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1. Soft Matter. 2023 Apr 26;19(16):2941-2948. doi: 10.1039/d3sm00273j.

Influence of a CO(2)-switchable additive on the surface and foaming properties 
of a cationic non-switchable surfactant.

Benedix RR(1), Botsch S(1)(2), Preisig N(1), Kovalchuk V(3), Jessop PG(2), 
Stubenrauch C(1).

Author information:
(1)Institute of Physical Chemistry, University of Stuttgart, Stuttgart, Germany. 
cosima.stubenrauch@ipc.uni-stuttgart.de.
(2)Department of Chemistry, Queen's University, Kingston, Ontario, Canada.
(3)Institute of Biocolloid Chemistry of the National Academy of Sciences of 
Ukraine, Kyiv, Ukraine.

Switchable materials in general and CO2-switchable materials in particular are 
of great interest in environmental research. The replacement of common 
non-switchable materials (solutions, solvents, surfactants, etc.) with their 
switchable counterparts has a great potential to make processes more 
environmentally friendly by enhancing reusability and circularity and thus 
reducing energy costs and material consumption. Inspired by this, the present 
work deals with the surface and foaming properties of aqueous solutions of a 
non-switchable surfactant in presence of a CO2-switchable additive. A 1 : 1 and 
a 1 : 5 (molar ratios) mixture of the non-switchable surfactant C14TAB 
(tetradecyltrimethylammonium bromide) and the CO2-switchable additive TMBDA 
(N,N,N,N-tetramethyl-1,4-butanediamine) were investigated. It was found that 
surface properties, foamability, and foam stability can be changed by switching 
the additive with CO2 as a trigger. This observation can be explained by the 
fact that TMBDA is surface active in its unprotonated, i.e. neutral form, which 
disturbs the tight packing of the surfactant molecules on the surface. As a 
consequence, foams generated with surfactant solutions containing the neutral 
TMBDA are less stable than their TMBDA-free counterparts. On the other hand, the 
switched diprotonated additive is a 2 : 1 electrolyte with hardly any surface 
activity and thus does not affect surface and foam properties.

DOI: 10.1039/d3sm00273j
PMID: 37013656


2. Biosens Bioelectron. 2018 Feb 15;100:161-168. doi: 10.1016/j.bios.2017.08.056.
 Epub 2017 Aug 30.

Novel amine-functionalized iron trimesates with enhanced peroxidase-like 
activity and their applications for the fluorescent assay of choline and 
acetylcholine.

Valekar AH(1), Batule BS(2), Kim MI(3), Cho KH(4), Hong DY(1), Lee UH(1), Chang 
JS(5), Park HG(6), Hwang YK(7).

Author information:
(1)Research Group of Nanocatalysts, Korea Research Institute of Chemical 
Technology (KRICT), Daejeon 34114, Republic of Korea; Department of Advanced 
Materials and Chemical Engineering, University of Science and Technology (UST), 
217 Gajeong-Ro, Yuseong, Daejeon 34113, Republic of Korea.
(2)Chemical & Biomolecular Engineering (BK21+ Program), KAIST, 291 Deahak-ro, 
Yuseong-gu, Daejeon 34141, Republic of Korea.
(3)Department of BioNano Technology, Gachon University, 1342 Seongnamdae-ro, 
Sujeong-gu, Seongnam, Gyeonggi 13120, Republic of Korea.
(4)Research Group of Nanocatalysts, Korea Research Institute of Chemical 
Technology (KRICT), Daejeon 34114, Republic of Korea.
(5)Research Group of Nanocatalysts, Korea Research Institute of Chemical 
Technology (KRICT), Daejeon 34114, Republic of Korea; Department of Chemistry, 
Sungkyunkwan University, Suwon 16419, Republic of Korea.
(6)Chemical & Biomolecular Engineering (BK21+ Program), KAIST, 291 Deahak-ro, 
Yuseong-gu, Daejeon 34141, Republic of Korea. Electronic address: 
hgpark@kaist.ac.kr.
(7)Research Group of Nanocatalysts, Korea Research Institute of Chemical 
Technology (KRICT), Daejeon 34114, Republic of Korea; Department of Advanced 
Materials and Chemical Engineering, University of Science and Technology (UST), 
217 Gajeong-Ro, Yuseong, Daejeon 34113, Republic of Korea. Electronic address: 
ykhwang@krict.re.kr.

We herein describe novel amine-grafted metal-organic frameworks (MOFs) as a 
promising alternative to natural peroxidase enzyme and their applications for a 
fluorescent assay of choline (Cho) and acetylcholine (ACh). Among diverse 
amine-functionalized MOFs, N,N,N',N'-tetramethyl-1,4-butanediamine 
(TMBDA)-functionalized MIL-100(Fe) (TMBDA-MIL-100(Fe)) exhibited the highest 
peroxidase activity by developing intense fluorescence from Amplex UltraRed 
(AUR) in the presence of H2O2, which was presumably due to the synergetic effect 
of the enhanced negative potential and precisely controlled molecular size of 
the grafted diamine. Based on the excellent peroxidase-like activity of 
TMBDA-MIL-100(Fe), choline and ACh were reliably determined down to 0.027 and 
0.036µM, respectively. Furthermore, practical applicability of this strategy was 
successfully demonstrated by detecting choline and ACh in spiked samples of milk 
and serum, respectively. This work highlights the advantages of amine-grafted 
MOFs for the preparation of biomimetic catalysts, extending their scope to 
biosensor applications.

Copyright © 2017 Elsevier B.V. All rights reserved.

DOI: 10.1016/j.bios.2017.08.056
PMID: 28888178 [Indexed for MEDLINE]


3. Dalton Trans. 2015 Jul 7;44(25):11470-81. doi: 10.1039/c5dt01355k.

New organically templated thiocyanatocadmates and chlorocuprate(II): synthesis 
and structural characterization.

Guo B(1), Zhang X, Yu JH, Xu JQ.

Author information:
(1)College of Chemistry, State Key Laboratory of Inorganic Synthesis and 
Preparative Chemistry, Jilin University, Changchun, Jilin 130012, China. 
jhyu@jlu.edu.cn xjq@mail.jlu.edu.cn.

With various organic base molecules as the countercations, five new 
thiocyanatocadmates [H2(tmen)][Cd(SCN)4] (tmen = 
N,N,N',N'-tetramethylethylenediamine) 1, [H2(tmba)][Cd2(SCN)6] (tmba = 
N,N,N',N'-tetramethyl-1,4-butanediamine) 2, [H2(teen)][Cd2(SCN)6] (teen = 
N,N,N',N'-tetra-ethylethylenediamine) 3, [H(amp)][Cd(SCN)2(CH3COO)] (amp = 
2-amino-6-methylpyridine) 4 and [H(abp)]4[Cd(SCN)4]SO4·H2O (abp = 
2-amino-6-bromopyridine) 5, and one new chlorocuprate(II) [H2(cha)][CuCl4] (cha 
= 1,4-cyclohexanediamine) 6 were obtained from a series of simple 
room-temperature self-assemblies at pH = 2 or 6.5. X-ray single-crystal 
diffraction analysis reveals that (i) templated by [(CH3)2NH(CH2)2NH(CH3)2](2+) 
(H2(tmen)(2+)), the anion [Cd(SCN)4](2-) in 1 shows a 1-D linear single-chain 
structure, whereas templated by [(CH3)2NH(CH2)4NH(CH3)2](2+) (H2(tmba)(2+)), the 
anion [Cd2(SCN)6](2-) in 2 shows a 1-D linear double-chain structure. The number 
of C atoms between the two N atoms in the templating agent controls the width of 
the anionic chain through the N(amino)-H···N(SCN) interactions; (ii) templated 
by [(C2H5)2NH(CH2)2NH(C2H5)2](2+) (H2(teen)(2+)), the anion [Cd2(SCN)6](2-) in 3 
exhibits a 3-D open-framework structure, which is based on zigzag anionic 
chains. A direct change of the substituent group from -CH3 to -C2H5 alters 
indirectly the shape of the anionic chain from a linear shape to a zigzag shape; 
(iii) 4 shows a 3-D supramolecular network structure, which is built up from the 
1-D zigzag anionic structures by the H(amp)(+) molecules via N-H···O 
interactions. The formation of the zigzag chain derives from the chelation of 
the CH3COO(-) groups to the Cd(2+) centers; (iv) 5 is indeed a double salt of 
[H(abp)]2[Cd(SCN)4] and [H(abp)]2SO4. SO4(2-) and H(abp)(+) form a 
supramolecular aggregation. Surrounded by the aggregations, the anion 
[Cd(SCN)4](2-) only shows a dinuclear structure; and (v) templated by 
H2(cha)(2+), the anion [CuCl4](2-) in 6 displays a 2-D perovskite layer 
structure. The photoluminescence analysis indicates that upon excitation (λ(ex) 
= 335 nm for 4, λ(ex) = 395 nm for 5), and emit light (λ(em) = 365 nm for 4, 
λ(em) = 470 nm for 5), which can be seen clearly under the UV lamp.

DOI: 10.1039/c5dt01355k
PMID: 26028497