Synergistic antibacterial brilliant blue/reduced graphene oxide/quaternary phosphonium salt composite with excellent water solubility and specific targeting capability

A water-soluble brilliant blue/reduced graphene oxide/tetradecyltriphenylphosphonium bromide composite (BB-rGO-TTP) was prepared by using noncovalent brilliant blue-functionalized reduced graphene oxide (BB-rGO) as the tetradecyltriphenylphosphonium bromide (TTP) carrier. Antibacterial performance of this novel composite was investigated for both Gram-positive and Gram-negative bacteria. The results showed that the novel BB-rGO-TTP, combing the advantages of graphene and TTP, displayed excellent synergistic antibacterial activity, specific targeting capability, water solubility, and mild cytotoxicity, suggesting the great potential application as sprayable graphene-based antibacterial solutions.     

Molecular tilting and its impact on frictional properties of n-alkane self-assembled monolayers

Hydrophobic, methyl-terminated self-assembled monolayer (SAM) surfaces can be used to reduce friction. Among methyl-terminated SAMs, the frictional properties of alkanethiol SAMs and silane SAMs have been well-studied. In this research, we investigated friction of methyl-terminated n-hexatriacontane (C36) SAM and compared its friction properties with the alkanethiol and silane SAMs. Alkane SAM does not have an anchoring group. The alkane molecules stand on the surface by physical adsorption, which leads to a higher surface mobility of alkane molecules. We found that C36 SAM has a higher coefficient of friction than that of octadecyltrichlorosilane (OTS) silane. When an atomic force microscope (AFM) tip was swiped across the alkane SAM with a loading force, we found that the alkane SAM can withstand the tip loading pressure up to 0.48 GPa. Between 0.48 and 0.49Ga, the AFM tip partially penetrated the SAM. When the tip moved away, the deformed SAM healed and maintained the structural integrity. When the loading pressure was higher than 0.49 GPa, the alkane SAM was shaved into small pieces by the tip. In addition, we found that the molecular tilting of C36 molecules interacted with the tribological properties of the alkane SAM surface. On one hand, a higher loading force can push the rod-like alkane molecules to a higher tilting angle; on the other hand, a higher molecular tilting leads to a lower friction surface.     

Biomimetic anchors for antifouling and antibacterial polymer brushes on stainless steel

Barnacle cement (BC) was beneficially applied on stainless steel (SS) to serve as the initiator anchor for surface-initiated polymerization. The amine and hydroxyl moieties of barnacle cement reacted with 2-bromoisobutyryl bromide to provide the alkyl halide initiator for the surface-initiated atom transfer radical polymerization (ATRP) of 2-hydroxyethyl methacrylate (HEMA). The hydroxyl groups of HEMA polymer (PHEMA) were then converted to carboxyl groups for coupling of chitosan (CS) to impart the SS surface with both antifouling and antibacterial properties. The surface-functionalized SS reduced bovine serum albumin adsorption, bacterial adhesion, and exhibited antibacterial efficacy against Escherichia coli (E. coli). The effectiveness of barnacle cement as an initiator anchor was compared to that of dopamine, a marine mussel inspired biomimetic anchor previously used in surface-initiated polymerization. The results indicate that the barnacle cement is a stable and effective anchor for functional surface coatings and polymer brushes.     

Biofunctionalization of a "clickable" organic layer photochemically grafted on titanium substrates

We have developed a general method combining photochemical grafting and copper-catalyzed click chemistry for biofunctionalization of titanium substrates. The UV-activated grafting of an α,ω-alkenyne onto TiO(2)/Ti substrates provided a "clickable" thin film platform. The selective attachment of the vinyl end of the molecule to the surface was achieved by masking the alkynyl end with a trimethylgermanyl (TMG) protecting group. Subsequently, various oligo(ethylene glycol) (OEG) derivatives terminated with an azido group were attached to the TMG-alkynyl modified titanium surface via a one-pot deprotection/click reaction. The films were characterized by X-ray photoelectron spectroscopy (XPS), contact angle goniometry, ellipsometry, and atomic force microscopy (AFM). We showed that the titanium surface presenting click-immobilized OEG substantially suppressed the nonspecific attachment of protein and cells as compared to the unmodified titanium substrate. Furthermore, glycine-arginine-glycine-aspartate (GRGD), a cell adhesion peptide, was coimmobilized with OEG on the platform. We demonstrated that the resultant GRGD-presenting thin film on Ti substrates can promote the specific adhesion and spreading of AsPC-1 cells.     

In-site mineralization of amorphous calcium carbonate particles: A facile and efficient approach to fabricate poly(l-lactic acid) based hybrids

The aim of this investigation is to obtain a polymer-based hybrid material with biodegradability, biocompatibility, and good mechanical properties and this object was realized via. in-situ introduction of the unmodified calcium carbonate (CaCO₃) into a poly(l-lactic acid) (PLLA) matrix. As verified by the measurements from scanning electron microscopy (SEM), optical microscopy, dynamic mechanical analysis (DMA) and thermogravimetric analysis (TGA), the hybrid films which possesses a uniform dispersion of calcium carbonate CaCO₃ in nano-meter scale, mechanically robustness and thermal stability could be fabricated by a mineralization-alike process. For example, the storage modulus increases from 441 MPa of neat PLLA to 1034 MPa of hybrid film containing 2% (w/w) CaCO₃. In addition, the hybrid films display a significant improvement in its UV-exposure resistance.     

Interfacial Studies for improving the adhesion of Cr/Al films on composites

The composites, such as CFRP and GFRP, have been widely applied in spaceflight, for their low specific gravity, low cost, and additional structural stability. However, the high resistivity of the composites severely inhibits their further applications. Therefore, Cr/Al films with low resistivity and high adhesion were deposited on composites by cathodic arc technique. The films were characterized by pull test, Dektak 8 Stylus Profilometer, SEM, XPS, XRD and Z‐82 standard four probes. Results show that the aluminum film of fcc structure is compact and uniform, with resistivity as low as bulk Al. The adhesion between Cr buffer layer and composite substrate was greatly enhanced because of the formation of the chemical bonds, such as Cr? C, Cr? O and Cr? N, at the Cr/composite interface. Copyright © 2011 John Wiley & Sons, Ltd.     

Tunable synthesis of propylene glycol ether from methanol and propylene oxide under ambient pressure

A series of basic and acidic ionic liquids, 1-butyl-3-methylimidazolium hydroxide (BMIMOH), 1-acetyl-3-methylimidazolium chloride (AcMIMCl) and AcMIMCl-FeCl₃, or analogues of AcMIMCl, namely 1-potassium acetate-3-methylimidazolium chloride (KAcMIMCl), 1-potassium (sodium, ammonium) acetate-3-methylimidazolium hydroxides (KAcMIMOH, NaAcMIMOH and NH₄AcMIMOH), were prepared and used as catalysts for catalytic synthesis of propylene glycol ether via reaction of propylene oxide (PO) with methanol under mild reaction conditions. KAcMIMOH exhibited outstanding catalytic performance with 94.2% of conversion of PO and 99.1% of selectivity to 1-methoxy-2-propanol (MP-2) at 60°C and ambient pressure for 4 h. However, AcMIMCl-FeCl₃ showed a good catalysis performance with high selectivity to 2-methoxy-1-propanol (MP-1). The tunable synthesis of MP-2 or MP-1 catalyzed by basic compound KAcMIMOH or acidic ionic liquid AcMIMCl-FeCl₃ was realized.     

Bifunctional cinchona alkaloids-catalyzed asymmetric [4+2] cycloaddition reaction of β,γ-unsaturated α-keto esters with oxazolones

A highly enantioselective [4+2] cycloaddition reaction of β,γ-unsaturated α-keto esters with oxazolones was realized with readily available cinchona alkaloids as the catalysts. Using this reaction, a series of highly functionalized δ-lactones with adjacent α-quaternary-β-tertiary stereocenters were obtained in high yields (up to 97%) and with good-to-excellent enantioselectivities (up to 97% ee).     

Control and Optimization of <Emphasis Type="Italic">Clostridium tyrobutyricum</Emphasis> ATCC 25755 Adhesion into Fibrous Matrix in a Fibrous Bed Bioreactor

The great performance of a fibrous bed bioreactor (FBB) is mainly dependent on the cell adhesion and immobilization into the fibrous matrix. Therefore, understanding the mechanism and factors controling cell adhesion in the fibrous matrix is necessary to optimize the FBB setup and further improve the fermentability. The adhesion behavior of a strain of Clostridium tyrobutyricum isolated from an FBB was studied, which was proven to be affected by the different environmental conditions, such as growth phase of cells, pH, ionic strength, ionic species, and composition of media. Our results also suggested that electrostatic interactions played an important role on bacteria adhesion into the fibrous matrix. This study demonstrated that the compositions of fermentation broth would have a significant effect on cell adhesion. Consequently, a two-stage glucose supply control strategy was developed to improve the performance of FBB with higher viable cell density in the operation of the FBB setup.     

Electrospray ionization tandem mass spectrometric characterization of DNA adducts formed by bromobenzoquinones

Bromobenzoquinones (BBQs) represent a class of reactive metabolites of various aromatic contaminants with bromine-containing substituents, including bromobenzene, bromophenols, polybrominated diphenyl ethers (PBDEs). Recently, 2,6-dibromobenzoquinone also has been detected directly from drinking water. The alternation of the genome caused by covalent binding of chemicals or their metabolites to DNA provides a viable mechanism for carcinogenicity. In the present study, electrospray ionization coupled with ion trap mass spectrometry (ITMS), triple quadrupole MS or quadrupole time-of-flight MS was applied for the analysis of DNA adducts formed by BBQs. The study demonstrated 2-monobromobenzoquinone and 2,6-dibromobenzoquinone could covalently bind to deoxyguanosine (dG) and DNA in vitro. The chemical structures of the DNA adducts were confirmed by accurate mass values, collision-induced fragmentation tandem mass spectra as well as isotopic patterns. Generally, the reaction mechanism for the DNA adduction involved Michael addition between the electron-deficient carbon from the quinone and the nucleophilic exocyclic nitrogen from the dG followed by reductive cyclization with loss of a small molecule such as H(2)O, or HBrO. It was of particular interest to note that some adducts were generated from the reaction of one dG molecule with two BBQ molecules. The obtained results provided new information for assessing the potential cancer risk associated with bromobenzene, bromophenols, PBDEs and BBQs.