Systematic control of the packing density of self-assembled monolayers using bidentate and tridentate chelating alkanethiols

The structural and interfacial properties of self-assembled monolayers (SAMs) on gold derived from the adsorption of a series of 1,1,1-tris(mercaptomethyl)alkanes (i.e., CH3(CH2)mC[CH2SH]3, where m = 9, 11, 13, 15) were investigated. The new SAMs, which possess uniformly low densities of alkyl chains, were characterized by ellipsometry, contact angle goniometry, and polarization modulation infrared reflection absorption spectroscopy. Additional analysis of the SAMs by X-ray photoelectron spectroscopy permitted a direct calculation of the packing densities of the SAMs on gold. The results as a whole, when compared to those obtained on SAMs generated from normal alkanethiols (CH3(CH2)m+2SH), 2-alkylpropane-1,3-dithiols (CH3(CH2)mCH[CH2SH]2), and 2-alkyl-2-methylpropane-1,3-dithiols (CH3(CH2)mC(CH3)[CH2SH]2) having analogous chain lengths, demonstrate that the 1,1,1-tris(mercaptomethyl)alkanes afford SAMs with alkyl chains having the lowest packing density and least conformational order.     

Self-assembled monolayers derived from a double-chained monothiol having chemically dissimilar chains

The structure and conformation of self-assembled monolayers (SAMs) derived from the adsorption of a specifically designed double-chained partially fluorinated thiol having the formula 12,12,13,13,14,14,15,15,16,16,17,17,18,18,19,19,19-heptadecafluoro -2-tetradecylnona-decane-1-thiol ( 2) onto the surface of evaporated gold were examined by ellipsometry, contact angle goniometry, polarization modulation infrared reflection-absorption spectroscopy (PM-IRRAS), and X-ray photoelectron spectroscopy (XPS). The results were compared to those of SAMs generated from normal hexadecanethiol ( 1) and a structurally related single-chained partially fluorinated thiol having the formula 12,12,13,13,14,14,15,15,16,16,17,17,18,18,19,19,19-heptadecafluorononadecane-1-thiol ( 3). Collectively, the studies demonstrate that the double-chained adsorbate 2 forms SAMs on gold in which the alkyl chains are less densely packed and less conformationally ordered than those in the SAMs derived from each of the single-chained adsorbates. Furthermore, the fluorocarbon moieties in the SAMs derived from 2 are more tilted from the surface normal than those in the SAMs derived from 3. The low values of contact angle hysteresis suggest, however, that the double-chained adsorbate 2 generates homogeneous monolayer films on the surface of gold.     

Loosely packed self-assembled monolayers on gold generated from 2-alkyl-2-methylpropane-1,3-dithiols

A series of 2-alkyl-2-methylpropane-1,3-dithiol derivatives with increasing alkyl chain lengths (i.e., CH3(CH2)mC(CH3)[CH2SH]2, where m = 7, 9, 11, 13, 15) were synthesized and used to generate self-assembled monolayers (SAMs) on gold. The resulting monolayers were analyzed by ellipsometry, contact angle goniometry, polarization modulation infrared reflection-absorption spectroscopy, and X-ray photoelectron spectroscopy. These data were compared with those obtained on SAMs on gold derived from normal alkanethiols (CH3(CH2)(m+2)SH) and 2-monoalkylpropane-1,3-dithiols (CH3(CH2)(m)CH[CH2SH]2) having the same number of carbon atoms in the primary chain. The results demonstrate that the 2-alkyl-2-methylpropane-1,3-dithiols generate conformationally disordered monolayer films in which the density of alkyl chains is less than those generated from normal alkanethiols and the 2-monoalkylpropane-1,3-dithiols.     

Structural effects on the barrier properties of self-assembled monolayers formed from long-chain omega-alkoxy-n-alkanethiols on copper

The adsorption of long-chain omega-alkoxy-n-alkanethiols [CH(3)(CH(2))(p-1)O(CH(2))(m)SH; m = 11, 19, 22; p = 18, 22] onto copper produces self-assembled monolayers (SAMs) that can provide protection against corrosion of the underlying metal substrate. The resulting films are 40-60 A in thickness and are isostructural with SAMs formed on copper from unsubstituted n-alkanethiols. As evidenced by electrochemical impedance spectroscopy (EIS), the barrier properties of these ether-containing SAMs depend on the chain length of the adsorbate and the position of the ethereal unit along the hydrocarbon chain. For SAMs where the ether substitution is farther from the copper surface, the initial coating resistances are similar to those projected for unsubstituted n-alkanethiolate SAMs of similar thickness. For SAMs where the ether substitution is nearer to the copper surface (m = 11), the resistances are significantly less than those for unsubstituted n-alkanethiolate SAMs of similar thickness, reflecting the effect of the molecular structure on the barrier properties of the film. Upon exposure to 1 atm of O(2) at 100% RH, the SAMs become less densely packed as observed by infrared (IR) spectroscopy, and their barrier properties deteriorate as observed by EIS. The rate that the SAMs lose their barrier properties upon exposure to oxidizing conditions is correlated to the strength of intermolecular interactions within the bulk state of the adsorbate.     

Synthesis of a series of oligo(ethylene glycol)-terminated alkanethiol amides designed to address structure and stability of biosensing interfaces.

A strategy for the synthesis of a series of closely related oligo(ethylene glycol)-terminated alkanethiol amides (principally HS(CH(2))(m)CONH(CH(2)CH(2)O)(n)H; m = 2, 5, 11, 15, n = 1, 2, 4, 6, 8, 10, 12) and analogous esters has been developed. These compounds were made to study the structure and stability of self-assembled monolayers (SAMs) on gold in the prospect of designing new biosensing interfaces. For this purpose, monodisperse heterofunctional oligo(ethylene glycols) with up to 12 units were prepared. Selective monoacylation of the symmetrical tetra- and hexa(ethylene glycol) diols as their mesylates with the use of silver(I) oxide was performed. The synthetic approach was based on carbodiimide couplings of various oligo(ethylene glycol) derivatives to omega-(acetylthio) carboxylic acids via a terminal amino or hydroxyl function. SAM structures on gold were studied with respect to thickness, wettability (water contact angles approximately 30 degrees ), and conformation. A good fit was obtained for the relation between monolayer thickness (d) and the number of units in the oligo(ethylene glycol) chain (n): d = 2.8n + 21.8 (A). Interestingly, the corresponding infrared spectroscopy analysis showed a dramatic change in conformation of the oligomeric chains from all-trans (n = 4) to helical (n > or = 6) conformation. A crystalline helical structure was observed in the SAMs for n > 6.     

New dialkyldithiophosphinic acid self-assembled monolayers (SAMs): influence of gold substrate morphology on adsorbate binding and SAM structure

We report the fabrication and characterization of new self-assembled monolayers (SAMs) formed from dihexadecyldithiophosphinic acid [(C(16))(2)DTPA] molecules on gold substrates. In these SAMs, the ability of the (C(16))(2)DTPA headgroup to chelate to the gold surface depends on the morphology of the gold substrate. Gold substrates fabricated by electron-beam evaporation (As-Dep gold) consist of ～50-nm grains separated by deep grain boundaries (～10 nm). These grain boundaries inhibit the chelation of (C(16))(2)DTPA adsorbates to the surface, producing SAMs in which there is a mixture of monodentate and bidentate adsorbates. In contrast, gold substrates produced by template stripping (TS gold) consist of larger grains (～200-500 nm) with shallower grain boundaries (<2 nm). On these substrates, the low density of shallow grain boundaries allows (C(16))(2)DTPA molecules to chelate to the surface, producing SAMs in which all molecules are bidentate. The content of bidentate adsorbates in (C(16))(2)DTPA SAMs formed on As-Dep and TS gold substrates strongly affects the SAM properties: Alkyl chain organization, wettability, frictional response, barrier properties, thickness, and thermal stability all depend on whether a SAM has been formed on As-Dep or TS gold. This study demonstrates that substrate morphology has an important influence on the structure of SAMs formed from these chelating adsorbates.     

Surface structure and chemical switching of thioctic acid adsorbed on Au(111) as observed using near-edge X-ray absorption fine structure

Thioctic acid (alpha-lipoic acid) is a molecule with a large disulfide-containing base, a short alkyl chain with four CH2 units, and a carboxyl termination. Self-assembled monolayer (SAM) films ofthioctic acid adsorbed on Au(111) have been investigated with near-edge X-ray absorption fine structure (NEXAFS) spectroscopy and X-ray photoelectron spectroscopy (XPS) to determine film quality, bonding, and morphology. Using standard preparation protocols for SAMs, that is, dissolving thioctic acid in ethanol and exposing gold to the solution, results in poor films. These films are highly disordered, contain a mixture of carboxyl and carboxylate terminations, have more than monolayer coverage, and exhibit unbound disulfide. Conversely, forming films by dissolving 1 mmol thioctic acid into 5% acetic acid in ethanol (as previously reported with carboxyl-terminated alkanethiols) forms ordered monolayers with small amounts of unbound sulfur. NEXAFS indicates tilted over endgroups with the carboxyl group normal on average 38 degrees from the surface normal. Slight angle-dependent intensity modulations in other features indicate alkyl chains statistically more upright than prostrate on the surface. Reflection-absorption Fourier transform infrared (RA-FTIR) spectra indicate hydrogen bonding between neighboring molecules. In such well-formed monolayers, a stark reorientation occurs upon deprotonation of the endgroup by rinsing in a KOH solution. The carboxylate plane normal is now about 66 degrees from sample normal, a much more upright orientation. Data indicate this reorientation may also cause a more upright orientation to the alkyl portion of the molecules.     

An Experimental and Theoretical Approach to Investigate the Effect of Chain Length on Aminothiol Adsorption and Assembly on Gold

Despite the numerous studies on the self‐assembled monolayers (SAMs) of alkylthiols on gold, the mechanisms involved, especially the nature and influence of the thiol–gold interface are still under debate. In this work the adsorption of aminothiols on Au(111) surfaces has been studied by using surface IR and X‐ray photoelectron spectroscopy (XPS) as well as by density functional theory (DFT) modeling. Two aminothiols were used, cysteamine (CEA) and mercaptoundecylamine (MUAM), which contain two and eleven carbon atoms, respectively. By combining experimental and theoretical methods, it was possible to draw a molecular picture of the thiol–gold interface. The long‐chain aminothiol produced better ordered SAMs, but, interestingly, the XPS data showed different sulfur binding environments depending on the alkyl chain length; an additional peak at low binding energy was observed upon CEA adsorption, which indicates the presence of sulfur in a different environment. DFT modeling showed that the positions of the sulfur atoms in the SAMs on gold with similar unit cells [(2√3×2√3)R30°] depended on the length of the alkyl chain. Short‐chain alkylthiol SAMs were adsorbed more strongly than long‐chain thiol SAMs and were shown to induce surface reconstruction by extracting atoms from the surface, possibly forming adatom/vacancy combinations that lead to the additional XPS peak. In the case of short alkylthiols, the thiol–gold interface governs the layer, CEA adsorbs strongly, and the mechanism is closer to single‐molecule adsorption than self‐assembly, whereas for long chains, interactions between alkyl chains drive the system to self‐assembly, leading to a higher level of SAM organization and restricting the influence of the sulfur–gold interface.     

Novel cyanoterphenyl self-assembly monolayers on Au(111) studied by ellipsometry, x-ray photoelectron spectroscopy, and vibrational spectroscopies

The self-assembled monolayers (SAMs) of two asymmetric disulfides derivatives (namely, LC1 and LC2) were prepared on Au(111). The disulfides contain a pure alkyl chain and an alkyl chain terminated by a cyanoterphenyl group. LC1 and LC2 differ by the way the cyanoterphenyl group is attached onto the alkyl chain: it is expected to be aligned with the alkyl chain in the case of LC1 and perpendicular to it in the case of LC2 (T shape). The consequences in terms of surface coverage, chemical composition, and molecular conformation of the two SAMs are studied using ellipsometry, x-ray photoelectron spectroscopy (XPS), reflection absorption infrared spectroscopy (RAIRS), and broadband femtosecond sum-frequency generation (SFG). A model of coverage and tilt angle based on ellipsometry and XPS results shows that the SAM "manages" the large size of the terphenyl group by lowering the terphenyl containing chain coverage and by increasing the tilt. In the case of LC2, the disulfide breaks during molecular assembly, less terphenyl chains adsorb than pure alkyl chains, and the overall chain coverage is smaller than for LC1. RAIRS and SFG results show that these differences in surface coverage correspond to a drastically different orientation of the terphenyl axis, which lies nearly parallel to the surface for LC2, while it is tilted by approximately 28 degrees for LC1. This shows that the terphenyl group takes much more space on the surface in the case of LC2 and explains why the terphenyl coverage is found smaller for LC2. The anomalous SFG relative intensities observed in the region of CH stretch between CH2 and CH3 modes, and symmetric and antisymmetric modes, show that the chains are not in the fully stretched, all-trans conformation, LC2 being probably more distorted than LC1. These distorsions allow the molecules to occupy the space available below the large terphenyl group. The relative intensities of symmetric and antisymmetric modes are discussed qualitatively for some typical molecular conformations and orientations of the alkyl chain.     

Preparation, characterization, and chemical stability of gold nanoparticles coated with mono-, bis-, and tris-chelating alkanethiols

A systematically varying series of monolayer-protected clusters (MPCs) was prepared by exposing small gold nanoparticles ( approximately 2 nm in diameter) to the following four adsorbates: n-octadecanethiol ( n - C18), 2-hexadecylpropane-1,3-dithiol ( C18C2), 2-hexadecyl-2-methylpropane-1,3-dithiol ( C18C3), and 1,1,1-tris(mercaptomethyl)heptadecane ( t - C18). The resultant MPCs were characterized by solubility studies, UV-vis spectroscopy, transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), and Fourier-transform infrared spectroscopy (FT-IR). All of the MPCs were soluble in common organic solvents; moreover, analysis by TEM showed that the core dimensions were unaffected by exposure to any of the adsorbates. Separate studies by XPS revealed that the sulfur atoms in all MPCs were predominantly bound to the surface of gold (i.e., approximately 85% or better). Analysis by FT-IR showed that MPCs functionalized with n - C18 possessed alkyl chains having the greatest conformational order in both the solid-state and dispersed in solution; in contrast, those generated from the other three adsorbates were more liquid-like with reduced conformational order (or crystallinity). The rate of nanoparticle decomposition induced by cyanide ions was monitored by UV-vis spectroscopy. While MPCs functionalized with n - C18 showed the fastest rate of decomposition, those functionalized with C18C3 were the most resistant to decomposition. Overall, the following trend in chemical stability was observed, C18C3 > C18C2 > t - C18 > n - C18.     

In situ deprotection and assembly of s-tritylalkanethiols on gold yields monolayers comparable to those prepared directly from alkanethiols

In this paper we describe a systematic study comparing the properties of self-assembled monolayers (SAMs) formed by in situ deprotection and assembly of S-triphenylmethyl (trityl)- and thiolacetate-protected alkanethiols to those of SAMs formed from the parent alkanethiols. The two in situ deprotections were carried out in trifluoroacetic acid and THF/ammonium hydroxide, respectively. Monolayers of octadecanethiol (ODT) and the peptide-containing alkanethiol 3-mercapto-N-n-pentadecylpropionamide (1ATC15) were assembled on gold using the two in situ methods and characterized by contact angle goniometry, X-ray photoelectron spectroscopy, polarization modulation infrared reflection absorption spectroscopy, and electrochemical characterization methods to assess how the monolayer properties compare to those of monolayers prepared by traditional methods. The results for the in situ deprotection of the trityl-protected molecules demonstrate that this method can afford high-quality monolayers that are nearly indistinguishable from those prepared directly from alkanethiols. The quality of the monolayers prepared using this method is shown to depend on the solubility of the trityl-protected compound in trifluoroacetic acid. The results for the in situ deprotection of acetyl-ODT indicate this method yields low-quality monolayers that contain mixtures of adsorbates bound as thiolates and thiolacetates. In situ trityl deprotection is a useful approach for monolayer formation that greatly simplifies the purification, handling, and assembly of thiol-containing monolayer precursors.     

硫醇自组装膜对金电极上吡咯电化学聚合的影响

用电化学聚合法在多种烷基硫醇自组装膜修饰金电极上制备了聚吡咯.通过计时安培法、循环伏安法和交流阻抗技术研究了自组装膜的烷基链长和端基功能团对吡咯聚合过程和性质的影响.当自组装膜较完美时,聚吡咯沉积在自组装膜表面;而当自组装膜有一定缺陷时,吡咯在针孔处成核,然后继续生长并完全覆盖在自组装膜表面.研究结果表明,烷基硫醇的链越短,吡咯聚合越容易;疏水的烷基硫醇自组装膜有利于聚吡咯在电极表面的生长.     

Electrochemical characterization of cationic surfactants’ adsorption on a disturbed n-alkanethiolate self-assembled monolayer-modified polycrystalline gold electrode

The adsorption of cetyltrimethylammonium bromide (CTAB) on disturbed n-alkanethiolate self-assembled monolayers (SAMs) was investigated by electrochemical methods with potassium ferricyanide [K₃Fe(CN)₆] as a probe. Compared with the completely restrained signal at ordinary compact n-alkanethiolate SAMs, the electrochemical response of K₃Fe(CN)₆ at the disturbed n-alkanethiolate SAMs was partly restored and became progressively reversible in the presence of increasing concentrations of CTAB, which was employed to characterize the adsorption of cationic surfactants on hydrophobic SAMs. The effect of CTAB concentration on electrochemical impedance spectroscopy (EIS) plots indicated that CTAB experienced two different types of adsorptive behavior at the disturbed n-alkanethiolate SAMs: monomer adsorption at low concentrations below 1×10^–6 M and monolayer adsorption at CTAB concentrations above 1×10^–5 M. The adsorption of a series of cationic surfactants with similar structures to CTAB on disturbed n-alkanethiolate SAMs was also explored. These surfactants had similar adsorptive behavior and showed nearly linear adsorption characteristics with the length of their hydrophobic tails.     

新型偶氮苯硫醇衍生物自组装膜的制备与结构表征

自组装单分子膜(ＳＡＭｓ)是近年来引起广泛注意的一种稳定的、二维有序的、致密的有机超薄膜体系,由于其优越的性能,在润滑、吸附、防腐、电化学及微电子等领域中显示出广阔的应用前景[1～4].自组装单分子膜是使用含有各种活性官能团(如-ＣＯＯＨ,-ＳＨ,-Ｓ-Ｓ-,-ＯＨ,-ＣＮ等)的分子,以化学键的形式与相应的基底(如Ａｕ,Ａｇ,Ｃｕ,Ｐｔ,Ｓｉ,Ｍｉｃａ等)相互作用从而自发地形成自组装膜.根据不同的研究或应用目的合理设计组装分子的结构及基底表面,从而得到具有所需功能的自组装单分子膜是近年来界面科学和材料科学等领域研究的热点之一.…     

新型偶氮苯硫醇衍生物自组装膜的制备与结构表征

Self Assembled Monolayers(SAMs) of a series of mercapto contained azobenzene derivatives with the structure of CnH2n+1AzoO(CH 2)mSH (where n =4,6,8,10,12; with m =3,5 respectively) were prepared and characterized. Wettability measurement of water on the SAMs demonstrates that molecular packing density in the monolayers increases while the alkyl chain in the molecules is lengthened. Both the n and m values have similar contribution to the wetting property of SAMs. The RA IR spectra reveal that the alkyl chains in the SAMs tilt away dramatically from the surface normal direction with the increase in their length. However, the orientation of azobenzene moiety is found to be influenced slightly by the alkyl chain length, which is due to the tenderness of the molecule.     

Structural characterization of microcontact printed arrays of hexa(ethylene glycol)-terminated alkanethiols on gold

This paper reports on the structural characteristics of microcontact printed oligo(ethylene glycol)-terminated alkanethiol layers, HS(CH2)15CONH-(CH2CH2O)6-H (hereafter EG6), on gold. Microwetting, contact angle goniometry, imaging null ellipsometry, and infrared reflection-absorption spectroscopy (IRAS) are used to characterize the printed EG6 layers, and the quality of these layers in terms of layer thickness and the crystallinity of the alkyl and ethylene glycol portions is compared with data obtained from analogous layers prepared by solution self-assembly. The outcome of the printing process is critically dependent on the experimental parameters used to prepare the patterns. It is found that high quality layers, consisting of densely packed all-trans alkyl chains terminated with relatively helical hexa(ethylene glycol) tails, are formed by inking the poly(dimethylsiloxane) (PDMS) stamp with a 1 mM EG6 solution and contacting it with gold for 15 min. The homogeneity of printed layers is not as good as the homogeneity of those prepared from solution under similar conditions, most likely because of simultaneous transfer of low molecular weight residues from the PDMS stamp. These residues, however, can be easily removed upon ultrasonication in ethanol without affecting the quality of the printed layer. Further on, the microscopic square-shaped bare gold patterns formed after microcontact printing (muCP) are subsequently filled with 16-hexadecanoic acid (hereafter THA) or HS(CH2)15CONH-(CH2CH2O)6-COOH (hereafter EG6COOH) to provide a microarray platform for further covalent attachment of biomolecules. Well-defined structures in terms of wettability contrast, sharpness, and height differences between the printed and back-filled areas are confirmed by imaging null ellipsometry and microscopic wetting.     

Preparation and electrochemistry of azobenzene self-assembled monolayers on gold--long range tunneling and end-group hydrogen bonding effect

A series of thiol-functionalied azobenzene derivatives (RAzoCnSH: R=H for n=3-6, abbreviated as AzoCnSH; R=CH(3)CONH for n=4, abbreviated as aaAzoC4SH) on gold electrodes were prepared and their self-assembly and electrochemical properties were studied by cyclic voltammetry. They all formed uniform and reproducible self-assembled monolayers (SAMs) on gold and showed well-behaved voltammetric responses in aqueous solution. Both the length of the alkyl chain spacer and the H-bonding of the end acetamino group had effects on the stability and the electrochemical kinetics of the SAMs, and the effect of the H-bonding was dominant. The surface coverage of the SAMs (AzoCnSH) is gradually increased with an increase of the alkyl chain spacer length, whereas the presence of the terminal acetamino group leads to a greater increase of the surface coverage. At a low scan rate, voltammetric responses corresponding to an irreversible two-electron, two-proton reduction/oxidation of the trans-azobenzene redox center were obtained in the range of +300 mV and -800 mV, which exhibited very large peak-to-peak splitting. At a high scan rate of 500 mV/s, two steps of reversible one-electron, one-proton reduction/oxidation corresponding to the cis-isomer in azobenzene-thiol SAMs (n is odd) was clearly observed between +300 and -200 mV. The apparent electron-transfer rate is decreased with increasing distance between the azobenzene redox center and the gold electrode. The existence of the end acetamino group which restricted the conformational change during the redox process also led to a decrease of the standard rate constant, and this restriction effect is more predominant than the distance effect.     

Odd-even chain length-dependent order in pH-switchable self-assembled layers

The reversible self-assembly of a series of bipolar amphiphiles, alpha,omega-bis(3- or 4-amidinophenoxy)alkanes (chain length n = 5-12), on mercaptoalkanoic acid-functionalized gold surfaces (chain length n = 10, 11, 14, 15) has been studied by in-situ ellipsometry, IR reflection absorption spectroscopy (IRAS), and atomic force microscopy (AFM). The layer order, amphiphile orientation, and tendency to form bilayers depends on the position of the amidine substituent, the alkyl chain length of both the amidine amphiphile and the underlying acid self-assembled monolayer (SAM), and whether the amidine alkyl chain contained an even or odd number of methylene groups. Thus, para-substituted bisbenzamidines containing more than six methylene groups (n>6) and with an odd number (n = 7, 9, 11) tended to form bilayered structures, whereas those containing an even number formed monolayers when adsorbed on SAMs of the long-chain acids (n = 14, 15). This behavior also correlated with the average tilt angle of the benzene moieties of the amphiphiles, as estimated by IRAS. The odd-numbered chains gave lower tilt angles than the even-numbered ones, and a possible model that accounts for these results is proposed. IRAS also revealed a higher order of the odd-numbered chains and an increasing hydrogen-bonding contribution with increasing chain length. Additional evidence for the proposed bilayered assemblies and their reversibility was obtained by AFM. Images obtained from the assembly of decamidine on a SAM of mercaptohexadecanoic acid in a pH 9 borate buffer revealed domains of similar size to that of the underlying acid SAM (20-30 nm), but less densely packed. By acidifying the solution, the second layer was destabilized and a very smooth layer with few defects appeared. Further acidification to pH 3 also destabilized the first layer.     

Irradiation sensitivity of self-assembled monolayers with an introduced "weak link"

The irradiation sensitivity of n-alkanethiolate SAMs can be enhanced by the incorporation of an irradiation-sensitive functionality as a predetermined breaking point into the alkyl chain. Following this general strategy, several different sulfur-derived functional entities with a variable position in the alkyl chain were tested. In some cases, the incorporation of these entities resulted in a noticeable enhancement of the irradiation-induced desorption (by about 30%), even though the chains were not exclusively cut at the position of the incorporated group, but the scission events related to the "weak links" were just added to those in the alkyl matrix. The position of the incorporated group along the alkyl chain was found to be most essential for its performance as a weak link; the enhancement of irradiation-induced desorption was observed only when the groups were placed close to the SAM-ambient interface.     

Effects of double-chained cationic surfactants n-dimethyldialkylammoniums on skin permeation of benzoic acid through excised guinea pig dorsal skin: comparison of their enhancement effects with hemolytic effects on erythrocytes

We examined the effects of the double-chained cationic surfactants dimethyidialkylammoniums (CH3)2N+ (CnH(2n+1))2 on the permeation of benzoic acid through excised guinea pig dorsal skin. Among five dimethyldialkylammoniums tested (n=10-18), dimethyldidecylammonium (n=10) had dose-dependent enhancement effects at concentrations of more than 20 microM. Compared with the marked enhancement effects of dimethyldialkylammoniums with relatively shorter alkyl chains, those of long-chain dimethyldialkylammoniums (n=16, 18) were much less. We compared the enhancement effects of these cationic surfactants on skin permeation with their hemolytic effects on guinea pig erythrocytes. Their enhancement effects corresponded to their hemolytic activity. The findings suggest that dimethyldialkylammoniums with relatively shorter alkyl chains, which form either vesicles with looser molecular packing or micelles and appear to be present as surfactant monomers in higher ratios than those with longer alkyl chains, favor the interaction with skin. Their enhancement mechanism is possibly similar to that of single-chained cationic surfactants.