Tertiary Amine Units Research Articles

Organocatalytic domino formation of (3R,3aS,9bR)-configured 3-aryl-3a-benzamido-1,3a,4,9b-tetrahydrochromeno[4,3-b]pyrroles in carbon dioxide medium

Asymmetric cycloaddition/intramolecular rearrangement domino reaction of 2-(2-hydroxybenzylideneamino)- malonates with 4-arylidene-2-phenyloxazol-5(4H)-ones can be efficiently carried out in sub- or supercritical carbon dioxide to afford (3R,3aS,9bR)-3-aryl-3a-benzamido-4-oxo-1,3a,4,9b-tetrahydrochromeno[4,3-b]pyrrole-2,2(3H)- dicarboxylates in high yields with up to 99% ee. Excellent stereoinduction is provided in this process by the use of bifunctional hybrid organocatalyst consisting of squaramide (thiourea) and chiral tertiary amine units.

PH-responsive polyaryl sulfide sulfone amide membrane containing tertiary amine unit: Oxidation and reversible acid-base treatment

Developing functional membranes with switchable pores for the separation of contaminants with different sizes has been challenging due to the lack of novel materials with adaptable and adjustable structures. Polymers containing the tertiary amine (TA) unit can be transformed via oxidation into amine oxide (AO) structure that can modulate the membrane pore size. In this study, new monomers containing pH-responsive TA units and diacyl chloride containing reducible thioether (-S-) groups were used to yield pore-size-adjustable membrane resin polyarylene sulfide sulfone amide/amide tertiary amine (PASSA/ATA) at room temperature. By varying the polymerization ratio of the reaction solution, membranes could be prepared directly through non-solvent induce phase separation (NIPS) method without extra treatment. By oxidizing the TA units to AO through acid condition (H2O2/H2SO4/CH3COOH), the PASSA/ATA membrane can be switched from ultrafiltration to loose-nanofiltration with the rejection of RO16 and rhodamine B increased from 18.4% to 34.3 % (pristine membrane) to 91.7 % and 98.5 %. The permeance and rejection rate of the oxidized membrane were found to recover to the initial state after alkali-treatment. The mechanism of the switchable pore size was elucidated by dissipative particle dynamics (DPD) simulations. Interestingly, the oxidized PASSA/ATA membrane showed good organic solvent resistance and in nanofiltration performance, as it was capable of retaining about 95 % of Congo red in N,N-dimethylformamide (DMF) with permeance of about 10 L m−2 h−1 bar−1. This work presents a facile and low-carbon approach to develop novel membranes with multiple filtration capabilities, potentially applicable in various separation processes.

Adaptable Polyurethane Networks Containing Tertiary Amines as Intrinsic Bond Exchange Catalyst

AbstractVitrimers exhibit unique properties, such as thermal recyclability akin to thermoplastics, while structurally mirroring thermosets in terms of strength, durability, and chemical resistance. However, a significant limitation of these materials is their dependence on an external catalyst. Consequently, this research aims to develop vitrimer materials that incorporate an intrinsic catalyst, thus maintaining excellent thermomechanical properties and recyclability. Polyaddition polymerization is employed to synthesize the desired polymer, incorporating a self‐synthesized tertiary amine unit, (bis(2‐hydroxyethyl)‐3,3′‐((2‐(dimethylamino)ethyl)azanediyl)dipropanoate) (N‐diol), as an internal catalyst for transcarbamoylation and potential transesterification reactions. The resulting polymer, with a gel content of 97% and a glass transition temperature of 29 °C, is fabricated into test samples for comprehensive thermal and mechanical evaluations. The material demonstrates an initial Young's modulus of 555 MPa, retaining 81% of this value after two recycling processes. Additionally, using stress relaxation analysis (SRA), a topology freezing temperature of 82 °C, indicative of the characteristic Arrhenius‐like relaxation behavior, is identified with a bond exchange activation energy of 163 kJ mol−1.

Water‐Soluble Hyperbranched Polyamidoamine Bearing Viologen Groups toward Electrochromic/Electrofluorochromic Dual‐Mode Aqueous Phase Devices

AbstractThe health and environmental concerns drive the exploration of electro‐optical materials featuring aqueous processability and environmental friendliness. This work presents a water‐soluble electroactive hyperbranched polyamidoamine toward electrochromic (EC)/electrofluorochromic (EFC) dual‐mode aqueous phase devices. The resultant polymer bearing viologen groups exhibit reversible electroactivity and desirable EC properties (ΔT% = 71.7%, coloration efficiency (CE) = 216 cm2 C−1). The aggregation‐induced quenching as well as the energy transfer between the electroactive viologen groups and autofluorescent tertiary amine units results in a simultaneous EFC behavior with acceptable fluorescence contrast (on/off = 8.5) and moderate switching speed (22.9/12.5 s). Furthermore, a reflective/emissive dual‐mode aqueous phase device is manufactured readily based on the resultant polymer, which displays a simultaneous EC and EFC performance with high optical contrast (ΔT% = 92%), moderate fluorescence contrast (4.5), competitive CE (108 cm2 C−1), and low switching voltage of −1.4 V.

CO2 and photo-controlled reversible conversion of supramolecular assemblies based on water soluble pillar[5]arene and coumarin-containing guest

In this communication, a new supramolecualr amphiphile was successfully constructed based on water soluble pillar[5]arene and a unique guest which contain a CO2 responsive tertiary amine unit and a UV responsive coumarin group. When guest molecule 1 dispersed in water, it self-assembled into sheet-like structures. Upon bubbling CO2, 1 transformed into 1H due to the tertiary amine unit was protonated, accompany the nano-sheets transformed into vesicles. Further irradiation of 1H with 365 nm light for 3 h, the coumarin group reacted with each other to form bola-type amphiphie 2H. In this case, vesicles collapsed and re-assembled into nano-tubes. However, when addition of WP5 into the solution of 1H, the vesicles transformed into micelles, this is due to the formation of supramolecular amphiphile WP5&1H. Upon irradiation of WP5&1H with 365 nm light for 3 h, nano-ribbons observed instead of micelles in the solution. Notably, nanotubes from 2H could also transform into nano-ribbons after adding WP5. The self-assembly process and the resultant assemblies were characterized by TEM, SEM, DLS, SAXS and NMR technologies. Due to both CO2 and light are “green” for living organisms, we anticipated our system can offer the possibilities in “on demand” drug absorption and release.

Synthesis and optical, magnetic, and electrochemical properties of 5,10,15,20-tetraaryl-5,15-diazaporphyrin — tertiary amine conjugates

We report on the synthesis and optical, magnetic, and electrochemical properties of nickel(II) and copper(II) complexes of 5,10,15,20-tetraaryl-5,15-diazaporphyrin–tertiary amine (TADAP–TA) conjugates. Metal-templated cyclization reactions of 9-(4-(dimethylamino)phenyl)amino-1-chloro-5-mesityldipyrrin and 9-(4-(diphenylamino)phenyl)amino-1-chloro-5-mesityldipyrrin (mesityl = 2,4,6-trimethylphenyl) with nickel(II) or copper(II) acetate afforded the corresponding metal(II) complexes of TADAP–TA. The 20[Formula: see text], 19[Formula: see text], and 18[Formula: see text] oxidation states of the DAP ring in the TADAP – TAs were reversibly interconvertible by redox reactions. NMR spectroscopy of the 20[Formula: see text] and 18[Formula: see text] Ni-TADAP – TAs revealed their antiaromatic and aromatic characters, respectively, whereas electron paramagnetic resonance spectroscopy of the 19[Formula: see text] Ni-TADAP–TAs showed effective delocalization of an unshared electron spin in the DAP ring. The interconversion between the three oxidation states of TADAP – TAs also caused a distinct change in the optical properties of the DAP [Formula: see text]-electron system. Notably, all the 18[Formula: see text] dications exhibited weak and broad absorption bands in the near infrared region owing to the charge-transfer from the peripheral tertiary amine units (donor) to the cationic DAP center (acceptor). Cyclic voltammetry of TADAP – TAs exhibited the reversible 20[Formula: see text]/19[Formula: see text] and 19[Formula: see text]/18[Formula: see text] redox couples and the irreversible amine oxidation at the periphery. The electrochemical oxidation of the Ni-TADAP–triphenylamine conjugate generated reactive ammoniumyl radicals, which underwent intermolecular coupling to form a polymer of TADAP–TA on the electrode surface.

Investigation of self-aggregation properties of amino functionalized zinc chlorins

Zinc chlorin derivatives consisting of primary, secondary and tertiary amine unit were prepared and their aggregation properties have been studied both in solution and in solid state in order to investigate the influence of the amine moiety on the formation of self-assembled nanostructures. The supramolecular organization ability of these derivatives have been investigated on the solid substrate, namely, highly oriented pyrolytic graphite (HOPG) by using AFM (atomic force microscopy) and STM (scanning tunneling microscopy) spectroscopy. The supramolecular organization of zinc chlorin derivatives in solution has been further supported by UV–vis spectroscopy. Zinc chlorins bearing primary, secondary amine exhibit well-ordered J-type aggregation in solution and well-defined self-organization on HOPG. On the other hand, the self-organization of tertiary amine substituted zinc chlorin both in solution and in solid state was less pronounced.

Highly luminescent palladium(ii) complexes with sub-millisecond blue to green phosphorescent excited states. Photocatalysis and highly efficient PSF-OLEDs.

Palladium(ii) complexes supported by tetradentate [N^C^C^N] and [O^N^C^N] ligand systems display sky blue to red phosphorescence with emission quantum yields and emission lifetimes up to 0.64 and 272 μs, respectively. Femtosecond time-resolved fluorescence (fs-TRF) measurements on these Pd(ii) complexes reveal a fast intersystem crossing from singlet to triplet manifolds with time constants of 0.6-21 ps. DFT/TDDFT calculations revealed that, as a result of the spiro-fluorene and bridging tertiary amine units of the ligands, the T1 excited state is more ligand-localized and has smaller structural distortion, leading to slower non-radiative decay as well as radiative decay of T1 → S0 transition and thereby highly emissive, long-lived triplet excited states. The Pd(ii) complexes have been found to be efficient catalysts for visible light-driven, reductive C-C bond formation from unactivated alkyl bromides with conversions and yields of up to 90% and 83%, respectively. These complexes have also been employed as photosensitizers for [2 + 2] cycloaddition of styrenes, with conversions and yields comparable to those of the reported Ir(iii) complexes. Both green and sky blue organic-light emitting devices (OLEDs) have been generated with these Pd(ii) complexes as guest emitters. Maximum external quantum efficiencies (EQE) of up to 16.5% have been achieved in the sky blue OLEDs. The long emission lifetimes render the Pd(ii) complexes good sensitizers for phosphor-sensitized fluorescent OLEDs (PSF-OLEDs). By utilizing these phosphorescent Pd(ii) complexes as sensitizers, highly efficient green and yellow PSF-OLEDs having high EQE (up to 14.3%), high colour purity and long operation lifetimes, with 90% of initial luminance (LT90) for more than 80 000 h, have been realized.

Microporous Ceramic Tubule Based and Dendrimer-Facilitated Immobilized Ionic Liquid Membrane for CO2 Separation

A solvent evaporation method has been used to prepare a supported ionic liquid (IL) membrane in a microporous ceramic tubule-based module; its separation performance for CO2–N2 and CO2–He mixtures has been reported here over a pressure range of 50−250 psig (344.7−1724 kPag) and temperatures up to 100 °C. Solutions of IL-ethanol having different IL contents were used to prepare 1-butyl-3-methylimidazolium dicyanamide ([bmim][DCA]) membranes having different thicknesses. Membranes prepared from 25 wt % IL in ethanol solution showed the best gas permeation and separation performance. Ionic liquid membranes prepared from 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide ([emim][Tf2N]) under the same conditions displayed a slightly higher gas permeance, but its separation capability was somewhat lower. Tests at higher temperatures using the [bmim][DCA] membrane generated obviously higher gas permeances, but the ideal separation factors of CO2 over N2 and He dropped sharply. These tests were carried out with a dry feed gas. Adding polyamidoamine (PAMAM) dendrimer generation 0 to IL did not show any improvement when the feed gas was dry. After the feed gas was humidified, both the permeance and the separation factor of CO2 over N2 and He were improved greatly. This is due to lower viscosity caused by dissolved water in the IL membrane and additional reactions between CO2 and tertiary amine units of dendrimer in the presence of water. A set of gas mixture-based test results confirmed the facilitating effects of dendrimer to enhance CO2 permeation with humidified feed gas.

Positively-charged nanofiltration membrane formed by quaternization and cross-linking of blend PVC/P(DMA-co-MMA) precursors

To explore low-pressure-driven nanofiltration (LPDNF) membranes with high permeate flux, a novel preparation route was proposed and investigated. First, an amphiphilic copolymer of poly (methyl methacrylate-co-dimethylaminoethyl methacrylate) (P(MMA-co-DMA)) was synthesized via free-radical copolymerization, and then blended with polyvinyl chloride (PVC) to fabricate precursor membranes via non-solvent induced phase separation (NIPS) process. Utilizing the quaternization and cross-linking reaction between p-xylylene dichloride (XDC) and tertiary amine units in PVC/PMMA-co-DMA precursor membranes, positively charged PVC/PMMA-co-DMA LPDNF membranes were obtained. Element alanalysis, X-ray photoelectron spectroscopy and scanning electron microscopy were employed to characterize the composition and morphology of the membranes. Effects of PMMA-co-DMA content and XDC concentration on the LPDNF membranes’ performance were studied and discussed. With the optimized condition, the NF membrane showed the highest salt rejection (R) and water flux (J), e.g., RMgCl2=89.1%, JMgCl2=22.1L/(m2h) and RNaCl=45.1%, JNaCl=27.6L/(m2h) at a pressure of 0.3MPa. Besides, the rejections of the LPDNF membranes for inorganic salts increased in an order of Na2SO4<MgSO4<NaCl<CaCl2<MgCl2. Together with the good stability, PVC/PMMA-co-DMA blend membrane was approved as a promising positively charged LPDNF membranes.

Synthesis, reaction, and optical properties of cyclic oligomers bearing 9,10-diphenylanthracene based on an aromatic tertiary amide unit

Novel cyclic aromatic amide oligomers containing highly fluorescent 9,10-diphenylanthracene units were prepared by condensation of a monomer with amino and ester functional groups using lithium bis(trimethylsilyl)amide. The cyclic trimer (C3A, 40%) and tetramer (C4A, 8%) were isolated using preparative gel permeation chromatography. Some of the aromatic proton signals derived from anthracene were observed in the upfield region (6.96–6.87 ppm) in the 1H nuclear magnetic resonance spectrum of C3A. X-ray crystallographic analysis indicated that three anthracene moieties are inclined with respect to the cyclic skeleton and partly overlap each other. The fluorescence peak maximum of C3A (438 nm) showed a small red-shift compared with that of an acyclic model compound (425 nm). Reduction of the amide carbonyl group in C3A gave the cyclic trimer HC3A, which has a tertiary amine unit. The fluorescence peak maximum of HC3A (489 nm) was largely red-shifted from that of C3A and exhibited strong solvent dependence. A linear correlation was observed between the Stokes shift (Δν), ranging from 2981 to 6646 cm−1, and the Reichardt's solvent polarity parameter [ET(30)].

Theoretical Mechanism Studies on the Enantioselectivity of aza-MBH-type Reaction of Nitroalkene to N-tosylimine Catalyzed by Thiourea-tertiary Amine

The enantioselective aza-Morita Baylis Hillman reaction of nitroalkene and N-tosylimine catalyzed by thiourea-tertiary amine has been investigated using density functional theory. Enantioselectivity is dominated by the cooperative effect of non-covalent and weak covalent interactions imposed by different units of catalyst. As Lewis base, the tertiary amine unit activates nitroalkene via weak covalent bond. The weak covalent interaction orients the reaction in a major path with smaller variations of this bond. The aromatic ring unit activates N-tosylimine via <TEX>${\pi}-{\pi}$</TEX> stacking. The non-covalent interaction selects the major path with smaller changes of the efficient packing areas. Thiourea unit donates more compact H-bonded network for species of the major path. The calculated ee value in xylene solution phase (97.6%) is much higher than that in N,N-Dimethylformamide (27.2%). Our conclusion is also supported by NBO analysis.

Photoswitchable Organic Mixed Valence in Dithienylcyclopentene Systems with Tertiary Amine Redox Centers

The electronic structures of the radical cations of two dithienylperfluorocyclopentene molecules with appended tertiary amine units were investigated by electrochemical and optical spectroscopic methods. The through-bond N-N distances in the photocyclized (closed) forms of the two systems are 9.3 and 17.6 Å, respectively, depending on whether the nitrogen atoms are attached directly to the two thienyl units or whether xylyl spacers are in between. In the case of the radical cation with the longer N-N distance, photocyclization of the dithienylperfluorocyclopentene core induces a changeover from class I to class II mixed valence behavior. In the case of the shorter system, the experimental data is consistent with assignment of the photocyclized form to a class III mixed valence species.

Synthesis and properties of lignin-highly branched poly (ester-amine) polymeric systems

Abstract Combined characteristics of hydrogen bonded/cross-linked polymer networks based on lignin motifs have been developed. This new type of polymeric material was prepared from an industrial lignin and a highly branched poly(ester-amine) (HBPEA) obtained by melt polycondensation of 1,1,1-triethanolamine (TEA) and adipic acid (AA). The lignin-HBPEA polymers were shown to be insoluble in common organic solvents and were characterized by FTIR and NMR spectroscopies. Thermo-mechanical measurements showed that melt mixing HBPEA with 40% lignin results in a flexible and tough material ( T g ; 7.7 °C and E′ 3.5 GPa). The hydrogen bonding recognition was based on various hydroxyl groups in lignin and aliphatic ester groups from HBPEA. The extent of interactions could be controlled by varying the amount of lignin added. These networks were thermally reversible and have highly tunable mechanical properties that were controlled by the extent of interactions. High level of mechanical properties could be achieved through the addition of lignin-poly(ester-amine) covalent cross-links. This study shows that the poly(ester-amine) structure plays an important role in the thermo-mechanical properties. By varying the spacer length between lignin and tertiary amine unit, materials with various thermo-mechanical properties were also obtained from the same parent polymer backbone.

Synthesis of metallic nanoparticles within pH-sensitive polymeric matrices

Two different classes of pH-responsive polymeric nanostructures have been utilised as nanoreactors for the growth of colloidal metal particles. The first class consists of the micellar cores of double hydrophilic block copolymers, whereas in the second case pH-sensitive microgels are used. The micelles are formed by PHEGMA-b-PDEAEMA diblock copolymers synthesised by group transfer polymerisation. The hydrophobic PDEAEMA block is pH-responsive: at low pH it can be protonated and it becomes hydrophilic, leading to molecular solubility, whereas at higher pH micelles are formed with the hydrophobic PDEAEMA blocks immobilised within the micellar cores; the behaviour is investigated by potentiometric titration, DLS, 1H-NMR and AFM. Lightly cross-linked latex particles based on DEAEMA monomer are synthesised by emulsion polymerisation. These particles exhibit reversible swelling properties in water studied by DLS. At low pH they exist as swollen microgels due to protonation of the tertiary amine units whereas deswelling occurs above pH 7 leading to the formation of the original latexes. Metal nanoparticles were synthesised within both the micellar cores and the microgels by the incorporation of H 2PtCl 6 and subsequent reduction using NaBH4. Micelle transformations upon metallation were studied using DLS. The polymer-metal interactions were investigated by UV-Vis spectroscopy whereas the nanoparticles were investigated by TEM and XRD.

A fluorescent guest encapsulated by a photoreactive azobenzene dendrimer

We have studied the adduct formed by N,N′-2,7-didecyldiazapyrenium (P2+), as the hexafluorophosphate salt, with a third generation dendrimer (D) that comprises 14 tertiary amine units in the interior, and 16 naphthyl and 16 trans-azobenzene units in the periphery. A strong charge-transfer interaction between the electron-accepting diazapyrenium dication and electron-donating amine units of the dendrimer interior leads to a host–guest complex with 1 : 1 stoichiometry, namely D(16t)⊃P2+. The self-assembly process can be easily monitored by strong changes in the absorption and emission spectra: (i) new absorption bands (λmax ≈ 445 and 565 nm) at lower energy compared to the isolated species arise, (ii) a strong quenching of the intense diazapyrenium fluorescence is observed, and (iii) a new broad emission band, typical of the charge-transfer complex, appears with a maximum at 660 nm at 298 K and 600 nm at 77 K. By global analysis of the absorption spectra, an association constant of 1.0 × 106 M−1 is obtained for D(16t)⊃P2+, compared to 3.0 × 104 M−1 in the case of the adduct of P2+ with triethylamine under the same experimental conditions. This result demonstrates that the presence of bulky substituents at the dendrimer periphery does not hinder the formation of a stable complex and suggests a cooperative effect due to the multiple amine groups of the dendrimer branching points. No energy transfer from the azobenzene or naphthyl chromophores to the charge-transfer complex has been evidenced. The self-assembly process can be reversed upon addition of an equimolar amount of trifluoromethanesulfonic acid. An adduct with 1 : 1 stoichiometry is formed also between P2+ and D(2t14c), a species obtained from D(16t) upon irradiation at 365 nm: the corresponding association constant is very similar to that of D(16t)⊃P2+, showing that the isomeric state of the peripheral azobenzene units does not affect the stability of the adduct.

Methyl Iodide Accelerated Asymmetric Epoxidation of Alkenes Catalyzed by Chiral Salen‐Mn(III) Complexes with Tertiary Amine Units.

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Photoswitchable Dendritic Hosts: A Dendrimer with Peripheral Azobenzene Groups

We have studied the adducts formed by eosin (E) with a fourth generation dendrimer (D) that comprises 30 tertiary amine units in the interior and 32 naphthyl and 32 trans azobenzene units in the periphery. We have found that: (i) the all trans dendrimer D(32t) can be converted by irradiation with 365 nm light (Phi=0.12) into species containing, as an average, 4 trans and 28 cis azobenzene units, D(4t28c), that at 313 K undergoes a D(4t28c) --> D(32t) thermal back reaction (k = 7.0 x 10(-5) s(-1)); (ii) D(32t) and D(4t28c) extract 8 and, respectively, 6 eosin molecules from water at pH 7, yielding the species D(32t) subset 8E and D(4t28c) subset 6E; (iii) eosin uptake is significantly faster for D(32t) than for D(4t28c); (iv) irradiation at 365 nm of the D(32t) subset 8E species at 298 K leads to the release of two eosin molecules with formation of a photostable D(15t17c) subset 6E species (Phi = 0.15) that is also obtained from the back thermal reaction of D(4t28c) subset6E at 313 K (k = 2.7 x 10(-5) s(-1)); (v) thermal release of E from D(32t) subset 6E is much faster than from D(4t28c) subset 6E; and (vi) excitation of E in the adducts sensitizes the cis --> trans (but not the trans --> cis) isomerization. The results obtained show that the isomerization of the 32 peripheral azobenzene units controls to some extent the hosting capacity of the dendrimer and, viceversa, eosin molecules hosted in the dendrimer affect the isomerization process of its azobenzene units.

Methyl Iodide Accelerated Asymmetric Epoxidation of Alkenes Catalyzed by Chiral Salen‐Mn(III) Complexes with Tertiary Amine Units

AbstractA series of chiral salen‐Mn(III) complexes featuring two tertiary amine units were synthesized and employed in the enantioselective epoxidation of unfunctionalized alkenes in the presence of pyridine N‐oxide and 2,6‐dimeth‐ ylpyridine N‐oxide as proximal ligands, respectively. Moderate to high enantioselectivity and acceptable yields were achieved when NaClO was used as terminal oxidant under CH2Cl2/H2O biphasic media. Methyl iodide was found to be an effective additive to accelerate the epoxidation, possibly owing to the formation of quaternary ammonium units on catalysts, which may facilitate the reaction in an oil/water biphasic medium. The subsequent stimulation experiment was carried out, and the resulting ESI‐HRMS analysis revealed the formation of a novel (salen)manganese(III) intermediate featuring two quaternary ammonium units, and bearing a pyridine N‐oxide and a molecule of water simultaneously axially‐coordinated backbone.

Cationic Amphiphilic Model Networks Based on Symmetrical ABCBA Pentablock Terpolymers: Synthesis, Characterization, and Modeling

Eight isomeric networks based on equimolar terpolymers were synthesized using group transfer polymerization (GTP) and were characterized in terms of their swelling properties. Two hydrophilic monomers, the nonionic methoxy hexa(ethylene glycol) methacrylate (HEGMA) and the ionizable 2-(dimethylamino)ethyl methacrylate (DMAEMA), and a hydrophobic (nonionic) monomer, methyl methacrylate (MMA), were employed for the syntheses. 1,4-Bis(methoxytrimethylsiloxymethylene)cyclohexane (MTSMC) was used as the bifunctional GTP initiator, while ethylene glycol dimethacrylate (EGDMA) served as the cross-linker. Seven of the networks were model networks, six of which were based on the symmetrical pentablock terpolymers ABCBA, ACBCA, BACAB, BCACB, CBABC, and CABAC, whereas the seventh model network was based on the statistical terpolymer. The eighth network was a randomly cross-linked network based on the statistical terpolymer, prepared by the simultaneous quaterpolymerization of the three monomers and the cross-linker. The molecular weights and molecular weight distributions of the linear pentablock terpolymer precursors, as well as those of their homopolymer and ABA triblock copolymer precursors, were characterized by gel permeation chromatography (GPC) in tetrahydrofuran. The sol fraction of each network was measured and found to be relatively low. The aqueous degrees of swelling of all networks were found to increase at acidic pH due to the ionization of the DMAEMA tertiary amine units. The acidic degrees of swelling of the pentablock terpolymer networks were lower than those of their statistical counterparts due to microphase separation in the former type of networks, also confirmed by thermodynamic calculations and small-angle neutron scattering experiments.