Mixed self-assembly of poly(ethylene oxide)-b-poly(epsilon-caprolactone) copolymers and sodium dodecyl sulfate in aqueous solution

Interaction of amphiphilic poly(ethylene oxide)-b-poly(epsilon-caprolactone) copolymers with anionic sodium dodecyl sulfate (SDS) has been investigated in aqueous solution. Formation of mixed micelles has been confirmed by surface tension measurements, whereas the influence of the surfactant on the copolymer self-assembling has been studied by measurement of the 1H NMR self-diffusion coefficients and by small-angle neutron scattering. As a rule, the surfactant decreases the heterogeneity of the micellar structures formed by the copolymer in water. Moreover, increasing the content of SDS results in the increasingly more important extension of the poly(ethylene oxide) (PEO) corona chains and the copolymer micelle deaggregation. The stability of the micelles against SDS increases with the length of the hydrophobic block. Preliminary two-dimensional NMR measurements with nuclear Overhauser enhancement have confirmed the spatial vicinity between SDS and the constitutive blocks of the copolymer.     

Effect of ionic surfactants on the hydration behavior of triblock copolymer micelles: a solvation dynamics study of coumarin 153

Dynamic fluorescence Stokes shift measurements of coumarin 153 (C153) have been carried out to study the influence of ionic surfactants (sodium dodecyl sulfate, SDS and hexadecyltrimethylammonium chloride, CTAC) on the hydration behavior of aqueous poly(ethylene oxide)(20)-poly(propylene oxide)(70)-poly(ethylene oxide)20 (P123) block copolymer micelles. Increase in SDS or CTAC concentration at a fixed P123 concentration induces the steady-state emission spectra of C153 to shift gradually toward lower energy. This is attributed to an increase in polarity (due to enhanced hydration) experienced by the probe as a consequence of incorporation of ionic head groups in the Corona region. The observed dynamic fluorescence Stokes shift value decreases more in mixed micellar systems than in pure copolymer micelles and the trends are quite similar in the presence of SDS and CTAC. The spectral shift correlation functions were observed to be nonexponential in nature. Critical analysis of the spectral shift correlation function indicates a fast solvation component (<0.2 ns) in P123 micelles, which was absent in the presence of ionic surfactants. Due to increased hydration in the presence of ionic surfactants, the initial fast solvation event was elusive in mixed copolymer-surfactant systems, reflecting the absence of faster solvation component and reduced observed Stokes shift in mixed systems. It has been argued that in the low surfactant concentration region, increase in hydration with the incorporation of ionic head groups in the Corona region is mainly due to increase in mechanically trapped water content. However, at higher surfactant concentrations, bound water content dominates and leads to slower solvation dynamics. The present results also indicate that though CTAC alters the Corona hydration more efficiently than SDS, the overall influence of ionic surfactants on the Corona hydration is grossly similar irrespective of the cationic or anionic nature of the surfactants. Interaction of SDS and CTAC with poly(ethylene oxide)(100)-poly(propylene oxide)(70)-poly(ethylene oxide)(100) (F127) block copolymer micelles has also been studied to comprehend the effect of copolymer composition. The overall trends in dynamic fluorescence Stokes shift and solvation times are similar in both the copolymer micelles.     

Block polyelectrolytes and colloidal stability

The interactions of sodium dodecyl sulfate (SDS) with poly(ethylene oxide)/poly(alkylene oxide) (E/A) block copolymers are explored in this study. With respect to the specific compositional characteristics of the copolymer, introduction of SDS can induce fundamentally different effects to the self-assembly behavior of E/A copolymer solutions. In the case of the E(18)B(10)-SDS system (E = poly(ethylene oxide) and B = poly(butylene oxide)) development of large surfactant-polymer aggregates was observed. In the case of B(20)E(610)-SDS, B(12)E(227)B(12)-SDS, E(40)B(10)E(40)-SDS, E(19)P(43)E(19)-SDS (P = poly(propylene oxide)), the formation of smaller particles compared to pure polymeric micelles points to micellar suppression induced by the ionic surfactant. This effect can be ascribed to a physical binding between the hydrophobic block of unassociated macromolecules and the non-polar tail of the surfactant. Analysis of critical micelle concentrations (cmc(*)) of polymer-surfactant aqueous solutions within the framework of regular solution theory for binary surfactants revealed negative deviations from ideal behavior for E(40)B(10)E(40)-SDS and E(19)P(43)E(19)-SDS, but positive deviations for E(18)B(10)-SDS. Ultrasonic studies performed for the E(19)P(43)E(19)-SDS system enabled the identification of three distinct regions, corresponding to three main steps of the complexation; SDS absorption to the hydrophobic backbone of polymer, development of polymer-surfactant complexes and gradual breakdown of the mixed aggregates.     

Breakdown kinetics of aggregates from poly(ethylene glycol‐bl‐propylene sulfide) di‐ and triblock copolymers induced by a non‐ionic surfactant

We explored the effects of addition of the nonionic surfactant Triton X‐100 on the stability of aggregates of poly(ethylene glycol‐bl‐propylene sulfide) di‐ and triblock copolymers. Fluorescence spectra of pyrene, used as a probe molecule, elucidated the various stages of transformation from pure copolymeric micelles to surfactant‐rich micelles. Turbidity measurements yielded insight into the mechanism of the interaction, the hydrophobicity of the copolymer driving the process. Triton X‐100 tends to strongly interact with highly hydrophobic copolymers by inserting into the core of the micellar aggregates. On the other hand, Triton X‐100 tends to interact with the corona of micelles formed by less hydrophobic copolymers which, for this reason, are more stable upon addition of this destabilizing agent. Kinetic data give evidence that only monomers, not micelles of surfactant, interact with the copolymer micelles. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 2477–2487, 2008     

A new design for light-breakable polymer micelles

A new and general design strategy is presented for amphiphilic block copolymers whose micellar aggregates can be dissociated by light. A diblock copolymer composed of hydrophilic poly(ethylene oxide) (PEO) and a hydrophobic polymethacrylate bearing pyrene pendant groups (PPy) was synthesized using ATRP. Upon UV light irradiation of polymer micellar solutions, the photosolvolysis of pyrene moieties results in their detachment from the polymer and converts the hydrophobic PPy block into hydrophilic poly(methacrylic acid). This effect leads to complete dissociation of polymer micelles.     

Effect of SDS on the self-assembly behavior of the PEO-PPO-PEO triblock copolymer (EO)20(PO)70(EO)20

The mixed micellar system comprising the poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide)-based triblock copolymer (EO)(20)(PO)(70)(EO)(20) (P123) and the anionic surfactant sodium dodecyl sulfate (SDS) has been investigated in aqueous media by small-angle neutron scattering (SANS) and viscosity measurements. The aggregation number of the copolymer in the micelles decreases upon addition of SDS, but a simultaneous enhancement in the degree of micellar hydration leads to a significant increase in the micellar volume fraction at a fixed copolymer concentration. This enhancement in the micellar hydration leads to a marked increase in the stability of the micellar gel phase until it is destroyed at very high SDS concentration. Mixed micellar systems with low and intermediate SDS concentrations form the micellar gel phase in much wider temperature and copolymer concentration ranges than the pure copolymer micellar solution. A comparison of the observed results with those for the copolymers (EO)(26)(PO)(40)(EO)(26) (P85) and (EO)(99)(PO)(70)(EO)(99) (F127) suggests that the composition of the copolymers plays a significant role in determining the influence of SDS on the gelation characteristics of the aqueous copolymer solutions. Copolymers with high PO/EO ratios show an enhancement in the stability of the gel phase, whereas copolymers with low PO/EO ratios show a deterioration of the same in the presence of SDS.     

The Effects of Salts and Ionic Surfactants on the Micellar Structure of Tri‐Block Copolymer PEO‐PPO‐PEO in Aqueous Solution

The micelles of two poly(ethylene oxide)‐poly(propylene oxide)‐poly(ethylene oxide) (PEO‐PPO‐PEO) block copolymers, P123 and F127 (same mol wt of PPO but different % PEO) in aqueous solution in the absence and presence of salts as well as ionic surfactants were mainly examined by dynamic light scattering (DLS). The study is further supported by cloud point and viscosity measurements. The change in cloud point (CP), as well as the size of micelles in aqueous solution in presence of salts obeys the Hofmeister lyotropic series. Addition of both cationic cetylpyridinium chloride (CPC) and anionic sodium dodecylsulfate (SDS) surfactants in the aqueous solution of P123 show initial decrease of micellar size from 20 nm to nearly 7 nm and then increasing with a double relaxation mode, further in the presence of NaCl this double relaxation mode vanishes. The effect of surfactant on F127, which has much bigger hydrophilic part is different than P123 and have no double relaxation. The relaxation time distributions is obtained using the Laplace inversion routine REPES. Two relaxation modes for P123 are explained on the bases of Pluronic rich mixed micelles containing ionic surfactants and the other smaller, predominantly surfactant rich micelles domains.     

Spontaneous generation of amphiphilic block copolymer micelles with multiple morphologies through interfacial Instabilities

We introduce a method for the formation of block copolymer micelles through interfacial instabilities of emulsion droplets. Amphiphilic polystyrene-block-poly(ethylene oxide) (PS-PEO) copolymers are first dissolved in chloroform; this solution is then emulsified in water and chloroform is extracted by evaporation. As the droplets shrink, the organic solvent/water interface becomes unstable, spontaneously generating a new interface and leading to dispersion of the copolymer as micellar aggregates in the aqueous phase. Depending on the composition of the copolymer, spherical or cylindrical micelles are formed, and the method is shown to be general to polymers with several different hydrophobic blocks: poly(1,4-butadiene), poly(-caprolactone), and poly(methyl methacrylate). Using this method, hydrophobic species dissolved or suspended in the organic phase along with the amphiphilic copolymer can be incorporated into the resulting micelles. For example, addition of PS homopolymer, or a PS-PEO copolymer of different composition and molecular weight, allows the diameter and morphology of wormlike micelles to be tuned, while addition of hydrophobically coated iron oxide nanoparticles enables the preparation of magnetically loaded spherical and wormlike micelles.     

Poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide)-g-poly(vinylpyrrolidone): association behavior in aqueous solution and interaction with anionic surfactants

In this work, we aimed to study the association and interaction behavior of poly(ethylene oxide)-b-poly(propylene oxide)-b-poly(ethylene oxide) block copolymers grafted with poly(vinylpyrrolidone). Critical micellization concentrations were determined using fluorescent probes (pyrene) and critical micellization temperatures characterizing temperature-dependent transitions from monomers to multimolecular micelles were measured. The thermal responsiveness of the copolymer is not affected by the grafting. The hydrodynamic radius of the graft copolymer micelles is found to be greater than that of the original copolymer micelles. The graft copolymer is found to form anisotropic aggregates. The structure of the graft copolymer micelles is less disrupted by the anionic surfactant sodium dodecyl sulfate, compared to the ungraft copolymer.     

Noncovalent triblock copolymers based on a coiled-coil peptide motif

The formation of a noncovalent triblock copolymer based on a coiled-coil peptide motif is demonstrated in solution. A specific peptide pair (E and K) able to assemble into heterocoiled coils was chosen as the middle block of the polymer and conjugated to poly(ethylene glycol) (PEG) and polystyrene (PS) as the outer blocks. Mixing equimolar amounts of the polymer-peptide block copolymers PS-E and K-PEG resulted in the formation of coiled-coil complexes between the peptides and subsequently in the formation of the amphiphilic triblock copolymer PS-E/K-PEG. Aqueous self-assembly of the separate peptides (E and K), the block copolymers (PS-E and K-PEG), and equimolar mixtures thereof was studied by circular dichroism, dynamic light scattering, and cryogenic transmission electron microscopy. It was found that the noncovalent PS-E/K-PEG copolymer assembled into rodlike micelles, while in all other cases, spherical micelles were observed. Temperature-dependent studies revealed the reversible nature of the coiled-coil complex and the influence of this on the morphology of the aggregate. A possible mechanism for these transitions based on the interfacial free energy and the free energy of the hydrophobic blocks is discussed. The self-assembly of the polymer-peptide conjugates is compared to that of polystyrene-b-poly(ethylene glycol), emphasizing the importance of the coiled-coil peptide block in determining micellar structure and dynamic behavior.     

Biodegradable/biocompatible ABC triblock copolymer bearing hydroxyl groups in the middle block

New biodegradable/biocompatible ABC block copolymers, poly(ethylene oxide)‐b‐poly(glycidol)‐b‐poly(L ,L ‐lactide) (PEO‐PGly‐PLLA), were synthesized. First, PEO‐b‐poly(1‐ethoxyethylglycidol)‐b‐PLLA was synthesized by a successive anionic ring‐opening copolymerization of ethylene oxide, 1‐ethoxyethylglycidyl ether, and L ,L ‐lactide initiated with potassium 2‐methoxyethanolate. In the second step, the 1‐ethoxyethyl blocking groups of 1‐ethoxyethylglycidyl ether were removed at weakly acidic conditions leaving other blocks intact. The resulting copolymers were composed of hydrophilic and hydrophobic segments joined by short polyglycidol blocks with one hydroxyl group in each monomeric unit. These hydroxyl groups may be used for further copolymer transformations. The PEO‐PGly‐PLLA copolymers with a molecular weight of PLLA blocks below 5000 were water‐soluble. Above the critical micellar concentration (ranging from 0.05 to1.0 g/L, depending on the composition of copolymer), copolymers formed macromolecular micelles with a hydrophobic PLLA core and hydrophilic PEO shell. The diameters of the micelles were about 25 nm. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3750–3760, 2003     

Soluble complexes of sodium poly(isoprene-b-methacrylate) micelles with cationic surfactants in aqueous media

Water-soluble complexes between sodium poly(isoprene-b-methacrylate) (NaIMA) amphiphilic block copolymer micelles and two cationic surfactants with different hydrophobic tail lengths, namely, dodecyltrimethylammonium bromide (DTMAB) and octyltrimethylammonium bromide (OTMAB), were prepared by mixing individual aqueous solutions of block copolymers and surfactants. The complexes were characterized in terms of size, overall charge, and micropolarity by dynamic light scattering, zeta-potential measurements, and fluorescence spectroscopy. Properties of the systems were investigated as a function of surfactant concentration and surfactant type and state in the initial solutions, as well as temperature. Experiments reveal surfactant complexation at the coronal sodium poly(methacrylate) (NaMA) chains, followed by an increase in mass and a decrease in size of the micelles. Complexation of individual surfactant micelles was observed when the DTMAB concentration in the starting solutions was higher than the surfactant cmc. The complexes show a temperature dependence of their dimension due to the hydrophobic effect.     

A critical assessment of capillary condensation and evaporation equations: a computer simulation study

Nonaqueous reverse micelles of brij surfactants are prepared in benzene and ethylammonium nitrate (EAN). The effect of polar head group bulk on reverse micellar size was studied with brij-52, brij-56 and brij-58 whereas the effect of polarity of hydrocarbon chain was investigated taking brij-52 and brij-93 with varying W(s) (W(s)=[EAN]/[surfactant]). Dynamic light scattering (DLS) has been employed to reveal the size and shape of the reverse micelles. Micropolarities of these reverse micelles were investigated by visible spectroscopy using methylene blue (MB) and methyl orange (MO) as molecular optical probes. It has been revealed from the experimental results that with increase in polar head group size reverse micellar size increases. Moreover, it is also observed that with increasing polarity of the hydrocarbon chain the average size of the reverse micelles decreases. It can be concluded that polar head group size and polarity of hydrocarbon chain play important roles in determining reverse micellar size of the brij surfactants apart from the W(s) ratio, nature of the solvent medium, and concentration of the surfactants.     

Study of molecular motion of block copolymers in solution by high-resolution proton magnetic resonance

Molecular motions of hydrophobic–hydrophilic water-soluble block copolymers in solution were investigated by high-resolution proton magnetic resonance (NMR). Samples studied include block copolymers of polystyrene–poly(ethylene oxide), polybutadiene–poly(ethylene oxide), and poly(ethylene oxide)–poly(propylene oxide)–poly(ethylene oxide). NMR measurements were carried out varying molecular weight, temperature, and solvent composition. For AB copolymers of polystyrene and poly(ethylene oxide), two peaks caused by the phenyl protons of low-molecular-weight (M?_n = 3,300) copolymer were clearly resolved in D₂O at 100°C, but the phenyl proton peaks of high-molecular-weight (M?_n = 13,500 and 36,000) copolymers were too broad to observe in the same solvent, even at 100°C. It is concluded that polystyrene blocks are more mobile in low-molecular-weight copolymer in water than in high-molecular-weight copolymer in the same solvent because the molecular weight of the polystyrene block of the low-molecular-weight copolymer is itself small. In the mixed solvent D₂O and deuterated tetrahydrofuran (THF-d₈), two peaks caused by the phenyl protons of the high-molecular-weight (M?_n = 36,000) copolymer were clearly resolved at 67°C. It is thought that the molecular motions of the polystyrene blocks are activated by the interaction between these blocks and THF in the mixed solvent.     

Functional and site-specific macromolecular micelles as high potential drug carriers

Since several years, macromolecular micelles based on amphiphilic block copolymers have attracted much interest as drug carriers. These micelles show a long term blood circulation time resulting from their small diameter and the steric repulsion created by the poly(ethylene oxide) chains which constitute micelle corona, as well as from their high thermodynamic stability. Besides this long term blood circulation time generating a passive targeting, an active targeting, chemical or physical affinity targeting, might allow the preparation of more efficient drug carriers. In order to obtain such double targeting properties, we have prepared two kinds of macromolecular micelles. The first one is based on amphiphilic poly(ethylene oxide)/poly(β-benzyl -aspartate) ---PEO/PBLA--- block copolymers having hydroxy groups at the free end of PEO chains. As a result of their structure, such micelles have hydroxy groups on their outer-shell which can be further modified in order to introduce a targeting moiety (sugar, etc.). The characteristics (diameter, critical micellar concentration (cmc), drug loading capacity) have been determined. Moreover, doxorubicin loaded -hydroxy PEO/PBLA micelles have been shown to be slightly more cytotoxic than the corresponding -methoxy PEO/PBLA micelles. The second type of micelles is based on thermosensitive amphiphilic poly(N-isopropyl acrylamide)/polystyrene ---PIPAAm/PSt--- block copolymers. Such micelles have a small diameter and a low cmc in addition to thermosensitivity properties which are similar to those of PIPAAm.     

Aqueous block copolymer-surfactant mixtures and their ability in solubilizing chlorinated organic compounds. A thermodynamic and SANS study

Within the topic of surfactant enhanced solubilization of additives sparingly soluble in water, volumetric, solubility, conductivity, and small-angle neutron scattering (SANS) experiments on mixtures composed of alpha,omega-dichloroalkane, surfactant, copolymer, and water were carried out at 298 K. The triblock copolymers (ethylene oxide)132(propylene oxide)50(ethylene oxide)132 (F108) and (ethylene oxide)76(propylene oxide)29(ethylene oxide)76 (F68) were chosen to investigate the role of the molecular weight keeping constant the hydrophilic/hydrophobic ratio. The selected surfactants are sodium decanoate (NaDec) and decyltrimethylammonium bromide (DeTAB) with comparable hydrophobicity and different charged heads. The alpha,omega-dichloroalkanes were chosen as contaminant prototypes. For the water + surfactant + copolymer mixtures, both the volume and the SANS results straightforwardly evidenced that (1) monomers of NaDec and copolymer unimers generate small mixed aggregates, (2) monomers of DeTAB combined with copolymer unimers do not form aggregates, and (3) unimeric copolymer is solubilized into NaDec and DeTAB micelles. The alpha,omeaga-dichloroalkanes presence induces the F108 aggregation even at very low copolymer composition. The addition of surfactant disintegrates the F108 aggregates and, consequently, the additive is expelled into the aqueous phase. Once F108 is in the unimeric state, it forms copolymer-micelle aggregates which incorporate the oil. In the case of F68 both the volumetric and the SANS data reveal that the additive does not alter the copolymer unimeric state. Moreover, they show that for the aqueous DeTAB-F68 system the additive trapping in both the copolymer-micelle aggregate and the pure micelles takes place being enhanced in the former aggregate in agreement with solubility experiments. For the NaDec-F68 mixtures, an additional solubilization process in the premicellar copolymer-surfactant microstructures occurs. SANS and conductivity data show that the additive incorporation into the mixed and the pure micelles does not essentially influence the structural properties of the aggregates.     

Investigation of the micropolarity in reverse micelles of nonionic poly(ethylene oxide) surfactants using 4-nitropyridine-N-oxide as absorption probe

The micropolarities of the reverse micelle (RM) interior of nonionic poly(ethylene oxide) surfactants of the alkyl ether type (poly(ethylene oxide)[4] lauryl ether (C12E4, Brij 30)), alkyl-aryl ethers (poly(ethylene oxide)[4] nonylphenyl ether (C9PhiE4), poly(ethylene oxide)[5] nonylphenyl ether (C9PhiE5), and poly(ethylene oxide)[5] octylphenyl ether (C8PhiE5)), and poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) (PEO-PPO-PEO) triblock copolymers (Pluronics P123, F127) were investigated as a function of the water content by applying the absorption probe technique, using 4-nitropyridine-N-oxide (NP) as a probe. The change in the micellar aggregate micropolarity in different solvents (cyclohexane, decane, n-butanol, and n-butyl acetate) at various water contents has been investigated. The research was focused on the determination of the effects of surfactant structure and solvent type on the hydration degrees of the PEO chains in the region at the core limit, where the NP probe was located. All results regarding the polarities in RM and PEO/water calibration mixtures have been expressed in terms of Kosower's Z values, using the linear dependence of E(NP) on Kosower's Z. The PPO/butanol mixtures have also been used for RM in butanol as a reference system. The data revealed that local polarity in RM is dependent on the surfactant type, block copolymer composition, solvent nature, and water content. At the same water content, the results clearly indicate a lower hydration degree of triblock copolymers, as compared to the surfactants of the alkyl ether and alkyl-aryl ether type, but for P123 and F127 Pluronics in n-butanol the hydration is higher owing to the behavior of butanol as cosurfactant and to its hydration.     

Fluorometric and isothermal titration calorimetric studies on binding interaction of a telechelic polymer with sodium alkyl sulfates of varying chain length

Steady-state fluorescence measurements and isothermal titration calorimetric experiments have been performed to study the interaction between a telechelic polymer, pyrene-end-capped poly(ethylene oxide) (PYPY), and sodium alkyl sulfate surfactants having decyl, dodecyl, and tetradecyl hydrocarbon tails. Fluorometric results suggest polymer-surfactant interaction in the very low range of polymer concentrations. The relative variation in the excimer to monomer pyrene emission intensities with varying surfactant concentration reveals that initial addition of surfactant favors intramolecular preassociation until the surfactant molecules start binding with the ethylene oxide (EO) chain. With the growing number of surfactant aggregates along the EO chain, the association becomes hindered due to the polyelectrolyte effect. The results from microcalorimetric titrations in the low concentration range of PYPY solution (approximately 10(-6) M) with alkyl sulfates suggest two kinds of surfactant-polymer interactions, one with the polymer hydrophobic end groups and the other with the ethylene oxide backbone. The overall polymer-surfactant interaction starts at a much lower surfactant concentration for the hydrophobically modified polymers compared to that in the case of unsubstituted poly(ethylene oxide) homopolymer. From the experiments critical aggregation concentration values and the second critical concentration where free micelles start forming have been determined. An endeavor has been made to unveil the mechanism underlying the corresponding associations of the surfactants with the polymer.     

Design of Stimuli-Responsive Dynamic Covalent Delivery Systems for Volatile Compounds (Part 2): Fragrance-Releasing Cleavable Surfactants in Functional Perfumery Applications

Amphiphilic imines prepared by condensation of a hydrophobic fragrance aldehyde with a hydrophilic amine derived from a poly(propylene oxide) and poly(ethylene oxide) diblock copolymer were investigated as cleavable surfactant profragrances in applications of functional perfumery. In water, the cleavable surfactants assemble into micelles that allow solubilization of perfume molecules that are not covalently attached to the surfactant. Dynamic headspace analysis on a glass surface showed that solubilized perfume molecules evaporated in a similar manner in the presence of the cleavable surfactant as compared with a non-cleavable reference surfactant. Under application conditions, the cleavable surfactant imine hydrolysed to release the covalently linked fragrance aldehyde. The profragrances were stable during storage in aqueous media, and upon dilution showed a blooming effect for the hydrolytical fragrance release and a more balanced performance of a solubilized perfume by retaining the more volatile fragrances and boosting the evaporation of the less volatile fragrances.