-mime ic nanoen i ies ha e
g own signi ican ly in ecen yea s.
7,8
In a seminal wo k,
Te ashima e al. epo ed Ru-con aining amphiphilic SCNPs o
ca alyse he educ ion o cyclohexanone o cyclohexanol in
wa e .
9
Pomposo e al. pionee ed he in oduc ion o me allo-
olded Cu(II)-con aining SCNPs showing ca aly ic selec i i y in
alkyne homocoupling eac ions,
6
and single-chain globules
mimicking he mo phology and polyme ase ac i i y o me al-
loenzymes.
10
He e al. p epa ed me allo- olded SCNPs con ain-
ing Ni- hiola e complexes showing excellen he mal s abili y
unde ae obic condi ions and excellen ac i i y and selec i i y
du ing he pho oca aly ic educ ion o CO
2
o CO.
11
Zimme man e al. de eloped “clickase”SCNPs displaying
enzyme-like “click”ca alysis in i o and enabling efficien cell
su ace glycan edi ing.
12
Ta on e al. epo ed SCNPs con ain-
ing Ag(I)-N-he e ocyclic ca bene (NHC) linkages as NHC p e-
ca alys s o he benzoin condensa ion eac ion.
13
Yang e al.
syn hesized me al-con aining SCNPs in concen a ed solu ions
a oom empe a u e ( . .) by in oducing elec os a ic epul-
sion and in a-chain c osslinking by coo dina ion wi h Cu(II)
o Fe(II)o Fe(III) ions.
14
Tan e al. syn hesized enzyme-mime ic
SCNPs wi h chi al Fe(II)-oxazoline complexes o efficien asym-
me ic sul a-Michael addi ion o hiols o α,β-unsa u a ed
ke ones in wa e a . .
15
Mo e ecen ly, Pomposo e al. de el-
oped a me hod o upcycling poly( inyl chlo ide) (PVC) was e o
efficien ca aly ic Cu(II)-con aining SCNPs.
16
Cu en ad ances
in ca alysis u ilizing SCNPs ha e been ecen ly e iewed by he
Ba ne -Kowollik eam.
17
Howe e , in oduc ion o a leas wo dis inc me al species
in SCNPs al hough highly desi able is s ill syn he ically chal-
lenging, since i equi es designing a polyme chain able o
complex bo h me al species while main aining hei o hogon-
ali y. In a pionee ing wo k, Lemcoffe al. syn hesized Rh(I)/
†Elec onic supplemen a y in o ma ion (ESI) a ailable. See DOI: h ps://doi.o g/
10.1039/d4n 01261e
a
Cen o de Física de Ma e iales (CSIC –UPV/EHU) –Ma e ials Physics Cen e MPC,
P°Manuel La dizabal 5, E-20018 Donos ia, Spain.
E-mail: [email p o ec ed]
b
Labo a oi e de Chimie des Polymè es O ganiques (LCPO), Uni e si é de Bo deaux
INP-ENSCBP, 16 a . Pey Be land, 33607 Pessac cedex, F ance
c
IKERBASQUE –Basque Founda ion o Science, Plaza Euskadi 5, E-48009 Bilbao,
Spain
d
Depa amen o de Políme os y Ma e iales A anzados: Física, Química y Tecnología.
Uni e si y o he Basque Coun y (UPV/EHU), P°Manuel La dizabal 3,
E-20800 Donos ia, Spain
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I (I) SCNPs al hough hei ca aly ic p ope ies we e no e alu-
a ed.
18
Subsequen ly, Ba ne -Kowollik e al. syn hesized he -
e obime allic Eu(III)/P (II)-SCNPs
19
and Au(I)/Y(III)-SCNPs
20
in
which only one o he wo me al ions, P (II) o Au(I), was used
o ca alysis, while he o he was employed o sensing o in a-
chain olding (Eu(III)o Y(III), espec i ely). Mo e ecen ly, he
same g oup deco a ed SCNPs olded h ough e ocene uni s
wi h Pd(II) a oms, which p o ed o be an ac i e ca alys o he
in amolecula hyd oamina ion o an aminoalkyne.
21
Ad anced he e obime allic nanoca alys s o ca ying ou
mul is ep chemical p ocesses in a single eac ion essel a e
cu en ly o g ea in e es in academia and indus y.
22
O en,
howe e , majo cos s o many consume p oduc s syn hesized
in mul is ep p ocesses a e incu ed in he pu i ica ion and iso-
la ion o in e media es.
23
Addi ionally, eplacemen o oxic
o ganic sol en s by g een sol en s has a ac ed signi ican
in e es .
24
To he bes o ou knowledge, bime allic SCNPs ha
would allow consecu i e one-po eac ions o be pe o med in
a g een sol en ha e no been epo ed. To ill his gap, we
epo he ein he p oo o concep o he e obime allic SCNPs
h ough he syn hesis o P (II)/Cu(II)-SCNPs, since hese SCNPs
could show syne gis ic effec s o ca alysis and o he appli-
ca ions. We show ha hese can se e as ad anced so nano-
ca alys s o pe o m consecu i e one-po alkyne semihyd o-
gena ion/alkene dioxygena ion eac ions in N-bu ylpy olidone
(NBP) as a g een sol en .
The syn he ic p ocedu e ollowed in his wo k o p oduce P
(II)/Cu(II)-SCNPs is depic ed schema ically in Fig. 1. Ini ially,
he monome s (2-ace oace oxy)e hyl me hac yla e (AEMA) and
me hyl me hac yla e (MMA) we e copolyme ized ia e e sible
addi ion agmen a ion chain- ans e (RAFT) polyme iza ion
6
yielding he andom copolyme P0 (Fig. 1A). Subsequen ly, P0
wi h a con en o β-ke oes e unc ional g oups o 30 mol%, a
weigh -a e age molecula weigh o M
w
= 73.6 kDa and a
na ow dispe si y o Đ= 1.17 was pos - unc ionalized wi h
19 mol% o α-diazo-β-ke oes e unc ional mo i s-using p-ca -
boxybenzenesul onazide (p-CBSA) as he diazo ans e
eagen -
25
lea ing 11 mol% β-ke oes e unc ional g oups
un eac ed (see Fig. 1B and ESI†). Upon he diazo ans e eac-
ion, he esul ing polyme ic p ecu so P1 showed M
w
=
75.3 kDa and Đ= 1.15, in e y good ag eemen wi h he
expec ed M
w
(75.4 kDa) based on i s chemical composi ion.
Fig. 1 Schema ic illus a ion o he syn hesis o P (II)/Cu(II)-SCNPs: (A) P epa a ion o a andom copolyme P0 con aining naked β-ke oes e unc-
ional g oups (30 mol%) ia e e sible addi ion agmen a ion chain- ans e (RAFT) polyme iza ion (MMA = me hyl me hac yla e; AEMA = (2-ace oa-
ce oxy)e hyl me hac yla e; AIBN = azobisisobu y oni ile; CPDB = 2-cyanop op-2-yl-di hiobenzoa e; E OAc = e hyl ace a e). (B) Deco a ion o P0
wi h α-diazo-β-ke oes e unc ional g oups (19 mol%) o gi e polyme ic p ecu so P1 (p-CBSA = p-ca boxybenzenesul onazide; E
3
N = ime hyl-
amine; CH
2
Cl
2
= dichlo ome hane). (C) Folding o p ecu so P1 a high dilu ion ia pho oac i a ed ca bene gene a ion a λ
exc
= 365 nm in he p es-
ence o dichlo o(1,5-cyclooc adiene)P (II) (P (COD)Cl
2
) o gene a e P (II)-SCNPs (DMF = dime hyl o mamide). (D) Addi ional olding o P (II)-SCNPs
a high dilu ion ia Cu(II) complexa ion by esidual β-ke oes e unc ional g oups o P (II)-SCNPs (11 mol%) o gi e he e obime allic P (II)/Cu(II)-
SCNPs (Cu(OAc)
2
= Cu(II) ace a e).
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In a ed (IR) spec oscopy measu emen s con i med he
appea ance o he cha ac e is ic in a ed ib a ion band o he
diazo moie ies cen ed a ν≈2200 cm
−1
(Fig. 2A).
He e obime allic P (II)/Cu(II)-SCNPs we e sequen ially syn-
hesized om P1 con aining bo h α-diazo-β-ke oes e and
un eac ed β-ke oes e unc ional g oups. Thus, P1 was i s
i adia ed wi h UV ligh a λ
exc
= 365 nm a high dilu ion in he
p esence o dichlo o(1,5-cyclooc adiene)P (II) (P (COD)Cl
2
) o
gene a e he highly eac i e ca bene species om he α-diazo-
β-ke oes e unc ional g oups and o p omo e in achain c oss-
linking ia P (II) bonding (see Fig. 1C).
Success ul olding o P1 o P (II)-SCNPs was con i med
h ough size exclusion ch oma og aphy (SEC) and dynamic
ligh sca e ing (DLS) measu emen s, whe eas he IR spec um
o P (II)-SCNPs showed he disappea ance o he cha ac e is ic
diazo IR ib a ion band a e 1 h o UV i adia ion (see
Fig. 2A). SEC esul s showed an inc ease in e en ion ime,
hence, a educ ion in hyd odynamic size o he P (II)-SCNPs
when compa ed o P1 (Fig. 2B). The a e age hyd odynamic dia-
me e o P1,D
h
= 12.5 nm as de e mined by DLS, was ound o
dec ease o D
h
= 9.9 nm upon o ma ion o he P (II)-SCNPs
(Fig. 2C). In a inal s ep, Cu(II) ions we e inco po a ed using
Cu(II) ace a e
6
o o m –in an o hogonal manne –Cu(II)-
(β-ke oes e )
2
complexes om ee β-ke oes e unc ional
g oups o he P (II)-SCNPs (11 mol%) affo ding he he e obi-
me allic P (II)/Cu(II)-SCNPs (see Fig. 1D). Success ul
(addi ional) olding o P (II)-SCNPs in o P (II)/Cu(II)-SCNPs
was e ealed by SEC (Fig. 2B) and DLS (Fig. 2C) analyses. The
a e age hyd odynamic diame e o P (II)/Cu(II)-SCNPs was
ound o be D
h
= 8.6 nm. The less p onounced educ ion in
hyd odynamic size upon he second olding e en can be
a ibu ed o he educed deg ees o eedom a ailable a e
Fig. 2 (A) In a ed (IR) spec a o polyme ic p ecu so P1,P (II)-SCNPs and P (II)/Cu(II)-SCNPs. (B) Size exclusion ch oma og aphy (SEC) aces
(diffe en ial e ac i e index (DRI) de ec o , DMF, 1 mL min
−1
)o P1,P (II)-SCNPs and P (II)/Cu(II)-SCNPs. (C) Dynamic ligh sca e ing (DLS) size dis-
ibu ions o P1,P (II)-SCNPs and P (II)/Cu(II)-SCNPs (see ESI† o de ails).
Table 1 Compa ison o P (II)/Cu(II)-SCNPs o diffe en con ol ca alys s o consecu i e alkyne semihyd ogena ion/alkene dioxygena ion eac ions
a . . (see ESI†)
a
Syn hesized-as a con ol- om P1 acco ding o he condi ions p o ided in Fig. 1C wi hou P (COD)Cl
2
.
b
Syn hesized-as a con ol- om P1-SCNPs
(en y 4) acco ding o he condi ions o Fig. 1D (NHPI = N-hyd oxyph halimide).
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he i s P (II)-induced compac ion.
26
Complexa ion o Cu(II)
ions by he esidual β-ke oes e g oups was con i med om
he IR spec um o he P (II)/Cu(II)-SCNPs. Fig. 2A indeed
shows he cha ac e is ic ib a ion bands loca ed a ca.
1600 cm
−1
(s e ching C O ib a ion, enol au ome bonded
o Cu) and ca. 1515 cm
−1
(s e ching C C ib a ion, enol au-
ome bonded o Cu).
6
Induc i ely coupled plasma-mass spec-
ome y (ICP-MS) measu emen s showed a con en o P (II)
and Cu(II) ions in he P (II)/Cu(II)-SCNPs o 9.7 μgmg
−1
and
9.5 μgmg
−1
, espec i ely (see ESI†).
Wi h he P (II)/Cu(II)-SCNPs in hand, we en isioned o use
hem as ad anced so nanoca alys s o consecu i e one-po
(incompa ible) eac ions. To his end, we a ge ed he p epa-
a ion o β-ke o-N-alkoxyph halimides, known in e media es o
g ea u ili y o he pha maceu ical and ag icul u al indus-
ies,
27
by using phenylace ylene subs a es.
Table 1 shows a compa ison o P (II)/Cu(II)-SCNPs wi h
diffe en con ol ca alys s o he consecu i e one-po phenyl-
ace ylene (1a) semihyd ogena ion/s y ene (2a) dioxygena ion
wi h ai and N-hyd oxyph halimide (NHPI) a . . o gi e he
β-ke o-N-alkoxyph halimide 3a as he a ge p oduc (see ESI†).
Wi h P (COD)Cl
2
(1 mol% P (II)) 1a was ans o med in o 2a in
DMF wi h 60% yield, along wi h a la ge po ion o 1a comple-
ely hyd ogena ed o e hylbenzene (Table 1, en y 1). As
expec ed, Cu(OAc)
2
(1 mol% Cu(II)) p o ed inefficien o he
semihyd ogena ion o 1a (Table 1, en y 2). A combina ion o
P (COD)Cl
2
o he semihyd ogena ion eac ion, and sub-
sequen ly adding Cu(OAc)
2
o he dioxygena ion eac ion
Fig. 3 Consecu i e one-po alkyne semihyd ogena ion/alkene dioxygena ion eac ions ca alysed by P (II)/Cu(II)-SCNPs in NBP a . .: (A) E olu ion
o he concen a ion o phenylace ylene (1a), s y ene (2a) and e hylbenzene (seconda y p oduc ) du ing he alkyne semihyd ogena ion eac ion. (B)
Reac ion kine ics o he semihyd ogena ion eac ion as ollowed by
1
H NMR spec oscopy h ough he disappea ance o alkyne p o on o 1a
deno ed as a, and he concomi an appea ance o he inylic p o ons deno ed as b,cand do 2a. No ice he p esence o a small peak (deno ed as
e) coming om e hylbenzene a e 210 min o eac ion ime. (C) E olu ion o he amoun o in e media e 2a and p oduc 3a (2-(2-oxo-2-pheny-
le hoxy)isoindoline-1,3-dione) du ing he dioxygena ion eac ion wi h ai and N-hyd oxyph halimide (NHPI). (D) Reac ion kine ics o he dioxygena-
ion o in e media e 2a as ollowed by
1
H NMR spec oscopy h ough he disappea ance o he inylic p o ons o 2a, and he simul aneous appea -
ance o he me hylene p o ons deno ed as o 3a.
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gi es a yield o 2a and 3a o 58% and 62%, espec i ely
(Table 1, en y 3). P (II)-SCNPs (i.e., 0.13 mol% P (II)) p o ided
2a in 90% yield (Table 1, en y 5) whe eas bo h P1-SCNPs syn-
hesized–as a con ol– om P1 wi hou P (COD)Cl
2
and Cu(II)-
SCNPs syn hesized also as a con ol om P1-SCNPs, we e
o ally inefficien (Table 1, en ies 4 and 6). A combina ion o
P (II)-SCNPs o he semihyd ogena ion eac ion, and sub-
sequen ly addi ion o Cu(II)-SCNPs (0.41 mol% Cu(II)) o he
dioxygena ion eac ion p o ided 2a and 3a in 93% and 82%
yield, espec i ely (Table 1, en y 7). Rema kably, he he e obi-
me allic P (II)/Cu(II)-SCNPs (0.14 mol% P (II) and 0.43 mol%
Cu(II)) allowed he consecu i e one-po semihyd ogena ion/
dioxygena ion eac ion o be ca ied ou in DMF wi h excep-
ional selec i i y and yield (Table 1, en y 8). Mo eo e , a
simila efficiency and selec i i y was ound o he he e obime-
allic P (II)/Cu(II)-SCNPs when he consecu i e one-po semi-
hyd ogena ion o 1a/dioxygena ion o 2a wi h ai and NHPI
was ca ied ou in NBP as a g een sol en o eplace oxic DMF.
Fig. 3A shows he ans o ma ion o 1a in o 2a o e ime
du ing he semihyd ogena ion eac ion in NBP, as moni o ed
by
1
H NMR spec oscopy. The kine ics o his eac ion was ol-
lowed h ough he disappea ance o he alkyne p o on o 1a,
deno ed as ain Fig. 3B and he concomi an appea ance o he
inylic p o ons, deno ed as b,cand do 2a (Fig. 3B). In he
la e s ages, i.e., a e 210 min o eac ion ime, hyd ogena ion
o 2a o e hylbenzene (seconda y p oduc ) akes place (see
Fig. 3B). A e 4 h o eac ion ime, he con e sion o 1a
eached comple ion wi h a inal yield in 2a o 95%. The u n-
o e numbe (moles o p oduc pe mole o ca alys , TON) o
he P (II)/Cu(II)-SCNPs in he semihyd ogena ion eac ion was
TON = 679 (a alue 10 imes highe han ha o P (COD)Cl
2
a
1 mol% P (II), see ESI, Table S3†). Wi hou isola ion o 2a, he
c ude p oduc o he semi-hyd ogena ion eac ion con aining
he bime allic P (II)/Cu(II)-SCNPs was used o he dioxygena-
ion o 2a wi h ai and NHPI a . . in he same eac ion essel.
Fig. 3C illus a es he consump ion o 2a and he gene a ion o
he β-ke o-N-alkoxyph halimide 3a, as he a ge p oduc , o e
eac ion ime. Also in his case, he kine ics o he dioxygena-
ion eac ion in NBP was di ec ly moni o ed by
1
H NMR spec-
oscopy h ough he disappea ance o he inylic p o ons,
deno ed as b,cand do 2a (Fig. 3D) and he simul aneous
appea ance o he me hylene p o ons deno ed as in Fig. 3D
o 3a. A e 7 h o eac ion, he con e sion o 2a was nea ly
comple e and he yield o 3a was 80%. The u no e numbe o
he P (II)/Cu(II)-SCNPs in he dioxygena ion eac ion was TON
= 186. This alue is 30- old highe han ha co esponding o
he classical p ocedu e
27
in ol ing Cu(OAc)
2
as ca alys s (see
Table S3†).
Finally, we in es iga ed he subs a e scope o he consecu-
i e one-po alkyne semihyd ogena ion/alkene dioxygena ion
eac ions ca alysed by P (II)/Cu(II)-SCNPs in NBP (see
Scheme 1). Subs i u ed phenylace ylene a he pa a-posi ion
wi h a me hoxy g oup ga e he β-ke o-N-alkoxyph halimide 3b
in 82% isola ed yield. The eac ion o phenylace ylene bea ing
a b omine a om a me a-posi ion p oduced he co esponding
β-ke o-N-alkoxyph halimide 3c in 78% isola ed yield. The in o-
duc ion o a i luo ome hyl sub i uen in phenylace ylene a
he pa a-posi ion affo ded he β-ke o-N-alkoxyph halimide 3d
in 84% isola ed yield. In con as , 4-e hynylpy idine ailed o
eac unde ou eac ion condi ions du ing he dioxygena ion
eac ion, which we a ibu e o he deac i a ion o he Cu(II)
ca aly ic si es induced by he p esence o he ni ogen a om in
he a oma ic ing. Fu he wo k–which is ou side he scope o
his communica ion–is gua an eed o gain insigh in o he
comple e eac ion mechanism (a en a i e mechanism is p o-
ided in Table S4†).
Conclusions
We epo bime allic SCNPs as highly efficien so nanoca a-
lys s allowing consecu i e one-po (incompa ible) eac ions o
be pe o med a . . in a g een sol en . Fo his pu pouse, a
polyme ic p ecu so , P1, con aining bo h α-diazo-β-ke oes e
and naked β-ke oes e unc ional mo i s was a ionally
designed. P (II) and Cu(II) ions we e sequen ially added no
only o igge in a-chain olding o P1 chains a high
dilu ion, bu also o ins all wo dis inc ype o me allic species
o consecu i e ca aly ic eac ions. Efficien compac ion was
e ealed by combining IR, SEC and DLS measu emen s, yield-
ing ca aly ically ac i e P (II)/Cu(II)-SCNPs. This unique he e o-
bime allic so nanoca alys was shown o be highly efficien
o consecu i e one-po alkyne semihyd ogena ion/alkene diox-
ygena ion eac ions a . . in NBP, as a non- oxic al e na i e
sol en o DMF, affo ding β-ke o-N-alkoxyph halimides as
in e media es o g ea u ili y o he pha maceu ical and ag i-
cul u al indus ies. C i ically, his wo k pa es he way o mul i-
s ep chemical eac ions in a single eac ion essel wi h
complex mul i-me allic SCNPs as ad anced nanoca alys s.
Scheme 1 Subs a e scope o he consecu i e one-po alkyne semihy-
d ogena ion/alkene dioxygena ion eac ions ca alysed by P (II)/Cu(II)-
SCNPs in NBP a . .
a
Isola ed yield.
b
Dioxygena ion o in e media e 2e
did no ake place.
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Conflic s o in e es
The e a e no con lic s o decla e.
Acknowledgemen s
We g a e ully acknowledge G an PID2021-123438NB-I00
unded by MCIN/AEI/10.13039/501100011033 and “ERDF A
way o making Eu ope”, G an TED2021-130107A-I00 unded
by MCIN/AEI/10.13039/501100011033 and Unión Eu opea
“Nex Gene a ionEU/PRTR”and G an IT-1566-22 om Eusko
Jau la i za (Basque Go e nmen ). E.V.-S. acknowledges inan-
cial suppo om RyC p og am (RYC2022-037590-I). The
au ho s since ely hank Da ide A ena o echnical suppo .
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