Factors resisting protein adsorption on hydrophilic/hydrophobic self-assembled monolayers terminated with hydrophilic hydroxyl groups

The hydroxyl-terminated self-assembled monolayer(OH-SAM),as a surface resistant to protein adsorption,exhibits substantial potential in applications such as ship navigation and medical implants,and the appropriate strategies for designing anti-fouling surfaces are crucial.Here,we employ molecular dynamics simulations and alchemical free energy calculations to systematically analyze the factors influencing resistance to protein adsorption on the SAMs terminated with single or double OH groups at three packing densities(∑=2.0 nm^(-2),4.5 nm^(-2),and 6.5 nm^(-2)),respectively.For the first time,we observed that the compactness and order of interfacial water enhance its physical barrier effect,subsequently enhancing the resistance of SAM to protein adsorption.Notably,the spatial hindrance effect of SAM leads to the embedding of protein into SAM,resulting in a lack of resistance of SAM towards protein.Furthermore,the number of hydroxyl groups per unit area of double OH-terminated SAM at ∑=6.5 nm^(-2) is approximately 2 to 3 times that of single OH-terminated SAM at ∑=6.5 nm^(-2) and 4.5 nm^(-2),consequently yielding a weaker resistance of double OH-terminated SAM towards protein.Meanwhile,due to the structure of SAM itself,i.e.,the formation of a nearly perfect ice-like hydrogen bond structure,the SAM exhibits the weakest resistance towards protein.This study will complement and improve the mechanism of OH-SAM resistance to protein adsorption,especially the traditional barrier effect of interfacial water.

Morphological Evolution of Self-Assembled Sodium Dodecyl Sulfate/Dodecyltrimethylammonium Bromide@Epoxy-β-Cyclodextrin Supramolecular Aggregates Induced by Temperature

Bio-based cyclodextrins(CDs)are a common research object in supramolecular chemistry.The special cavity structure of CDs can form supramolecular self-assemblies such as vesicles and microcrystals through weak interaction with guest molecules.The different forms of supramolecular self-assemblies can be transformed into each other under certain conditions.The regulation of supramolecular self-assembly is not only helpful to understand the self-assembly principle,but also beneficial to its application.In the present study,the self-assembly behavior of epoxy-β-cyclodextrin(EP-β-CD)and mixed anionic and cationic surfactant system(sodium dodecyl sulfate/dodecyltrimethylammonium bromide,SDS/DTAB)in aqueous solution was studied.Morphological and particle size characterization found that the SDS/DTAB@EP-β-CD complex,as the basic building unit,self-assembled into worm-like micelles at lower temperatures and vesicles at higher temperatures.Nuclear magnetic resonance(NMR)and Fourier transform infrared spectroscopy(FT-IR)analysis revealed that the driving force for the formation of vesicles and worm-like micelles was the hydrogen bonds between EP-β-CD molecules,while water molecules played an important role in promoting vesicle formation between SDS/DTAB@EP-β-CD units.Herein,the mechanism of the morphologic transformation of SDS/DTAB@EP-β-CD supramolecular aggregates induced by temperature was elucidated by exploring the self-assembly process,which may provide an excellent basis for the development of delivery carriers.

Attachment of tyrosinase on mixed self-assembled monolayers for the construction of electrochemical biosensor

A mixed self-assembled monolayers （SAMs） of thioctic acid （T-COOH） and thioctic acid amide （T-NH2） were used to immobilize tyrosinase for fabricating biosensor. The results showed that the mixed SAMs prepared from solution at the ratio of 1：4 provided an excellent microenvironment for enzymatic reaction between tyrosinase and substrate. The biosensor exhibited a fast response and high sensitivity for sensing substrate.

Characterization of Self-assembled Monolayers on Gold Electrode Using Electrochemical Quartz Crystal Microbalance

The electrochemical quartz crystal microbalance (EQCM) is used to investigate the characteristics of the thiolated self-assembled monolayer(SAM) on gold surface.A 5MHz QCM element serves as both the mass-sensitive sensor and the working electrode of the electrochemical system.The 6-mecapto-1-hexanol and and the 16-mer oligonucleotide with a mercaptohexyl group at the 5'-phosphate end are utilized to form the SAM on the gold electrode.The frequency response of the QCM during cyclic voltammetry (CV) scanning and cbronoamperometry are recorded together with the electrochemical current.The experimental results indicates that the frequency response is more sensitive to the surface coverage.Therefore,the response of the EQCM reveals more details of the SAM on gold electrode.It is especially useful for analysing the immobilization quality,such as probe orientation and coverage,of the SAM.

Preparation and Characterization of SrTiO_3 Thin Film on Functional Organic Self-Assembled Monolayers

SrTiO3 thin film was successfully prepared on the functionalized organic self-assembled monolayers（SAMs） by the Liquid Phase Deposition（LPD） method.The as-prepared samples were characterized by X-ray diffraction（XRD）,atomic force microscope（AFM）,scanning electron microscopy（SEM） and metallographic microscope.Measurement of contact angle showed that the hydrophobe substrate was changed into hydrophile by UV irradiation.AFM photographs of octadecyl-trichloro-silane self-assembled monolayer（OTS-SAM） surface approved that UV irradiation did change the morphology of OTS monolayer and provided evidence for the conversion of hydrophilic characteristic.Photographs of Metallographic Microscope showed that OTS-SAM had an active effect on the deposition of SrTiO3 thin film.XRD and SEM indicated that the thin film was of pure cubic phase SrTiO3 and composed of nanosized grains with a size in the range of 100-500 nm.The formation mechanism of the SrTiO3 film was proposed.

Preparation and characterization of 3-mercaptopropyl trimethoxysilane self-assembled monolayers

Silane coupling regent （3-mercaptopropyl trimethoxysilane （MPTS）） was prepared on the single-crystal silicon substrate to form 2-dimensional self-assembled monolayers （SAMs）. The growth behavior of SAMs formed from 3-MPTS was investigated using atomic force microscopy （AFM）, contact angle measurements, ellipsometry, and X-ray photoelectron spectroscopy （XPS）. The formation behavior of MPTS SAMs was investigated by a series of AFM images and the roughness of MPTS SAMs on silicon substrates with the assembling time from 1 min to 24 h. The water contact angle measurements indicated the growth behavior of MPTS that correlated with the AFM measurements at different immersion times, too. The chemical states of the typical elements in the MPTS SAMs were analyzed using X-ray photoelectron spectroscopy. The results show that MPTS is self-assembled on the substrate.

A MEMS Based Amperometric Immunosensor with Self-assembled Monolayers Immobilization Technique

Based on MEMS technology,immunosensor with an'Au,Pt,Pt'three-microelectrode system enclosed in a SU-8 micro pool was fabricated.Employing SAMs technique,the Au electrode was modified by cysteamine(Cys)to assemble gold nanopanicles(nanogold)layer,subsequently,a layer of protein G(PG)was immobilized on nanogold layer to further capture antibody orientedly.Compared with the immunosensors using bulky gold electrode and direct PG binding to electrode immobilization technique for antibody,it has attractive advantages,such as miniaturization,good compatibility,broad linear range for human immunoglobulin(HIgG)and easy to be designed into array.

Direct electrochemistry and electrocatalysis of horseradish peroxidase immobilized on L-glutathione self-assembled monolayers

A novel hydrogen peroxide biosensor has been fabricated based on covalently linked horseradish peroxidase （HRP） onto L- glutathione self-assembled monolayers （SAMs）. The SAMs-based electrode was characterized by electrochemical methods, and direct electrochemistry of HRP can be achieved with formal potential of-0.242 V （vs. saturated Ag/AgCl） in pH 7 phosphate buffer solution （PBS）, the redox peak current is linear to scan rate and rate constant can be calculated to be 0.042 s^-1. The HRP-SAMs- based biosensors show its better electrocatalysis to hydrogen peroxide in the concentration range of 1 × 10^-6 mol/L to 1.2 × 10^-3 mol/L with a detection limit of 4 × 10^-7 mol/L. The apparent Michealis-Menten constant is 3.12 mmol/L. The biosensor can effectively eliminate the interferences of dopamine, ascorbic acid, uric acid, catechol and p-acetaminophen.

Surface Dissociation Properties of Short Chain Carboxyl Mercaptan Self-Assembled Monolayers by Impedance Titration

Impedance titration was used to determine the surface dissociation characteristics of short-chain carboxyl mercaptan self-assembled monolayers （SAMs）. Based on the change of the cyclic voltammetric peak current and the charge-transfer resistance, which was related to pH value of the solution, the surface pKa of mercaptoacetic acid（MA）, 3-mercaptopropionic acid（MPA） and ω-mercaptohexanic acid（MHA） self-assembled membranes, with ionic strength being 0.1 mol/L, were determined to be 5.20, 4.80, 7.40, respectively. In addition, factors such as time needed for assembling, structure of monolayers and ionic strength, which effected the surface pKa, were studied as well. Such surface pKa shifts were sufficiently explained by interactions between interfacial molecules and hydrophobicity.

Studies of Self-assembled Monolayers Formed by Imidazofine on Iron Surface by SEM and SECM

The self-assembled monolayers （SAMs） of imidazoline （IM） on the iron surface were characterized by scanning electron microscope （SEM） and scanning electrochemical microscopy （SECM）. The results showed that SAMs were an effective inhibition film for iron.

The Intermolecular Interaction in Self-Assembled Monolayers on Gold Electrode

The intermolecular interaction in an azobenzene self-assembled monolayers (SAMs) on gold electrode was investigated by controlling the assembling time and using mixed self-assembled techniques, and the variation of apparent electron transfer rate constant (k(s)) of azobenzene SAMs with different molecular packing density is reported.

Characterization of Formation Kinetics of Self-Assembled Thiol Monolayers on Gold by Electrochemical Impedance Spectroscopy

Self-assembled monolayers of octadecanethiol (ODT) on gold have been studied by electrochemical impedance spectroscopy (EIS). The fractional coverage has been examined as a function of immersion time of Au in ODT deposition solution. The fractional coverage exhibits two distinct adsorption steps: an initial rapid step followed by a slow one. The fractional coverage of ODT monolayer increases sharply from zero to more than 99% of its maximum within the first minute. However. it takes a day for the fractional coverage to approach its final value.

A New Thionine Modified Electrode by Anchorage to Bi-(2-aminoethyl)-aminodithiocarboxyl Acid Self-assembled Monolayers through Coordination with Cu^(2+#)

A new method for preparing chemically modified gold electrode by anchoring thionine to self-assembled bi - (2 -aminoethyl) -aminodithiocarboxyl acid(BANTC) monolayers through coordination with Cu2+ is described. This thionine modified electrode exhibits two-new redox couples.Two protons were involved in the electrochemical process undergone by the couple I in the pH range of 5.0-10.0. The apparent surface electron transfer rate constant is about 0.050s-1.

Stability Behaviour of Monolayer Tetraether Lipids on the Amino-Silanised Silicon Wafer: Comparative Study between Langmuir-Blodgett Monolayers with Self-Assembled Monolayers

This study investigated the stability behaviour of molecular monolayer symmetric chemically modified tetraether lipids caldarchaeol-PO4 on the amino-silanised silicon wafer using Langmuir-Blodgett films, Self Assembling Monolayers (SAMs), ellipsometry, and atomic force microscopy (AFM). The monolayers of caldarchaeol-PO4 were stable on the solid surface amino-silanised silicon wafer. The organizations of molecular monolayers caldarchaeol-PO4 by Langmuir-Blodgett method and SAMs have been analyzed. The surface of pressure in Langmuir-Blodgett processing is carried out monolayers caldarchaeol-PO4 more flat island inhomogeneous. Another method of monolayers caldarchaeol-PO4 by SAMs is showed a large flat domain. Monolayers caldarchaeol-PO4 by Langmuir-Blodgett method seems to be stable and chemically resistant after washing with organic solvent and an additional treatment ultrasonification with various thickness lipids arround 2 nm to 6 nm. Conversely, monolayer caldarchaeol-PO4 by SAMs appears fewer than monolayers caldarchaeol-PO4 by Langmuir-Blodgett method, the thickness of various from 1 nm to 3 nm.

Self-Assembled Monolayers (SAMs): Which Perspectives in Implant Dentistry?

Self-assembled monolayers (SAMs) are ordered organic films formed by adsorption of an active organic coating on a solid surface. Their formation provides an alternative, highly innovative, to current traditional chemical treatments of the titanium surfaces. For this reason the structural phases, the formation and the growth of SAMs is described from a surface science point of view. Particulars are given to SAMs on titanium concerning surface morphology, chemical composition and affinity of specific head group for Ti surfaces (silanes, siloxane, phosphonates and phosphates). Preparation, coating methodologies, limitations and techniques used for the characterization of SAMs are reported. For their physicochemical characteristics and micro-nano scale features some perspectives of using SAMs in biomedical application are outlined.

The Pattern Growth of Carbon Nanotubes by Self-assembled Monolayers Techniques

The well controllable selective growth of carbon nanotubes (CNTs)on the desired area is an important issue for their future applications. In this study, a novel method for selective growth of CNTs was proposed by using the technology of self-assembly monolayers (SAMs) and the Fe-assisted CNTs growth. The Si wafers with the a : Si/Si3N4 layer patterns were first prepared by low pressure chemical vapor deposition (LPCVD)and lithography techniques to act as the substrates for selective deposition of SAMs. The selectivity of SAMs from APTMS solution (N-(2-aminoethyl)-3-aminopropyltrimethoxsilane) is based on its greater reactivity of head group on a-Si than Si3N4 films. The areas of pattern with SAMs will first chelate the Fe3+ ions by their diamine-terminated group. The Fe3+ ions were then consolidated to become Fe-hydroxides in sodium boron hydride solution to form the Fe-hydroxides pattern. Finally, the Fe-hydroxides pattern was pretreated in H plasma to become a well-distributed Fe nano-particles on the surface, and followed by CNTs deposition using Fe as catalyst in a microwave plasma-chemical vapor deposition (MP-CVD) system to become the CNTs pattern. The products in each processing step, including microstructures and lattice images of CNTs, were characterized by contact angle measurements, scanning electron microscopy (SEM), XPS, Auger spectroscopy, transmission electron microscopy (TEM) and high resolution TEM (HRTEM)deposition. The results show that the main process parameters include the surface activation process and its atmosphere, consolidation time and temperature, H plasma pretreatment. The function of each processing step will be discussed.

Electrochemical Behavior and Determination of Trifluoperazine at Decanethiol Self-Assembled Monolayer Modified Gold Electrodes

The electrochemical behavior of trifluoperazine at decanethiol self-assembledmonolayer (SAM) modified gold electrodes (i. e. C_(10) H_(21) SH/Au) has been studied,Trifluoperazine can effectively accumulate on C_(10) H_(21) SH/Au electrodes and generate asensitive anodic peak at about 0.63 V (vs. SCE) in 0.05 mol/L pH 9.4 Na_2 B_4 O_7 buffer solution.Under the selected conditions, the anodic peak current was linear to trifluoperazine concentrationin the range of 5.0 X 10^(-7)-3.O X 10^(-3) mol/Lwith correlation coefficient of 0.997, thedetection limit was 3.0 X 10^(-5) mol/L. This method was applied to the determination oftrifluoperazine in drug samples and the recovery was 97.3%-104.0% It was found that sodium dodecylsulfate (SDS) could make the anodic peak current increase. In the presence of SDS, the peak at about0.63 V turned into two peaks, resulting from the change of the electrochemical mechanism.

The Molecular Recognition Characteristics of ω-MercaptoMethoxy Poly(Ethylene Glycol) Self-assembled Monolayer at Gold Electrode and the Detection of Dopamine in Serum

Self assembled monolayers (SAMs) of to-mercapto methoxy poly(ethylene glycol)(MPEG) on gold electrode were used as a means to detect dopamine. Dopamine (DA) had good response at the MPEG film electrode and ascorbic acid (AA) was repelled from the SAMs. TheMPEG film is a biocompatible film, there was no adsorption of biosample and no inactivation atelectrode surface when it was used to detect DA in biosamples.