A novel stimuli-responsive hydrogel for K-induced controlled-release

A novel family of stimuli-responsive smart hydrogel is developed in this study for K⁺-induced self-regulated controlled-release, which is featured with isothermally K⁺-induced pulse-release mode at a certain temperature due to the isothermally K⁺-induced shrinking behavior of the hydrogel by recognizing the increase of K⁺ concentration in the environment. The proposed poly(N-isopropylacrylamide-co-benzo-15-crown-5-acrylamide) hydrogel is composed of crown ether 15-crown-5 as ion-signal sensing receptor and poly(N-isopropylacrylamide) as actuator. The selective formation of stable 2:1 “host-guest” complexation between the crown ether 15-crown-5 and potassium ion drives the polymeric network of the hydrogel to shrink; as a result, the hydrogel exhibits especial and selective response to potassium ions. A K⁺-recognition pulse-release performance of loaded drug from the fabricated hydrogel is achieved by using the K⁺-induced isothermal shrinkage property of the hydrogel. The proposed hydrogel provides a new mode of K⁺-recognition volume change for stimuli-responsive smart actuators, which is highly attractive for targeting drug delivery systems, biomedical devices, and sensors and so on.     

Spacer-chromoionophores — polymethine dye substituted aza-crown ethers with increased complexation ability

Aromatic aldehyde derivatives of N-phenyl-aza-15-crown-5 ( 2 ), N-phenyl-aza-18-crown-6 ( 8 ), and benzo-15-crown-5 ( 10 ) are condensed with malononitrile and 2-amino-1,1,3-tricyano-1-propene to give light yellow to orange colored crown ether derivatives 4 , 5a , 9a , 11 , and 12 . 5a and 9a were acylated with ethyl chloroformate to give the magenta colored dyes 5b and 9b , respectively. By condensation of N-(4-nitrosophenyl)-aza-15-crown-5 3 with 2-amino-1,1,3-tricyano-1-propene the magenta dye 6a is obtained. Acylation of 6a with ethyl chloroformate leads to the deep blue colored dye 6b . In these derivatives the nitrogen or oxygen atoms of the crown ethers are part of the chromophoric system, and binding properties are affected. Further chromophoric derivatives of aza-crown ethers are studied in which these are separated from the chromophoric moiety by a spacer. N-(ω-chloroalkyl)-N-alkylanilines 14a-c were attached to aza-15-crown-5 13a-c and aza-18-crown-6 13b-c to yield the spacer crown ether derivatives 15a-c and 16a-c , respectively. The formylated spacer crown ether derivatives 17a-c and 18b were condensed with 2-amino-1,1,3-tricyano-1-propene to give the orange spacer-chromoionophores 19a-c and 20 . In these crown ether derivatives the extended conjugation is interrupted by the spacer, and good binding properties are obtained. The complex formation constants of the crown ether derivatives with Na⁺ and K⁺ are determined using ¹H NMR spectroscopy.     

(N-Phenyl-aza-Krone)-ethenyl-acridine – Komplexbildende Chromoionophore und Vorstufen für tiefblau gefärbte Hemicyanine

(N-Phenyl-aza-crown)-ethenyl-acridines – Complexing Chromoionophores and Precursors for Deep Blue Coloured Hemicyanines Aromatic aldehyde derivatives of N-phenyl-aza-15-crown-5 and N-phenyl-aza-18-crown-6 ( 1a–b ) are condensed with 9-methylacridine to give yellow phenyl-ethenylacridine derivatives 3a–b which are reversibly converted by protonation into deep blue colored hemicyanines, Using 9,10-dimethylacridinium perchlorate in the condensation with the crown ether aldehyde 1 the blue hemicyanine 6 is directly obtained. UV/VIS absorption spectra of the basic/acidic forms of the acridine derivatives are presented. The complex formation of the crown ether derivatives with Na⁺ and K⁺ are studied using ¹H-NMR and UV/VIS spectroscopy.     

Binding of the cationic fluorophore Auramine-0 to neutral and charged poly(vinylbenzo-18-crown-6) in water

Summary The cationic fluorophore Auramine-0 strongly interacts with poly(vinylbenzo-18-crown-6), a polymer which in water behaves as a typical polysoap. The intrinsic binding constant at 25°C was found to be 2.2 × 10⁴ M^–1. The binding can be modified by adding crown ether-complexable cations such as K⁺ or Cs⁺. Complexation converts the neutral polycrown ether into a polycation causing repulsion of the cationic fluorophore and a decrease in the observed fluorescence. There is some indication that the cation of the dye specifically interacts with a crown ligand.     

EXTRACTION OP MANGANESE(II) BT MIXTURES OP DIDODECYLNAPHTHALENESOLFONIC ACID AND r-BUTYL- CYCLOHEXANO-15-CROWN-5: SPECTRAL EVIDENCE FOR THE FORMATION OF A MANGANESE(II) - CROWN ETHER COMPLEX

Addition of t-butylcyclohexano-15-crown-5 (tBC-15C5) induces a synergistic effect in the extraction of Mn²⁺ ion with didodecylnaphthalenesulfonic acid (HDDNS). This synergism is the result of the inner-sphere complexation of the crown ether to the manganese(II) ion. The formation of this complex, first suggested by distribution studies, has been confirmed by FTIR experiments. The C-O-C stretching bands for the crown ether ligand shift to lower frequency when Mn²⁺ ion is extracted into a CC14 solution of HDDNS and tBC15C5. A similar C-O-C Btretching band is observed for the crystalline complex [Mn(15C5 ) (Bu₃CS0₃)₂] (where 15C5 = 15-crown-5 and Bu = n-butyl).Formation of analogous complexes is not observed for Fe³⁺, co²⁺,N²⁺,cu²⁺, or zn²⁺ under similar conditions.     

Dual thermo-responsive and ion-recognizable monodisperse microspheres

A novel type of dual stimuli-responsive microspheres that simultaneously exhibit ion-recognition property based on the supramolecular host-guest complexation of crown ether receptors (benzo-18-crown-6-acrylamide) (BCAm) with specific ions and thermo-sensitivity based on the phase transition of poly(N-isopropylacrylamide) (PNIPAM) is fabricated in this study. The prepared poly(N-isopropylacrylamide-co-benzo-18-crown-6-acrylamide) (P(NIPAM-co-BCAm)) microspheres are characterized by FT-IR spectroscopy, UV-vis absorption spectroscopy, scanning electron microscopy (SEM), and dynamic light scattering (DLS). SEM images and DLS data show that the synthesized microspheres exhibit nearly perfect spherical shape and high monodispersity. Moreover, according to the DLS results, P(NIPAM-co-BCAm) microspheres exhibit satisfactory thermo-responsive behavior and ion-recognition property. In K⁺ solutions, due to the formation of crown ether/K⁺ complexes, the LCST of P(NIPAM-co-BCAm) microspheres shifts to a higher temperature and the colloidal stability is increased. The P(NIPAM-co-BCAm) microspheres undergo a volume change from shrunken state to swollen network isothermally at a certain temperature by the addition of metal ions. Due to dual thermo-responsive and ion-recognition behaviors, this kind of microspheres would serve as promising candidates for sensors, controlled drug delivery systems and possibly new biomaterials.     

Ion-Pair Sorption of Alkali Metal Chlorides by Crown Ether Carboxamide Resins

Abstract

Ten crown ether carboxamide resins are prepared by condensation polymerization of N,N-dialkyl sym-(R)dibenzo-16-crown-5-oxyacetamide monomers with formaldehyde in formic acid. Competitive ion-pair sorption of alkali metal chlorides from aqueous methanol solutions by these novel resins reveals that both sorption selectivity and efficiency are influenced by: 1) the conformational positioning of the pendant carboxamide group with respect to the crown ether cavity; 2) the length of the N,N-dialkyl chains on the pendant carboxamide group; 3) the methanol content of the aqueous methanol solution; 4) the concentration of alkali metal chlorides in the sample solution; and 5) the temperature of the sample solution. The highest sorption efficiency and Na⁺ selectivity are obtained for a resin prepared from N.N-dibutyl sym-(propyl)dibenzo-16-crown-5-oxacetamide monomer in which the geminal propyl group orients the carboxamide-containing side arm over the crown ether cavity. Lengthening the alkyl chains in the carboxamide group is detrimental to both sorption efficiency and selectivity. A very sharp response of alkali metal chloride sorption to the methanol content of the sample solution is noted for the crown ether resins which possess preorganized carboxamide side arms.     

From potassium alkalide and benzyl glycidyl ether to crown-like macroinitiator with alkoxide active centres

Cyclic oligoether with alkoxide groups is obtained in the reaction of alkalide K⁻, K⁺(15-crown-5)₂ with benzyl glycidyl ether. This oligoether contains potassium glycidoxide units and benzyl glycidyl ether units. Its use as a macroinitiator should lead to star-shaped polymers with a cyclic core.     

The Synerqistic Solvent Extraction of Manganese by Macrocyclic Crown Ethers in Combination with Didodecylnaphthalene Sulfonic Acid: Effect of Macrocycle Substituents

Abstract

Crown ethers in combination with organophilic cation exchangers synergize the extraction of certain metai ions from aqueous solutions, and their selectivity has been thought largely dependent on the correspondence between the crown other's cavity diameter and the metal ion diameter. This work focuses on two crown ethers, tert. -butylbenzo -15-crown-5 (tBB15C5). and tert, -butylcyclohexano 15-crown-5 (tBC15C5) each of which has a cavity diameter of 1.7 to 2.2 × 10^?10 m. and their extraction of Mn²⁺ (ionic diameter 1.4 to 2.2 × 10^?10 m) from aqueous nitrate solutions. The organophilic cation exchanger used was didodecylnaphthalene sulfonic acid (HDDNS). The data show no observable complexes of the manganese salt of HDDNS     

EXTRACTION OF URANYL IONS BY SYNERGISTIC MIXTURES OF THENOYLTRIFLUOROACETONE AND MACROCYCLIC DONORS

A linear polyether, 1, 13-bis[8-qulnoly]-l,4,7,10,13-pentaoxa-trldecane (K-5) and an aza-crown ether, 4,13-didodecyl-1,7,10,16-tetraoxadiazacyclooctadecane (K22DD) when combined with thenoyltrlfluoroacetone (HTTA) have been shown to exhibit a synergistic effect on the extraction of uranyl ion. The effects of the addition to the organic phase of K-5, K22DD, and tert-butylcyclohexyl-15-crown-5 (15-C-5) on the extraction of UO₂ ⁺² by HTTA in chloroform from 0.5 M NaNO₃ at 25°C have been measured. The results indicate the extraction is enhanced by the formation of an adduct, UO₂(TTA)₂S for K-5 and K22DD. No enhancement of the extraction was seen with the crown ether. The organic phase stability constants for both K-5 and K22DD were evaluated and found to be similar in magnitude. These results suggest that the major factor in the formation of the synergistic adduct is the presence of the nitrogen atom in the synergist.     

RADIUM SEPARATION THROUGH COMPLEXATION BY AQUEOUS CROWN ETHERS AND ION EXCHANGE OR SOLVENT EXTRACTION

ABSTRACT

The effect of three water-soluble, unsubstituted crown ethers (15-crown-5 (15C5), 18-crown-6 (18C6) and 21-erown-7 (21C7) on the uptake of Ca, Sr, Ba and Ra cations by a sulfonic acid cation exchange resin, and on the extraction of the same cations by xylene solutions of dinonylnaphthalenesulfonic acid (HDNNS) from aqueous hydrochloric acid solutions has been investigated. The crown ethers enhance the sorption of the larger cations by the ion exchange resin, thereby improving the resin selectivity over calcium, a result of a synergistic interaction between the crown ether and the ionic functional groups of the resin. Similarly, the extraction of the larger alkaline earth cations into. xylene by HDNNS is strongly synergized by the presence of the crown ethers in the aqueous phase. Promising results for intra-Group IIa cation separations have been obtained using each of the three crown ethers as the aqueous ligands and the sulfonic acid cation exchange resin. Even greater separation factors for the radium - calcium couple have been measured with the crown-ethers and HDNNS solutions in the solvent extraction mode. The application of the uptake and extraction results to the development of radium separation schemes it discussed and a possible flowchart for the determination of ²²⁶Ra/²²⁸Ra in natural waters is presented.

     

EXTRACTION OF CESIUM NITRATE FROM CONCENTRATED SODIUM NITRATE SOLUTIONS WITH 21-CROWN-7 ETHERS: SELECnVITY AND EQUILIBRIUM MODELING

ABSTRACT

The extraction of cesium nitrate from a high concentration of sodium nitrate by a family of 21-crown-7 ethers in 1,2-dichloroethane has been investigated. Dibenzo-21-crown-7 (DB21C7) and bis[4(5),4′(5′)-rm-butylbenzo]-21-crown-7 (BtBB21C7) ethers have higher selectivity for cesium but lower extraction efficiency than dicyclohexano-21-crown-7 (DC21C7) ether. As measured by the distribution coefficient ratio D_cs/D_Na, the cesium selectivity averaged 78 and 93 for DB21C7 and BtBB21C7, respectively. However, in the case of DC21C7, the cesium selectivity was lower and decreased approximately three-fold from 10 to 3 as cesiüm loading increased. Alkyl substitution on the benzo group has only a small effect on the extraction behavior. It was shown by use of the equilibrium modeling program SXLSQI that the extraction of sodium and cesium could be adequately modeled by augmenting the previously determined cesium nitrate equilibrium model with a 1:1 Na⁺:crown organic-phase complex. No evidence for a mixed-metal species was found. In accord with our previous study, cesium nitrate extraction entails formation of a 1:1 Cs⁺:crown complex, but a minor 1:2 complex also forms in the case of DC21C7. Although the sodium and cesium made possible by the U. S. Department of Energy Postgraduate Research Program administered by the Oak Ridge Associated Universities.     

Extraction of Alkali Metal Cations by Lipophilic Dibenzo-14-crown-4-carboxylic Acids

Abstract

The extraction of alkali metal cations by the lipophilic crown ether, bis-t-octylbenzo-14-crown-4 (BOB14C4), three derivatives of BOB14C4 having pendant carboxylic acid sidearms, and a lipophilic carboxylic acid, 2-methyl-2-heptylnonanoic acid (HMHN) was studied by two-phase potentiometric titration and ion-chromatography. The lipophilic, ionizable crown ethers, BOB14C4-acetic acid (BOB14C4AA), BOB14C4-propanoic acid (BOB14C4PA), and BOB14C4-oxyacetic acid (BOB14C4OAA) extract cations efficiently from aqueous mixed alkali metal chloride solutions into 1-octanol by an ion-exchange mechanism in the range p[H] > 7, as does HMHN. The mode of attachment of the ionizable sidearm, via an ether linkage (BOB14C4OAA) versus a carbon linkage (BOB14C4AA and BOB14C4PA), has a significant effect on the cation selectivity and extraction efficiency of these extractants. BOB14C4 exhibits no p[H] dependent extraction behavior and has no significant effect on the extraction of alkali metal cations by HMHN in a mixture of these two compounds. Although BOB14C4AA and BOB14C4PA extract cations at lower p[H] than HMHN, all three compounds exhibit similar selectivity for Li⁺ over Na⁺, K⁺, Rb⁺ and Cs⁺. A significant reversal in selectivity is observed with BOB14C4OAA, which extracts Na⁺ and K⁺ selectively over Li⁺, Rb⁺, and Cs⁺ and at significanty lower p[H] than BOB14C4AA, BOB14C4PA, or HMHN. The unique behavior of BOB14C4OAA may be attributed to the presence of the ether linkage between the crown ether and the pendant carboxylic acid.     

新型冠醚功能化离子液体［A（benzo15C5）HIM］［(CF3SO2）2N］的合成

通过Williamson反应、Friedel-Crafts酰基化等反应合成了新型冠醚功能化离子液体1-烯丙基-3-（6′-氧代苯并-15-冠-5-己基）咪唑双三氟甲磺酰亚胺（［A（benzo15C5）HIM］［（CF₃SO₂）₂N］）,并以IR、¹H NMR对其结构进行了表征。初步探讨了双酚A（BPA）在多壁碳纳米管-离子液体（MWCNTs-IL）修饰玻碳电极上的电化学行为。     

基于冠醚的离子识别响应型智能材料研究新进展

金属离子对生物体的生命活动起着核心的作用,而一些重金属离子(如Pb²⁺、Hg²⁺)在很低浓度时就对生物具有极强的毒性;因此,研究具有金属离子识别特性的智能材料具有重要的理论价值和实用意义。冠醚具有选择性地络合金属离子的能力,研究者们将冠醚的离子识别特性与聚(N-异丙基丙烯酰胺)的相变行为特性相结合制备了一系列离子识别响应型智能材料。综述了近年来基于18-冠-6和15-冠-5两种冠醚分子的离子识别响应型智能材料的研究新进展。目前,基于冠醚的离子识别响应型智能材料仍多处于基础研究阶段,还需要进一步系统深入研究和开发完善。     

Ion‐Selective Ionic Polymer Metal Composite (IPMC) Actuator Based on Crown Ether Containing Sulfonated Poly(Arylene Ether Ketone)

This study introduces the concept of ion selective actuation in polymer metal composite actuators, employing crown ether bearing aromatic polyether materials. For this purpose, sulfonated poly(arylene ether ketone) (SPAEK) and crown ether containing SPAEK with molar masses suitable for membrane preparation are synthesized. The synthesized polymers are characterized using Nuclear magnetic resonance (NMR) and fourier transform infrared spectroscopy (FTIR) spectroscopy, thermal gravimetric analysis (TGA), and differential scanning calorimetry (DSC). Ionic polymer metal composite (IPMC) actuators are fabricated by electroless chemical deposition of a platinum (Pt) layer on both sides of SPAEK and crown‐ether containing SPAEK membranes, resulting in electrode layers of around 120 nm thickness. Actuation experiments demonstrate cation specific responses and bending degrees of the IPMC actuators. Incorporation of crown ether units in the polymer backbone results in an improved and ion‐selective bending displacement compared with SPAEK actuators. S(25)C(50)PAEK actuators show an increased bending displacement of 28% for Na⁺ and 20% for K⁺ ions.

     

Synthesis of SPR Nanosensor using Gold Nanoparticles and its Application to Copper (II) Determination

This research describes a colorimetric assay for Cu (II) ions that is highly selective over other metal ions. It is based on the measurement of changes in the surface plasmon resonance absorbance (at 525 nm) of gold nanoparticles (Au NPs) modified with 1,7-diaza-15-crown-5 (Crown-Au NPs). The unique structure of crown ethers and presence of heteroatoms enable the crown-Au NPs to recognize very low concentrations of Cu (II) ions. After aggregation, the surface plasmon absorption band has a red shift so that the nanoparticle solution shows a violet color. The TEM images data show that this color change is a result of crown-Au NPs aggregation upon addition of Cu (II), In contrast, other metal ions Al³⁺, Ca²⁺, Cd²⁺, Co²⁺, Cr³⁺, Ag⁺, Fe²⁺, Fe³⁺, Hg²⁺, K⁺, Mg²⁺, Mn²⁺, Na⁺, Ni²⁺, Pb²⁺, and Zn²⁺ do not aggregate. The recognition mechanism is attributed to the formation of a sandwich (2+1) between the Cu (II) ion and two diaza-15-crown-5 moieties that are attached to separate nanoparticles. This simple and fast method can be used to determine the Cu (II) ions with a detection limit as low as 200 nM.     

The synthesis and complexation study of some novel 3-methoxyphenyl chromenone crown ethers using conductometry

7,8-Dihydroxy-3-(3,4-dimethoxyphenyl)-2H-chromenones, 7,8-dihydroxy-3-(3,5-dimethoxyphenyl)-2H-chromenones and 7,8-dihydroxy-3-(3,4,5-trimethoxyphenyl)-2H-chromenones, o-dihydroxy-3-methoxyphenylcoumarins, were prepared from 2,3,4-trihydroxybenzaldehyde and corresponding methoxyphenylacetic acid in NaOAc/Ac₂O, respectively. 3-Methoxyphenyl-7,8-dihydroxy-2H-chromenone reacted with the polyethylene glycol ditosylate or dichloride in CH₃CN/alkali carbonate to afford [12]crown-4, [15]crown-5 and [18]crown-6-chromonones.The chromatographically purified novel chromenone crown ethers were identified with IR, ¹H NMR, ¹³C NMR and low and high resolution mass spectroscopy and elemental analysis.Stability constants for the 1:1 complexes of Na⁺ and K⁺ with different substituted methoxyphenyl derivatives of coumarino[12]crown-4, coumarino[15]crown-5 and coumarino[18]crown-6 (5a–5i) have been determined by conductometry at 25 °C in a binary solvent, dioxane/water. For all the coumarino crown ether derivatives, the stability constant decreases for K⁺ ion compared to Na⁺ ion.The selectivity sequence of these crown ethers in dioxane/water has showed an irregular order with respect to their cavity size.     

Synthesis,characterization, and properties of co-poly(ether–urethane–urea)s containing lariat cryptand 22: Li<Superscript>+</Superscript> harvesting polymers

In this work, some segmented poly(ether–urethane–urea)s (PEUUs) containing aza crown ether (cryptand) were prepared and characterized. These polymers were synthesized via the reaction of kryptofix 22 with 2 mol excess of 4,4′-methylene-bis-(4-phenylisocyanate) (MDI), and different molecular weights of polyethylene glycols (PEGs). Morphology, thermal, and complexation properties of these polymers were studied by Fourier-transform infrared spectroscopy (FT-IR), differential scanning calorimetry (DSC), thermal gravimetric analysis (TGA), atomic absorption spectroscopy (AAS), and solid state NMR (S-NMR). The data confirmed complexation ability of these polymers for Li⁺ ion absorption and revealed the effect of Li⁺ ion complexation on the morphology and thermal behavior of the PEUUs.     

Extractive Separation of Lithium Isotopes by Crown Ethers

Abstract

Separative abilities of crown ethers to lithium isotopes were investigated for the number of oxygen atoms composing crown rings and for the substituted groups to 15-crown-5. The separation factors at 0°C were 1.057 for 12-crown-4, 1.042 for benzo-15-crown-5, 1.041 for lauryloxymethyl-15-crown-5, 1.043 for tolyloxymethyl-15-crown-5, and 1.024 for dicyclohexano-18-crown-6. The enthalpy change of the isotopic equilibrium in the absolute value was the greatest for 12-crown-4; ΔH° = ?0.78 kJ/mol. In the substituted 15-crown-5s the separation factor was greatest for tolyloxymethyl-15-crown-5, and ΔH° values decreased in the order: benzo- > tolyloxymethyl- > lauryloxymethyl-15-crown-5. For enthalpy changes, benzo-15-crown-5 has the possibility of giving a larger separation factor than the present one, α = 1.042, by choosing more suitable conditions. In spite of its large distribution coefficient, dicyclohexano-18-crown-6 is not superior for isotopic separation of lithium in regard to the small enthalpy change of isotopic equilibrium; ΔH° = ?0.15 kJ/mol. The addition of DMSO to the initial solution of LiI caused a remarkable increase in the distribution coefficient without changing the isotopic separation factors.