Physico-Chemical Investigations of Mixed Micelles of Cationic Gemini and Conventional Surfactants: a Conductometric Study

The interaction of cationic gemini and cationic conventional surfactants by conductivity was systematically overviewed, paying attention to synergism observed in micellization. These mixed systems were found to show remarkable synergism in micelle formation. The experimental critical micelle concentration values being lower than the value predicted by ideal solution theory indicate that the mixed micellization is due to attractive interaction between the two components. Gemini/conventional systems form mixed micelle due to attractive interactions (negative β values). The values of micellar mole fraction of constituent 1 (X ₁) in surfactant mixtures are more than in the ideal state (X ₁ ^ideal ), which means that, the mixed micelles are rich in conventional surfactants in comparison to that in the ideal state.     

Synthesis and Surface Properties of Novel Gemini Imidazolium Surfactants

Five new Gemini imidazolium surfactants were synthesized from imidazole and 1-bromoalkane (C₈, C₁₀, C₁₂, C₁₄, C₁₆) to get 1-alkylimidazole, which was further reacted with 1,3-dichloropropan-2-ol to form the surfactant molecule, 1,1′-(propane-1,3-diyl-2-ol) bis(3-alkyl-1H-imidazol-3-ium) chloride. The structures of the five new surfactants and intermediates were characterized by ¹H-NMR, ¹³C-NMR and IR spectra. Thermal properties of the five new surfactants were studied with thermogravimetric analysis and differential scanning calorimetry, the five new surfactants showed a transition from a crystalline phase to a thermotropic liquid–crystalline phase at around ca. 100 °C, which transformed to an isotropic liquid phase at around ca. 165 °C. The five new surfactants critical micelle concentrations (CMC) in the aqueous solutions were determined by surface tension and electrical conductivity methods. The surface tension measurements provided a series of parameters, including critical micelle concentration (CMC), surface tension at the CMC (γ _CMC), adsorption efficiency  (pC ₂₀), and effectiveness of surface tension reduction (π_CMC). In addition, with application of the Gibbs adsorption isotherm, maximum surface excess concentration (Γ_max) and minimum surface area/molecule (A_min) at the air–water interface were obtained. The parameters β (degree of counterion binding to micelles), ΔG _ads ^θ (Gibbs free energy of adsorption), and ΔG _mic ^θ (Gibbs free energy change of micellization) were also derived. The results indicated that the five new Gemini surfactants exhibited very low CMC and a good efficiency in lowering the surface tension of water. The foamability and foam stability of the five new surfactants were also examined at different CMC.     

Mixtures of Nonionic Surfactants made from Renewable Resources with Alkyl Sulfates and Sodium n-Alkanecarboxylates: Comparison of Mixing Behavior using Rubingh’s Treatment

Binary aqueous mixtures of (1) alkyl glucopyranosides (glycosides), (2) alkyl maltopyranosides (maltosides), or (3) alkyl N-methyl glucamines with (1′) sodium alkyl sulfates or (2′) sodium n-alkyl carboxylates were investigated in an effort to evaluate physiochemical properties for mixtures of surfactants from renewable resources. Solutions at various concentrations and mixture ratios were tested and evaluated to determine critical micelle concentrations (CMCs). The greatest reduction in CMC was found for surfactants with long and intermediate hydrophobe lengths. In agreement with other studies, an increase in hydrophilic group size and flexibility decreased the electrostatic repulsion of ionic-nonionic mixed micelles as evidenced by a more negative Rubingh’s β parameter. However, at low hydrophobe length, carboxylate and glycoside headgroup mixtures produced mixed micelle interactions displaying synergism at low nonionic surfactant mole fractions and slight antagonism at high nonionic mole fractions. The asymmetry in interaction produces an S-shaped CMC curve and demonstrates that the one-parameter Rubingh model is insufficient in describing both synergism and antagonism for this binary mixture.     

Synthesis and Physicochemical Investigation of Novel Quaternary Ammonium Salt Cationic Gemini Surfactant Derived from Cyanuric Chloride

Three novel quaternary ammonium salt cationic gemini surfactants (QAS C _n ?C2?CC _n where n represents the hydrocarbon chain lengths of aliphatic amine, i.e., 6, 8, 12) were synthesized from 2,4,6?Ctrichloro?C1,3,5?Ctriazine, ethylenediamine, N,N?Cdimethylpropane?C1, 3?Cdiamine and benzyl chloride. ¹H-NMR, ¹³C-NMR, ESI?CMS spectra and elemental analysis were used to confirm the chemical structures of the prepared compounds. Their critical micelle concentrations (CMC) in the aqueous solutions were determined by surface?Ctension, electrical conductivity and steady?Cstate fluorescence methods respectively. With the increasing length of the hydrophobic chain, the values of their CMC decreased. The values of CMC, ?? _CMC, pC ₂₀, ??_max, and A _min were derived from surface tension measurements, while the thermodynamic parameters of micellization (?G _mic ^° and ?G _ads ^° ) were determined by electrical conductivity. These properties are significantly influenced by the hydrophobic chain length.     

Synthesis,Surface Property and Antimicrobial Activity of Cationic Gemini Surfactants Containing Adamantane and Amide Groups

A series of novel cationic gemini surfactants, namely 1,3-adamantanedicarboxylic acid bis(alkyldimethyl-3-ammoniopropyl amide) dibromide designated as [Ad-2(amC _n )] (n = 12, 14, 16), containing adamantane, two amide groups, and two hydrocarbon chains, were synthesized from 1,3-adamantanedicarboxylic acid. The surface-active properties of the surfactants were investigated through surface tension and electrical conductivity measurement. A series of thermodynamic parameters such as standard free energy \(\left( {\Delta G^\circ_{\text{m}} } \right)\) , enthalpy \(\left( {\Delta H^\circ_{\text{m}} } \right)\) , and entropy \(\left( {\Delta S^\circ_{\text{m}} } \right)\) of micellization were evaluated from electrical conductivity measurements in the temperature range from 288 to 308 K. The micellization for [Ad-2(amC _n )] is entropy-driven at low temperature and enthalpy-driven at high temperature. Further, the antimicrobial activity of the synthesized gemini surfactants against both Gram-positive and Gram-negative bacteria was also investigated, and this study showed that the compound [Ad-2(amC₁₂)] has excellent antibacterial activity against all studied bacteria.     

Interaction Between Cationic and Anionic Surfactants: Detergency and Foaming Properties of Mixed Systems

The micellar and interfacial behavior of mixtures of the anionic surfactant (alcohol ether sulfate, AES) with quaternary ammonium type cationic surfactants dodecyltrimethyl ammonium chloride (DTAC), dodecyl-(2-hydroxyethyl)-dimethyl ammonium chloride (DHDAC), dodecyl-di(2-hydroxyethyl)-methyl ammonium chloride (DHHAC) were investigated by means of surface tension measurements. Various physicochemical properties such as surface activity parameters (CMC, γ _CMC, Г _max, A _min), the micellar and interfacial compositions (x ₁ ^m , x ₁ ^σ ), interaction parameters (β ^m , β ^σ ), and activity coefficients ( \(f_{1}^{m}\) , \(f_{2}^{m}\) , \(f_{1}^{\sigma }\) , \(f_{2}^{\sigma }\) ) were evaluated. The influence of the hydroxyethyl groups of cationic surfactant component on the physicochemical properties of mixed systems has been analyzed. It is observed that the CMC values of the three mixed systems decrease with increases in the number of hydroxyethyl groups of the cationic surfactant component. From the results of β ^σ and β ^m values, the interactions between molecules for the three surfactant mixtures at the air/liquid interface increase in the following order DHHAC/AES < DHDAC/AES < DTAC/AES, but it is the opposite for the interactions in mixed micelles. The detergency and foaming properties of mixed systems were also studied. As expected, complex surfactant systems exhibit good detergency and foaming properties.     

Surface Adsorption and Aggregation Properties of Novel l-Lysine-Based Gemini Surfactants

Four chiral l-lysine-based gemini surfactants with different spacers were synthesized, namely, disodium (18R,23R)-12,20,21,29-tetraoxo-13,19,22,28-tetraazatetracontane-18,23-dicarboxylate([C₁₂-2-C₁₂]Na₂), disodium (18R,25R)-12,20,23,31-tetraoxo-13,19,24,30-tetraazadotetracontane-18,25-dicarboxylate([C₁₂-4-C₁₂]Na₂), disodium(18R,27R)-12,20,25,33-tetraoxo-13,19,26,32-tetraazatetratetracontane-18,27-dicarboxylate([C₁₂-6-C₁₂]Na₂), disodium(2R,2′R)- 2,2′-(6-chloro-1,3,5-triazine-2,4-diyl)bis(azanediyl)bis(6-dodecanamidohexanoate) ([C₁₂-T-C₁₂]Na₂). The chemical structures of the prepared compounds were confirmed by ¹H-NMR, ESI–MS and IR spectra. Further, the critical micelle concentration (CMC) of these surfactants in aqueous solutions was determined by surface tension and conductometry methods at 25 °C. Moreover, the adsorption and micellization behaviors of these surfactants were estimated by pC₂₀, the minimum average area per surfactant molecule (A_min), and standard free energy for micellization and adsorption ( \( \Updelta G_{\text{mic}}^{^\circ } \) and \( \Updelta G_{\text{ads}}^{^\circ } \) ). The results show that the four gemini surfactants have low CMC values and significantly low surface tension. Furthermore, the surfactants show strong adsorption at the air–water interface. The CMC and A_min values of the surfactants were found to be in the order of [C₁₂-2-C₁₂]Na₂ < [C₁₂-4-C₁₂]Na₂ < [C₁₂-6-C₁₂]Na₂ < [C₁₂-T-C₁₂]Na₂, which were in agreement with the sequence of \( \Updelta G_{\text{mic}}^{^\circ } \) and \( \Updelta G_{\text{ads}}^{^\circ } \) . The circular dichroism of the surfactants indicated the formation of chiral aggregates above the CMC values.     

Micellar and Interfacial Behavior of Cationic Benzalkonium Chloride and Nonionic Polyoxyethylene Alkyl Ether Based Mixed Surfactant Systems

Micellar and interfacial properties of mixed surfactant systems comprising benzalkonium chloride, a cationic surfactant and nonionic polyoxyethylene alkyl ether surfactants (POE: C₁₀E₇, C₁₀E₈, C₁₀E₉, C₁₀E₁₀) have been investigated by surface tension, fluorescence and dynamic light scattering techniques. Critical micelle concentration (CMC) for different mixing mole fractions has been investigated by surface tension and fluorescence measurements. Ideal CMC, mixed micellar composition (X ₁ ^m , X ₁ ^σ ), interaction parameters for mixed micelles (β ^m) and adsorption monolayer (β ^σ ), surface excess concentration (Г_max), minimum area per molecule (A _min) and related thermodynamic properties have also been determined. Lowering of the CMC and negative interaction parameter values indicate synergism in the mixed micelle and monolayer formed, whereas, thermodynamic parameters evaluated for the proposed mixed systems indicate stability of the resulting micelles and monolayer. Micellar aggregation number (N _agg) and hydrodynamic diameter (D _h) computed from fluorescence and dynamic light scattering measurements respectively illustrate micellar growth in the mixed state. Results obtained for the proposed mixed systems can be helpful in designing smart materials for industrial surfactant based formulations.     

Surface and Solution Properties of Amphiphilic Drug-Nonionic Surfactant Systems

A surface tension study was performed on mixed amphiphilic drug-nonionic surfactant systems. The drugs used were adiphenine hydrochloride and nortriptyline hydrochloride whereas surfactants were ethoxylated sorbitan esters and polyethylene oxide?Cpolypropylene oxide?Cpolyethylene oxide triblocks. The critical micelle concentration (CMC) and CMC^id (CMC at ideal mixing condition) values suggest nonideal and attractive interactions among the components. The micellar mole fraction $ (X_{ 1}^{\text{m}} ) $ values calculated using Rubingh??s model indicate predominance of the nonionic surfactant in micelle formation. The mole fraction of surfactant in mixed monolayer $ (X_{1}^{\sigma } ) $ values are greater than $ X_{ 1}^{\text{m}} $ values, indicating a greater contribution of surfactant in monolayer formation. Thermodynamic parameters, viz. Gibbs energy of micellization $ (\Updelta G_{\text{m}}^{\text{o}} ) $ , Gibbs energy of adsorption $ (\Updelta G_{\text{ad}}^{\text{o}} ) $ , and excess free energy of mixed micelles $ (\Updelta G_{\text{ex}}^{\text{m}} ) $ and monolayers $ (\Updelta G_{\text{ex}}^{\sigma } ) $ were also evaluated. All these values suggest stable mixed micelle and mixed monolayer formation.     

Interactions Between a Sulfobetaine-Type Zwitterionic Gemini Surfactant and Fatty Acid Alkanolamide in Aqueous Micellar Solution

The critical micelle concentration (CMC) of 1,2-bis[N-methyl-N-(3-sulfopropyl)-alkylammonium]-ethane betaine (GCS12) was measured using a tensiometric method in the presence of inorganic salts. Inorganic salt has a little impact on the surface tension and CMC of zwitterionic gemini surfactant. The CMC value of GCS12 is 0.07 mmol/L in distilled water, while all CMC values are around 0.04–0.05 mmol/L in the presence of 0.5 % NaCl, 2 % NaCl, and 2 % NaCl + 0.05 % CaCl₂. The interactions between GCS12 and non-ionic surfactant lauric acid diethanolamide (CDA) were investigated by measuring the CMC of their mixtures at different molar ratios. CDA and GCS12 form mixed micelles and exhibit synergism when the mole fraction of CDA is higher than 0.25. Both the steric effect of the head group and GCS12 charge affect the formation and stability of the mixed micelles. Small amounts of GCS12 with a lower CMC penetrate into the micelle of nonionic surfactant with a higher CMC and reduce its degree of hydration inducing an attractive interaction between the two surfactants.     

Structure and Biological Behaviors of Some Metallo Cationic Surfactants

In this study, different cationic surfactants were prepared by esterification with bromoacetic acid of different fatty alcohols, i.e., dodecyl, tetradecyl and hexadecyl species. The products were then reacted with diphenyl amine, and the resulting tertiary amines were quaternized with benzyl chloride to produce a series of quaternary ammonium salts. The metallocationic surfactants were prepared by complexing the cationic surfactants with nickel and copper chlorides. Surface tension of these surfactants were investigated at different temperatures. The surface parameters including critical micelle concentration (CMC), maximum surface excess (Γ _max), minimum surface area (A _min), efficiency (PC₂₀) and effectiveness (π _CMC) were studied. The thermodynamic parameters such as the free energy of micellization ( $\Updelta G_{\text{mic}}^{^\circ }$ ) and adsorption ( $\Updelta G_{\text{ads}}^{^\circ }$ ), enthalpy ( $\Updelta H_{\text{m}}^{^\circ }$ ), ( $\Updelta H_{\text{ads}}^{^\circ }$ ) and entropy ( $\Updelta S_{\text{m}}^{^\circ }$ ), ( $\Updelta S_{\text{ads}}^{^\circ }$ ) were calculated. FTIR spectra and ¹H-NMR spectra were obtained to confirm the compound structures and purity. In addition, the antimicrobial activities were determined via the inhibition zone diameter of the prepared compounds, which were measured against six strains of a representative group of microorganisms. The results indicate that these metallocationic surfactants exhibit good surface properties and good biological activity on a broad spectrum of microorganisms.     

Synthesis and Properties of X-Type Alkyl Sulfonate Gemini Surfactants Derived from Cyanuric Chloride

A series of X-type alkyl sulfonate Gemini surfactants (XC_n, n?=?6, 8, 10) was synthesized by a simple method. The chemical structures of the prepared compounds were confirmed by ¹H NMR, ¹³C NMR, ESI?CMS and Elementary analysis. The surface activity and thermodynamic properties of micellization of the X-type alkyl sulfonate Gemini surfactants were compared with sodium dodecylsulfate by means of surface tension. The properties of XC_n are superior to those of SDS such as the ??_CMC and CMC of XC₁₀ are 26.3?mN/m and 0.2?mmol/L respectively. The adsorption isotherms for XC_n were established by fitting the pre-CMC surface tension data with a quadratic function. The thermodynamic parameters of micellization ( $ \Updelta G_{m}^{ \circ } $ , $ \Updelta H_{m}^{ \circ } $ , $ \Updelta S_{m}^{ \circ } $ ) derived from electrical conductivity indicate that the micellization of XC_n is entropy-driven.     

Surface and Biological Activity of Some Prepared Iminium Surfactants Based on Schiff Bases

A series of novel iminium surfactants were prepared through quaternization of different prepared fatty Schiff bases with benzyl chloride. The chemical structures were confirmed using FTIR, ¹H-NMR and mass spectroscopy. The surface properties and biological activity of these surfactants were investigated. The surface parameters including critical micelle concentration (CMC), maximum surface excess (Γ_max) and minimum surface area (A _min), Efficiency (PC₂₀) and Effectiveness (π_CMC) as well as the free energy of micellization ( $ \Updelta G_{\text{mic}}^{\text{o}} $ ) and adsorption ( $ \Updelta G_{\text{ads}}^{\text{o}} $ ) were calculated. It was found that the prepared compounds have good surface and biological activity.     

Synthesis and Physico-Chemical Studies of Ester-Quat Surfactants in the Series of (Dodecanoyloxy)propyl n-Alkyl Dimethyl Ammonium Bromide

Ester-quat surfactants in the series of (dodecanoyl oxy) propyl n-alkyl dimethyl ammonium bromide referred to here as LC₃Cm (where m is the hydrocarbon chain lengths 8, 12 and 14) were synthesized and characterized by the usual spectroscopic methods (NMR, IR, MS…). Their physico-chemical properties were investigated by surface tension and conductimetric measurements. From surface tension measurements, isotherms and thermodynamic adsorption parameters were determined. The critical micelle concentration (CMC), the degree of counter ion dissociation (α) of micelles in the water and the standard Gibbs free energy $( \Updelta G_{\text{m}}^{0}) $ , of micellization were also determined by conductimetric measurements. The results obtained from both methods were compared to the similar surfactants in the series of quaternary ammonium surfactants. Optical microscopy was also used to study the behavior of anhydrous surfactants and the binary water/surfactant system as a function of temperature.     

Density, ultrasonic velocity, viscosity and their excess parameters of the binary mixtures of N,N-dimethylaniline+1-alkanols (C3-C5), +2-alkanols (C3-C4), +2-methyl-1-propanol, +2-methyl-2-propanol at 303.15K

The density, ultrasonic velocity of sound and viscosity of binary mixtures of N,N-dimethyl aniline (N,NDMA) with 1-propanol, +2-propanol, +1-butanol, +2-butanol, +1-pentanol, +2-methyl-1-propanol, +2-methyl-2-propanol were measured at 303.15 K. These experimental data have been used to calculate excess volume V ^E , excess ultrasonic speeds u ^E , excess intermolecular free length L _f ^E , excess acoustic impedance Z ^E , excess isentropic compressibility κ _s ^E , deviation in viscosity Δη and excess Gibbs free energy of activation of viscous flow (G* ^E ). The values of L _f ^E and κ _s ^E are negative over the wide range of composition for all the binary mixtures, while the values of Z ^E are positive. These results have been used to discuss the nature of interaction between unlike molecules in terms of hydrogen bonding, dipole-dipole interaction, proton-acceptor interaction and dispersive forces. The viscosity data have been correlated using three equations: Grunberg and Nissan, Katti & Chaudhri and Hind et al. The excess/deviations were fitted by a Redlich-Kister equation and the results were analyzed in terms of specific interactions present in these mixtures.     

Aggregation and Phase Separation Phenomenon of Amitriptyline Hydrochloride Under the Influence of Pharmaceutical Excipients

The interaction between the amphiphilic drug amitriptyline hydrochloride (AMT) and the nonionic surfactants used in drug delivery has been investigated. Herein, we report the micellization behavior of AMT in presence of ethoxylated alkyl phenols in aqueous medium and the clouding phenomenon in the absence and presence of different nonionic surfactants in buffer solution. The values of critical micelle concentration (CMC) of AMT obtained using the conductivity method, decrease as nonionic surfactant concentration increases. With an increase in temperature, the CMC first increases and then decreases. At 303.15 K, the maximum CMC values were obtained with or without nonionic surfactant. The results obtained indicate attractive interactions (synergism) between the two mixing amphiphiles in solution. The experimentally obtained critical micelle concentration (CMC) values are always lower than ideal CMC values. Micellar mole fraction (X₁) values, calculated by different proposed models, show the contribution of nonionic surfactant concentration. At a fixed drug concentration (50 mmol kg^?1) and pH (=6.7) nonionic surfactants show continuous increase in cloud point (CP). Increase in drug concentration and pH, in the presence of fixed amounts of nonionic surfactant, increases and decreases the CP, respectively.     

Increased total sulfur content in coal from Donets and other basins

The ash composition is used to assess the conditions of coal-bed formation in the Donets and L’vovsk-Volynsk basins. The experimental data are inconsistent with some aspects of the hypothesis that pyrite and secondary organic sulfur are formed in the coal. The lack of a relationship between the total sulfur content S _t ^d in the coal and the MgO content in its ash does not agree with the notion that sulfates from sea water provide the basis source of nonvegetative sulfur in coal. The actual S _t ^d values do not always correspond to the theory that the source of sulfur depends on the alkalinity of the water and the reducing medium where the deposits accumulate. In the conditions that are most favorable to the formation of coal with high total sulfur content (S _t ^d > 4 wt %) according to the existing hypothesis, the actual value of S _t ^d is no more than 1.5%. The source of pyrite and organic sulfur in coal requires further discussion.     

Comparative e.m.f. study of CaF2 and β-alumina cells with Ni/NiF2 and Fe/FeF2 or Cr/CrF2 electrodes

The reliability of employing beta-alumina as electrolyte for fluorine potential measurement is examined by measuring the e.m.f.s of the galvanic cells with metal/metal fluoride electrodes and comparing with those obtained by using CaF₂ as electrolyte under identical conditions. The results from both types of galvanic cell can be superimposed to give the following standard Gibbs energy of formation, ΔG _f ⁰ , of FeF₂ and CrF₂ over extended ranges of temperature: $$\begin{gathered} \Delta G_f^0 (FeF_2 ) = - 702.0 + 0.125 20T (K) ( \pm 0.70) kJ mol^{ - 1} (506 - 1063K) \hfill \\ \Delta G_f^0 (CrF_2 ) = - 732.8 + 0.087 90T (K) ( \pm 0.64) kJ mol^{ - 1} (497 - 1063K) \hfill \\ \end{gathered} $$ The absence of significant temperature-dependent errors in both these measurements are verified by a third law treatment of the data yielding values of ?716.8 and ?777.4 kJ mol^?1 for ΔH _f.298 ⁰ of FeF₂ and CrF₂, respectively. The feasibility of using beta-alumina electrolyte cells for e.m.f. measurements on other metal/metal fluoride systems is discussed in the light of the existence of a useful potential domain of beta-alumina. High sodium potential in the electrode system can lead to sodium depletion. Likewise, low sodium potential may result in oxidation of the metals in the electrodes. Both these limiting factors are also examined.     

Synthesis and single-crystal structure of lead oxide nanoclusters in zeolite Y, |Pb 15.5 2+ (Pb4O4(Pb 16/19 2+ Pb 3/19 4+ )4)4.75|[Si117Al75O384]-FAU

A single crystal of excessively Pb²⁺-exchanged zeolite Y (|Pb _15.5 ²⁺ (Pb₄O₄(Pb _16/19 ²⁺ Pb _3/19 ⁴⁺ )₄)_4.75|[Si₁₁₇Al₇₅O₃₈₄]-FAU) was prepared by exchange of Na–Y (|Na₇₅|[Si₁₁₇Al₇₅O₃₈₄]-FAU, Si/Al = 1.56) with an aqueous stream 0.05 M Pb(C₂H₃O₂)₂ at 294 K, followed by vacuum dehydration at 1 × 10^?6 Torr and 693 K. Its structure was determined at 100 K, by X-ray diffraction techniques in the cubic space group Fd $ \overline{3} $ 3 ¯ m and was refined to the final error indices R ₁/wR ₂ = 0.0639/0.1323. About 53.5 Pbⁿ⁺ ions per unit cell occupy three different equipoints; 26 are at site I′, 19 are at site II, and the remaining 8.5 are at another site II. Three Pb⁴⁺ ions at some of the positions must have higher oxidation states due to elevated dehydration temperature; Pb(IIa) is supposed to coexist with Pb²⁺ and Pb⁴⁺ ions assuming the charge balance of the zeolite framework. A distorted Pb₄O₄ cube, alternating Pb²⁺ at Pb(I′) and O^2? at O(5), coordinates with four Pb²⁺ and/or Pb⁴⁺ ions through its oxygen atoms to give a [Pb ₄ ²⁺ O ₄ ^2? (Pb _16/19 ²⁺ Pb _3/19 ⁴⁺ )₄]^176/19+ cluster in 4.75 of eight sodalite cavities per unit cell in zeolite Y.