Bidentate Adsorbates Research Articles

Automatic mechanism generation involving kinetics of surface reactions with bidentate adsorbates

RMG was expanded with multidentate functionalities, which enables the automated discovery of mechanisms for the complex non-oxidative dehydrogenation of ethane.

Defects Formation and Amorphization of Zn-MOF-74 Crystals by Post-Synthetic Interactions with Bidentate Adsorbates.

The controlled introduction of defects into MOFs is a powerful strategy to induce new physiochemical properties and improve their performance for target applications. Herein, we present a new strategy for defect formation and amorphization of the canonical MOF-74 frameworks based on fine-tuning of adsorbate-framework interactions in the metal congener, hence introducing structural defects. Specifically, we demonstrate that controlled interactions between the MOF and bidentate ligands adsorbed in the pores initiates defect formation and eventual amorphization of the crystal. These structural features unlock properties that are otherwise absent in the ordered framework, such as broad-band fluorescence. The ability to introduce defects by adsorbate-framework interactions, coupled with the inherent tunability and modularity of these structures, provides a new route for the synthesis of diverse heterogeneous and hybrid materials.

Olefin-Bridged Bidentate Adsorbates for Generating Self-Assembled Monolayers on Gold

A series of custom-designed olefin-bridged bidentate adsorbates composed of an olefin group linking symmetrical hydrocarbon moieties of varying chain lengths was synthesized and used for the preparation of self-assembled monolayers (SAMs) on gold. The structures of the adsorbates are in the form Z-[CH3(CH2)m]2(C═C)[CH2SH]2 (OBCnSH) where m = 12-15 and n = m + 3 (OBC15SH, OBC16SH, OBC17SH, and OBC18SH). The influence of the olefin linker on the structural and interfacial properties of the SAMs was investigated and compared to SAMs formed from analogous n-alkanethiols. Characterization techniques included ellipsometry, X-ray photoelectron spectroscopy (XPS), polarization modulation-infrared reflection-adsorption spectroscopy (PM-IRRAS), and contact angle measurements. The OBCnSH SAMs exhibited ellipsometric thicknesses that were similar to their monodentate counterparts, suggesting that the new olefin-bridged adsorbates pack similarly to the monodentate analogs. Characterization by PM-IRRAS revealed that the OBCnSH SAMs were as conformationally ordered as those derived from the reference n-alkanethiols with the exception of the adsorbate with the shortest chain length OBC15SH, which exhibited low coverage and a liquid-like structure. Unlike the SAMs derived from the n-alkanethiols, the OBCnSH SAMs failed to exhibit "odd-even" effects. However, the OBCnSH SAMs displayed similar hexadecane contact angles as their n-alkanethiol counterparts with the exception of OBC15SH, which exhibited markedly diminished hexadecane contact angles. The similar structural and interfacial properties of the OBCnSH SAMs, when compared to analogous n-alkanethiol SAMs, render the molecular architecture of the olefin-bridged dithiol as a robust platform for the synthesis of adsorbates with two chemically distinct tailgroups for use in the preparation and study of phase-incompatible "conflicted" interfaces.

Quaternary Ammonium-Terminated Films Formed from Mixed Bidentate Adsorbates Provide a High-Capacity Platform for Oligonucleotide Delivery.

The exposure of quaternary ammonium groups on surfaces allows self-assembled monolayers (SAMs) to serve as architectural platforms for immobilizing oligonucleotides. The current study describes the preparation of SAMs derived from four unique bidentate adsorbates containing two different ammonium termini (i.e., trimethyl- and triethyl-) and comparison to their monodentate analogs. Our studies found that SAMs derived from the bidentate adsorbates offered considerable enhancements in oligonucleotide binding when compared to SAMs derived from their monodentate analogs. The generated SAMs were analyzed using ellipsometry, X-ray photoelectron spectroscopy, contact angle goniometry, polarization modulation infrared reflection-absorption spectroscopy, and electrochemical quartz crystal microbalance. These analyses showed that the immobilization of oligonucleotides was affected by changes in the terminal functionalities and the relative packing densities of the monolayers. In efforts to enhance further the immobilization of oligonucleotides on these SAM surfaces, we explored the use of adsorbates having aliphatic linkers with systematically varying chain lengths to form binary SAMs on gold. Mixed monolayers with 50:50 ratios of adsorbates showed the greatest oligonucleotide binding. These studies lay the groundwork for oligonucleotide delivery using gold-based nanoparticles and nanoshells.

Unsymmetrical Spiroalkanedithiols Having Mixed Fluorinated and Alkyl Tailgroups of Varying Length: Film Structure and Interfacial Properties.

A custom-designed series of unsymmetrical spiroalkanedithiols having tailgroups comprised of a terminally fluorinated chain and a hydrocarbon chain of varying lengths were synthesized and used to prepare self-assembled monolayers (SAMs) on gold substrates. The specific structure of the adsorbates was of the form [CH3(CH2)n][CF3(CF2)7(CH2)8]C[CH2SH]2, where n = 7, 9, and 15 (designated as F8H10-C10, F8H10-C12, and F8H10-C18, respectively). The influence of the length of the hydrocarbon chain in the bidentate dithiol on the structure and interfacial properties of the monolayer was explored. A structurally analogous partially fluorinated monodentate alkanethiol and the corresponding normal alkanethiols were used to generate appropriate SAMs as reference systems. Measurements of ellipsometric thickness showed an unexpectedly low film thickness for the SAMs derived from the bidentate adsorbates, possibly due to disruptions in interchain packing caused by the fluorocarbon chains (i.e., phase-incompatible fluorocarbon-hydrocarbon interactions), ultimately giving rise to loosely packed and disordered films. Analysis by X-ray photoelectron spectroscopy (XPS) were also consistent with a model in which the films were loosely packed; additionally, the XPS spectra confirmed the attachment of the sulfur headgroups of the bidentate adsorbates onto the gold substrates. Studies of the SAMs by polarization modulation-infrared reflection-adsorption spectroscopy (PM-IRRAS) suggested that as the length of the hydrocarbon chain in the adsorbates was extended, a more ordered surface was achieved by reducing the tilt of the fluorocarbon segment. The wettability data indicated that the adsorbates with longer alkyl chains were less wettable than those with shorter alkyl chains, likely due to an increase in interchain van der Waals forces in the former.

Homogeneously Mixed Monolayers: Emergence of Compositionally Conflicted Interfaces.

The ability to manipulate interfaces at the nanoscale via a variety of thin-film technologies offers a plethora of avenues for advancing surface applications. These include surfaces with remarkable antibiofouling properties as well as those with tunable physical and electronic properties. Molecular self-assembly is one notably attractive method used to decorate and modify surfaces. Of particular interest to surface scientists has been the thiolate-gold system, which serves as a reliable method for generating model thin-film monolayers that transform the interfacial properties of gold surfaces. Despite widespread interest, efforts to tune the interfacial properties using mixed adsorbate systems have frequently led to phase-separated domains of molecules on the surface with random sizes and shapes depending on the structure and chemical composition of the adsorbates. This feature article highlights newly emerging methods for generating mixed thin-film interfaces, not only to enhance the aforementioned properties of organic thin films, but also to give rise to interfacial compositions never before observed in nature. An example would be the development of monolayers formed from bidentate adsorbates and other unique headgroup architectures that provide the surface bonding stability necessary to allow the assembly of interfaces that expose mixtures of chains that are fundamentally different in character (i.e., either phase-incompatible or structurally dissimilar), producing compositionally "conflicted" interfaces. By also exploring the prior efforts to produce such homogeneously blended interfaces, this feature article seeks to convey the relationships between the methods of film formation and the overall properties of the resulting interfaces.

Bidentate Aromatic Thiols on Gold: New Insight Regarding the Influence of Branching on the Structure, Packing, Wetting, and Stability of Self-Assembled Monolayers on Gold Surfaces.

A series of 2-phenylpropane-1,3-dithiol derivatives with single (R1ArDT), double (R2ArDT), and triple (R3ArDT) octadecyloxy chains substituted at the 4-, 3,5-, and, 3,4,5-positions, respectively, on the aromatic ring were synthesized and used to form self-assembled monolayers (SAMs) on gold. Insight into the relationship between the surface chain and headgroup packing densities was investigated by varying the number of surface chains for the bidentate adsorbates in these monolayers. Characterization of the resulting SAMs using ellipsometry, X-ray photoelectron spectroscopy, polarization modulation infrared reflection-absorption spectroscopy, and contact angle goniometry revealed that the tailgroups become more comformationally ordered and more densely packed as the number of alkyl chains per adsorbate was increased. Conversely, the molecular packing density (i.e., number of molecules per unit area) decreased as the number of alkyl chains per adsorbate was increased. Of particular interest, the desorption profiles obtained in isooctane at 80 °C suggested that the bidentate adsorbate with the most densely packed alkyl chains, R3ArDT, was significantly more stable than the other SAMs, producing the following relative order for thermal stability for the dithiolate SAMs: R3ArDT > R2ArDT > R1ArDT.

Two Are Better than One: Bidentate Adsorbates Offer Precise Control of Interfacial Composition and Properties

Mixed self-assembled monolayers (SAMs) generated from perfluoro-, n-alkyl-, and oligo(ethylene glycol)-terminated alkanedithiols were utilized to prepare two-dimensional interfaces with precise composition and wettability. Interfacial control was afforded simply by adjusting the mole fraction of the adsorbates present in the development solutions and was modulated by the dual contributions of the tailgroups of the bidentate thiols. In contrast, the composition and wettability of mixed SAMs generated from traditional monodentate thiols bearing analogous tailgroups failed to track systematically with the mole fractions of the adsorbates in the development solutions, reflecting a greater dependence on solvent/adsorbate interactions. All of the SAMs were thoroughly characterized by contact angle goniometry, ellipsometry, X-ray photoelectron spectroscopy (XPS), and polarization modulation infrared reflection–absorption spectroscopy (PM-IRRAS). Furthermore, solution-phase displacement tests performed to evaluat...

Robust Maleimide-Functionalized Gold Surfaces and Nanoparticles Generated Using Custom-Designed Bidentate Adsorbates.

A series of custom-designed alkanethioacetate ligands were synthesized to provide a facile method of attaching maleimide-terminated adsorbates to gold nanostructures via thiolate bonds. Monolayers on flat gold substrates derived from both mono- and dithioacetates, with and without oligo(ethylene glycol) (OEG) moieties in their alkyl spacers, were characterized using X-ray photoelectron spectroscopy, polarization modulation infrared reflection-absorption spectroscopy, ellipsometry, and contact angle goniometry. For all adsorbates, the resulting monolayers revealed that a higher packing density and more homogeneous surface were generated when the film was formed in EtOH, but a higher percentage of bound thiolate was obtained in THF. A series of gold nanoparticles (AuNPs) capped with each adsorbate were prepared to explore how adsorbate structure influences aqueous colloidal stability under extreme conditions, as examined visually and spectroscopically. The AuNPs coated with adsorbates that include OEG moieties exhibited enhanced stability under high salt concentration, and AuNPs capped with dithioacetate adsorbates exhibited improved stability against ligand exchange in competition with dithiothreitol (DTT). Overall, the best results were obtained with a chelating dithioacetate adsorbate that included OEG moieties in its alkyl spacer, imparting improved stability via enhanced solubility in water and superior adsorbate attachment owing to the chelate effect.

Entropy-Driven Conformational Control of α,ω-Difunctional Bidentate-Dithiol Azo-Based Adsorbates Enables the Fabrication of Thermally Stable Surface-Grafted Polymer Films.

Thermally stable radical initiator monolayers were prepared from uniquely designed α,ω-difunctional adsorbates with bidentate headgroups for the growth of nanoscale polymer films on metal surfaces. The length of the spacer separating the bidentate headgroups was varied to afford 4,4'-(diazene-1,2-diyl)bis(N-(16-(3,5-bis(mercaptomethyl)phenoxy)hexadecyl)-4-cyanopentanamide) (B16), 4,4'-(diazene-1,2-diyl)bis(N-(16-(3,5-bis(mercapto-methyl)phenoxy)decyl)-4-cyanopentanamide) (B10), and 4,4'-(diazene-1,2-diyl)bis(N-(4-(3,5-bis(mercaptomethyl)phenoxy)butyl)-4-cyanopentanamide) (B4). The structural features of the self-assembled monolayers (SAMs) derived from B16, B10, and B4 were characterized by X-ray photoelectron spectroscopy (XPS), ellipsometry, and polarization modulation infrared reflection-absorption spectroscopy (PM-IRRAS) and compared to those derived from an analogous α,ω-difunctional adsorbate with monodentate headgroups, 4,4'-(diazene-1,2-diyl)bis(4-cyano-N-(16-mercaptohexadecyl)pentanamide (M). These studies demonstrate that the conformation (i.e., hairpin vs standing up) of the bidentate initiator adsorbates on gold surfaces was easily controlled by adjusting the concentration of the adsorbates in solution. The results of solution-phase thermal desorption tests revealed that the radical initiator monolayers generated from B16, B10, and B4 exhibit an enhanced thermal stability when compared to those generated from M. Furthermore, a study of the growth of polymer films was performed to evaluate the utility of these new bidentate adsorbate SAMs as film-development platforms for new functional materials and devices. Specifically, surface-grafted polystyrene films were successfully generated from SAMs derived from B16. In contrast, attempts to grow polystyrene films from SAMs derived from M under a variety of analogous conditions were unsuccessful.

Robust Thick Polymer Brushes Grafted from Gold Surfaces Using Bidentate Thiol-Based Atom-Transfer Radical Polymerization Initiators.

A new bromoisobutyrate-terminated alkanethiol, 16-(3,5-bis(mercaptomethyl)phenoxy)hexadecyl 2-bromo-2-methylpropanoate (BMTBM), was designed as a bidentate adsorbate to form thermally stable bromoisobutyrate-terminated self-assembled monolayers (SAMs) on flat gold surfaces to conduct atom-transfer radical polymerizations (ATRPs). The monolayers derived from BMTBM were characterized by ellipsometry, X-ray photoelectron spectroscopy (XPS), and polarization modulation infrared reflection-absorption spectroscopy (PM-IRRAS) and compared to the monolayers formed from 16-mercaptohexadecyl 2-bromo-2-methylpropanoate (MBM), 16-(3-(mercaptomethyl)phenoxy)hexadecyl 2-bromo-2-methyl-propanoate (MTBM), and octadecanethiol (C18SH). In this study, although the monolayer derived from BMTBM was less densely packed than those derived from MBM and MTBM, the bidentate adsorbates demonstrated much higher thermal stability in solution-phase thermal desorption tests, owing to the "chelate effect". The enhanced stability of the BMTBM SAMs ensured the development of thick brushes of poly(methyl methacrylate) and polystyrene at elevated temperatures (60, 90, 105, and 120 °C). In contrast, SAMs derived from MBM and MTBM failed to grow polymer brushes at temperatures above 100 °C.

Self-Assembled Monolayers Generated from Unsymmetrical Partially Fluorinated Spiroalkanedithiols.

Self-assembled monolayers (SAMs) were prepared on gold substrates from an unsymmetrical partially fluorinated spiroalkanedithiol adsorbate with the specific structure of [CH3(CH2)7][CF3(CF2)7(CH2)8]C[CH2SH]2 (SADT) and compared to SAMs formed from the semifluorinated monothiol F8H10SH [CF3(CF2)7(CH2)10SH] of analogous chain length and n-octadecanethiol. The adsorbate with two alkyl chains, one terminally fluorinated and the other nonfluorinated, was designed to form monolayers in which the bulky helical fluorocarbon segments assemble on top of an underlying layer of well-packed trans-extended alkyl chains. Different combinations of deposition solvents and temperatures were used to produce the bidentate SAMs. Characterization of the resulting monolayers revealed that SAMs formed in DMF at room temperature allow complete binding of the sulfur headgroups to the surface and exhibit higher conformational order than those produced using alternative solvent/temperature combinations. The reduced film thicknesses and enhanced wettability of the SADT SAMs, as compared to the SAMs generated from F8H10SH, suggest loose packing and an increase in the tilt of the terminal fluorocarbon chain segments. Nevertheless, the density of the underlying hydrocarbon chains of the SADT SAMs was higher than that of the F8H10SH SAMs, owing to the double-chained structure of the new adsorbate. The conformational orders of the SAM systems were observed to decrease as follows: C18SH > F8H10SH > SADT. However, the SAMs formed from this new double-chained bidentate adsorbate in DMF expose a fluorinated interface with a relatively low surface roughness, as determined by contact-angle hysteresis.

Boc-protected ω-amino alkanedithiols provide chemically and thermally stable amine-terminated monolayers on gold.

Four custom-designed bidentate adsorbates having either ammonium or Boc-protected amino termini and either methanethiol or ethanethioate headgroups were prepared for the purpose of generating amine-terminated self-assembled monolayers (SAMs) on evaporated gold surfaces. These adsorbates utilize a phenyl-based framework to connect the headgroups to a single hexadecyloxy chain, extending the amino functionality away from the surface of gold, providing two regions within the adsorbate structure where intermolecular interactions contribute to the stability of the fully formed thin film. The structural features of the resulting SAMs were characterized by ellipsometry, X-ray photoelectron spectroscopy, and polarization modulation infrared reflection-absorption spectroscopy. The collected data were compared to those of eight additional SAMs formed from analogous monodentate alkanethiols and alkanethioacetates having either a similar aromatic framework or a simple alkyl chain connecting the headgroup to the tailgroup. The analysis of the data obtained for the full set of SAMs revealed that both the tailgroup and headgroup influenced the formation of a well-packed monolayer, with the Boc-protected amine-terminated alkanethiols producing films with superior surface bonding and adsorbate packing as compared to those formed with ammonium tailgroups or alkanethioacetate headgroups. A comparison of the structural differences before and after deprotection of the Boc-protected amine-terminated thiolate SAMs revealed that the bidentate adsorbate was the most resistant to desorption during the Boc-deprotection procedure. Furthermore, solution-phase thermal desorption tests performed to evaluate the thermal stability of the Boc-deprotected amine-terminated alkanethiolate films provided further evidence of the enhanced stability associated with SAMs formed from these bidentate adsorbates.

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.

Adsorption and dissociation of NH3 on clean and hydroxylated TiO2 rutile (110) surfaces: A computational study

The adsorption and dissociation of NH(3) on the clean and hydroxylated TiO(2) rutile (110) surfaces have been investigated by the first-principles calculations. The monodentate adsorbates such as H(3)N-Ti(a), H(2)N-Ti(a), N-Ti(a), H(2)N-O(a), HN-O(a), N-O(a) and H-O(a), as well as the bidentate adsorbate, Ti-N-Ti(a) can be formed on the clean surface. It is found that the hydroxyl group enhances the adsorption of certain adsorbates on the five-fold-coordinated Ti atoms (5c-Ti), namely H(2)N-Ti(a), HN-Ti(a), N-Ti(a) and Ti-N-Ti(a). In addition, the adsorption energy increases as the number of hydroxyl groups increases. On the contrary, the opposite effect is found for those on the two-fold-coordinated O atoms (2c-O). The enhanced adsorption of NH(x) (x = 1-2) on the 5c-Ti is due to the large electronegativity of the OH group, increasing the acidity of the Ti center. This also contributes to diminish the adsorption of NH(x) (x = 1-2) on the two-fold-coordinated O atoms (2c-O) decreasing its basicity. According to potential energy profile, the NH(3) dissociation on the TiO(2) surface is endothermic and the hydroxyl group is found to lower the energetics of H(2)N-Ti(a)+H-O(a) and HN-Ti(a)+2{H-O(a)}, but slightly raise the energetic of Ti-N-Ti(a)+3{H-O(a)} compare to those on the clean surface. However, the dissociation of NH(3) is found to occur on the hydroxylated surface with an overall endothermic by 31.8 kcal/mol and requires a barrier of 37.5 kcal/mol. A comparison of NH(3) on anatase surface has been discussed. The detailed electronic analysis is also carried out to gain insights into the interaction nature between adsorbate and surface.

Covalent functionalization of ZnO surfaces: A density functional tight binding study

We have demonstrated the covalent functionalization of 101̱0-ZnO surfaces with carboxylic acids by employing self-consistent charge density functional tight binding (SCC-DFTB) calculations. We have found two thermodynamically stable surface configurations: (i) a monolayer coverage with a bidentate chelating ligand and (ii) a half-monolayer coverage with a bidentate bridging ligand. In both cases, the electronic band structures show the presence of covalent surface/adsorbate interactions. Besides, a nonbonding carboxylate character is verified for the bidentate adsorbate. Our results are consistent with infrared spectroscopy experiments on functionalized ZnO nanostructures, and open possibilities for further investigations on functionalized ZnO-based materials for bio/chemical sensing.

Adsorption Configuration and Dissociative Reaction of NH3 on Anatase (101) Surface with and without Hydroxyl Groups

This study investigates the possible adsorption configurations and dissociative reactions of NH3 on the anatase (101) surface by employing the first principles calculations. In addition, the hydroxyl group effect is also included to study how this effect influences the adsorption and the dissociative reactions. Without the presence of the hydroxyl group, the most stable adsorbate is the bidentate adsorbate Ti-N-O (Eads = 44.9 kcal/mol), and the second is the bidentate adsorbate Ti-(H)N-O (Eads = 40.8 kcal/mol). NH3 can also be adsorbed on 5c-Ti, forming H3N-Ti, which is the third most stable adsorbate (Eads = 27.5 kcal/mol). The hydroxyl group present on the surface has the effect of significantly enhancing the adsorption of the monodentate adsorbates H2N-Ti and HN-Ti. However, such a presence only slightly enhances the bidentate adsorbate Ti-N-O. In addition, the adsorption energy increases as the number of hydroxyl groups on the surface increases. The hydroxyl group also has the effect to diminish the a...