Antimicrobial anilinium polymers: The properties of poly(N,N‐dimethylaminophenylene methacrylamide) in solution and as coatings

Antimicrobial polymers have been widely reported to exert strong biocidal effects against bacteria. In contrast with antimicrobial polymers with aliphatic ammonium groups, polymers with anilinium groups have been rarely studied and applied as biocidal materials. In this study, a representative polymer with aniline side functional groups, poly(N,N‐dimethylaminophenylene methacrylamide) (PDMAPMA), was explored as a novel antimicrobial polymer. PDMAPMA was synthesized and its physicochemical properties evaluated. The methyl iodide‐quaternized polymer was tested against the Gram‐positive Staphylococcus aureus, with a minimum inhibitory concentration (MIC) and minimum bactericidal concentration (MBC) of 16–32 and 64–128 μg mL^?1, respectively. Against the Gram‐negative Escherichia coli, the MIC and MBC were both 64–128 μg mL^?1. To broaden the range of applications, PDMAPMA was coated on substrates via crosslinking to endow the surface with contact‐kill functionality. The effect of charge density of the coatings on the antimicrobial behavior was then investigated, and stronger biocidal performance was observed for films with higher charge density. This study of the biocidal behavior of PDMAPMA both in solution and as coatings is expected to broaden the application of polymers containing aniline side groups and provide more information on the antimicrobial behavior of such materials. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 1908–1921     

Biocompatible antimicrobial cotton modified with tricarbimide‐based N‐halamine

Two N‐halamine precursors, 1‐glycidyl‐s‐triazine‐2,4,6‐trione and 1‐(2,3‐dihydroxypropyl)‐s‐triazine‐2,4,6‐trione, were synthesized and tethered onto cotton fabrics via the crosslinking agent 1,2,3,4‐butanetetracarboxylic acid. The modified samples were characterized by Fourier Transform Infrared Spectroscopy (FTIR) and Scanning Electron Microscope (SEM). The modified fabrics were rendered biocidal activities upon exposure to dilute hypochlorite solutions. The chlorinated cotton swatches were challenged with Staphylococcus aureus (ATCC 6538) and Escherichia coli O157:H7 (ATCC 43895) and exhibited excellent biocidal efficacy. The stability and rechargeability of the modified samples during washing and ultraviolet irradiation were also investigated. In vitro cell cytocompatibility studies demonstrated that the antibacterial cotton has good biocompatibility. Copyright © 2014 John Wiley & Sons, Ltd.     

Antimicrobial coatings on textiles–modification of sol–gel layers with organic and inorganic biocides

Antimicrobial textile materials were produced by sol–gel coatings with embedded biocidal compounds. For preparation a sol–gel procedure was used, starting from pure silica sols and 3-glycidyloxypropyltriethoxysilane (GLYEO) containing silica sols. These sols were modified with silver compounds, hexadecyltrimethyl-ammonium-p-toluolsulfonat (HTAT) and copper compounds, respectively. The investigations were performed on viscose fabrics as function of the concentration of biocidal compounds and of thermal treatment of textile after dip-coating between 80 up to 180 °C. The use of modified silica coatings leads to a decreased growth of fungi (Aspergillus niger) and bacteria (Bacillus subtilis and Pseudomonas putida) with increasing amount of the biocide embedded in the coating. The addition of GLYEO supports the biocidal effect of the coatings and enhances the stability of the coating solutions. For preparation of antimicrobial silica coatings the biocides silver, copper or HTAT can be used alone but the combination of these compounds leads to enhanced results against both fungi and bacteria. Therefore silica sols containing a combination of different types of biocides may be used for antimicrobial modification of textiles in some practical applications. For industrial applications the here presented coating solutions are especially advantageous, because of 90% water content in the solvent.     

Impact of micelles on the biocidal efficiency in a diesel–water interface

Biodegradation occurs in the diesel/water interface in petroleum product pipelines. The microbial contamination can result in inhibitor/fuel degradation, leading to unacceptable levels of turbidity, filter plugging, storage tank corrosion and stored product souring. Therefore, selection of the biocide/inhibitor plays an important role in the transportation of petroleum products through pipelines. Three biocides (cationic and nonionic) were employed to study the biodegradation in a diesel‐water interface. The biocidal efficiency against degradation of diesel was examined by employing Fourier‐transform infrared (FTIR) spectroscopy, nuclear magnetic resonance (NMR) spectroscopy and gas chromatography mass spectrometry (GC‐MS) techniques. Bronopol (2‐bromo‐2‐nitro‐propane‐1, 3‐diol) was found to have higher bactericidal efficiency than N‐cetyl‐N,N, N‐trimethyl ammonium bromide (CTAB) and cetyl pyridinum bromide (CPB). But the cationic biocides (CTAB and CPB) showed good biocidal efficiency at the interface. The data are explained in terms of a model that postulates the formation of a ‘micelle’ at the diesel‐water interface. Copyright © 2007 John Wiley & Sons, Ltd.     

Polysiloxane cationic biocides with imidazolium salt (ImS) groups, synthesis and antibacterial properties

Novel polysiloxanes with pendant biocidal N,N′-dialkylimidazolium salt (ImS) groups were synthesized and compared with polysiloxanes bearing conventional biocidal quaternary ammonium salt (QAS) groups. The bacteriostatic power of these polymers was tested and compared under the same conditions in aqueous solution against two common strains of Gram positive bacteria and three strains of Gram negative bacteria. These new ImS containing polymers exhibited high antibacterial potency against all bacteria studied, similar to those substituted with QAS groups. The advantage of the imidazolium substituted polysiloxane stems from its higher thermal stability, as compared with the quaternary alkylammonium functionalized polymer, as demonstrated by thermogravimetric studies.     

Antibacterial membranes based on chitosan and quaternary ammonium salts modified nanocrystalline cellulose

Etherification of nanocrystalline cellulose (NCC) with three kinds of quaternary ammonium salts epoxypropyltrimethylammonium chloride, N,N‐dimethyl‐N‐dodecyl‐N‐(1,2‐epoxypropyl) ammonium chloride (DMDEPAC), and N,N‐dimethyl‐N‐octadecyl‐N‐(1,2‐epoxypropyl) ammonium chloride (DMOEPAC) was successfully performed via a nucleophilic addition reaction. The synthesized DMDEPAC and DMOEPAC were characterized by nuclear magnetic resonance. The modified NCC particles, NCC epoxypropyltrimethylammonium chloride, NCC‐DMDEPAC, and NCC‐DMOEPAC, were characterized by energy dispersive spectrometer. Nanocomposite films based on chitosan (CS) containing quaternary ammonium salts modified NCC were prepared with nanoparticle loadings of 5.0, 7.5, and 10.0%, respectively. The effect of nanoparticle content on the tensile strength of composite films was studied. The results indicated that the films with 5.0% nanoparticle loading exhibited the biggest increase in tensile strength. Surface morphology, smoothness, and antibacterial properties of composite films containing 5% modified NCC were also studied. CS/NCC‐DMDEPAC‐5.0 and CS/NCC‐DMOEPAC‐5.0 displayed excellent biocidal abilities against both Gram‐positive Staphylococcus aureus (ATCC 6538) and Gram‐negative Escherichia coli O157:H7 (ATCC 43895). The bio‐based nanocomposite films with increased mechanical strength and excellent antibacterial properties show great potential as food packaging materials. Copyright © 2017 John Wiley & Sons, Ltd.     

Improved UV stability of antibacterial coatings with N-halamine/TiO2

The outstanding advantages of N-halamine materials over other antimicrobial materials are their durable and rechargeable antimicrobial properties, as well as their efficacies in inactivating a broad spectrum of pathogens. Theoretically, the oxidative chlorine of antimicrobial cotton coated with N-halamine hydantoin diol can be restored upon loss of its biocidal efficacy after exposure to ultraviolet light. In this work nano-titania particles were added into the coating solutions containing N-halamine diol and 1,2,3,4-butanetetracarboxylic acid (BTCA), and the coatings were applied to produce antimicrobial cellulose with improved UV stability. The treated cotton fabrics were characterized by FT-IR, SEM, XRD, and XPS. The effects of the coatings on tensile strength and wrinkle recovery angle were investigated. Biocidal efficacies of fabrics coated with hydantoin diol and diol/TiO₂ against Staphylococcus aureus (ATCC 6538) and Escherichia coli O157:H7 (ATCC 43895) were determined using a modified AATCC 100-1999 method and showed excellent antimicrobial properties against these two bacterial species within a brief contact times. It was found that the addition of Nano-TiO₂ in the antimicrobial coatings, especially rutile titanium dioxide, could improve the UV light stability of the chlorinated fabrics coated with hydantoin diol significantly. The UV light stability of N-halamine coatings were enhanced with increasing amounts of rutile TiO₂.     

Facile synthesis and biological evaluation of novel fluorine-containing <Emphasis Type="Italic">N</Emphasis>-nitro-<Emphasis Type="Italic">N</Emphasis>′-substituted phenylurea

Twenty-two novel N-nitro-N′-substituted phenyl-N-(2,6-dibromo-4-fluorophenyl)urea derivatives were designed and synthesized via a simple and convenient BTC ‘one-pot’ procedure using DMAP as the catalyst. The structures of all newly synthesized compounds were confirmed by IR, ¹H NMR, and elemental analysis, and a part has been identified by ¹³C NMR. The preliminary bioassay indicates that the target compounds possesses moderate herbicidal activity against Sorghum sudanense. However, some of the title compounds presented high plant growth regulating activity against rape.     

Surface characterisation of TiCxN1 − x coatings processed by cathodic arc physical vapour deposition: XPS and XRD analysis

The properties of titanium carbonitride (TiCN) can be controlled by maintaining the C―N ratio within the coating to a certain level. An experimental study was carried out to vary the composition and properties of TiCN using cathodic arc physical vapour deposition (CAPVD). The substrate used was tungsten carbide (WC-6Co), which was prepared in-house through a powder metallurgy process. In order to form the TiC_xN_1 − x coatings, titanium (Ti) was used as the cathode, while methane (CH₄) and nitrogen (N₂) gases were used as sources for C and N, respectively. X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD) were used to investigate the composition, chemical state, and bonding structure of the deposited coatings. The results show that the composition, intensity of elements, lattice parameter, and d-value of TiC_xN_1 − x coatings were successfully varied by controlling the CH₄ fraction (CH₄/N₂ ratio). With the increase in CH₄ fraction, the intensity of C and N within the TiC_xN_1 − x coatings increased and decreased, respectively. Consequently, the C―Ti and C―N bonds were increased and N―Ti bonds were decreased.     

N-halamine biocidal coatings via a layer-by-layer assembly technique

Two N-halamine copolymer precursors, poly(2,2,6,6-tetramethyl-4-piperidyl methacrylate-co-acrylic acid potassium salt) and poly(2,2,6,6-tetramethyl-4-piperidyl methacrylate-co-trimethyl-2-methacryloxyethylammonium chloride) have been synthesized and successfully coated onto cotton fabric via a layer-by-layer (LbL) assembly technique. A multilayer thin film was deposited onto the fiber surfaces by alternative exposure to polyelectrolyte solutions. The coating was rendered biocidal by a dilute household bleach treatment. The biocidal efficacies of tested swatches composed of treated fibers were evaluated against Staphylococcus aureus and Escherichia coli. It was determined that chlorinated samples inactivated both S. aureus and E. coli O157:H7 within 15 min of contact time, whereas the unchlorinated control samples did not exhibit significant biocidal activities. Stabilities of the coatings toward washing and ultraviolet light exposure have also been studied. It was found that the stability toward washing was superior, whereas the UVA light stability was moderate compared to previously studied N-halamine moieties. The layer-by-layer assembly technique can be used to attach N-halamine precursor polymers onto cellulose surfaces without using covalently bonding tethering groups which limit the structure designs. In addition, ionic precursors are very soluble in water, thus promising for biocidal coatings without the use of organic solvents.     

Antimicrobial Poly(2‐methyloxazoline)s with Bioswitchable Activity through Satellite Group Modification

Biocides are widely used for preventing the spread of microbial infections and fouling of materials. Since their use can build up microbial resistance and cause unpredictable long‐term environmental problems, new biocidal agents are required. In this study, we demonstrate a concept in which an antimicrobial polymer is deactivated by the cleavage of a single group. Following the satellite group approach, a biocidal quaternary ammonium group was linked through a poly(2‐methyloxazoline) to an ester satellite group. The polymer with an octyl‐3‐propionoate satellite group shows very good antimicrobial activity against Gram‐positive bacterial strains. The biocidal polymer was also found to have low hemotoxicity, resulting in a high HC₅₀/MIC value of 120 for S. aureus. Cleaving the ester satellite group resulted in a 30‐fold decrease in antimicrobial activity, proving the concept valid. The satellite group could also be cleaved by lipase showing that the antimicrobial activity of the new biocidal polymers is indeed bioswitchable.     

Contact bactericides and fungicides on the basis of amino‐functionalized poly(norbornene)s

This study is aimed at investigating the microbiocidal potential of amino‐functionalized poly(norbornenes) in the solid state. A series of norbornene‐type monomers that carry secondary or tertiary amine functions as well as hexyl and dodecyl groups were prepared. Ring‐opening metathesis polymerization was used to prepare homopolymers of the amine bearing monomers and random copolymers of amine‐ and alkyl‐substituted monomers of high average molar mass. The resulting polymers were characterized by nuclear magnetic resonance, thermogravimetry, differential scanning calorimetry, infrared spectroscopy, and contact angle measurements, and their contact biocidal potential was evaluated according to the Japanese Industry standard Z2801. Tested microorganisms comprised Pseudomonas aeruginosa, Escherichia coli, Staphylococcus aureus, Candida albicans, and Aspergillus niger. Microbiocidal activity of selected polymer films against E. coli, S. aureus, and A. niger was found, whereas against C. albicans and P. aeruginosa microbiostatic behavior was observed. Moreover, the most potent copolymer revealed no cytotoxicity rendering a biocidal polymer with potential applications in mammalian‐, and in particular, human‐related fields. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010     

In vitro antibacterial and antifungal assay of poly‐(ethylene oxamide‐N,N′‐diacetate) and its polymer–metal complexes

A new polyester, poly‐(ethylene oxamide‐N,N′‐diacetate) (PEODA), containing glycine moiety was synthesized by the reaction of oxamide‐N,N′‐diacetic acid and ethylene glycol and its polymer–metal complexes were synthesized with transition metal ions. The monomer oxamide‐N,N′‐diacetic acid was prepared by the reaction of glycine and diethyl oxalate. The polymer and its metal complexes were characterized by elemental analysis and other spectroscopic techniques. The in vitro antibacterial activities of all the synthesized polymers were investigated against some bacteria and fungi. The analytical data revealed that the coordination polymers of Mn(II), Co(II) and Ni(II) are coordinated with two water molecules, which are further supported by FTIR spectra and TGA data. The polymer–metal complexes showed excellent antibacterial activities against both types of microorganisms; the polymeric ligand was also found to be effective but less so than the polymer–metal complexes. On the basis of the antimicrobial behavior, these polymers may be used as antifungal and antifouling coating materials in fields like life‐saving medical devices and the bottoms of ships. Copyright © 2007 John Wiley & Sons, Ltd.     

Mechanically Robust and Transparent N‐Halamine Grafted PVA‐co‐PE Films with Renewable Antimicrobial Activity

Antimicrobial polymeric films that are both mechanically robust and function renewable would have broad technological implications for areas ranging from medical safety and bioengineering to foods industry; however, creating such materials has proven extremely challenging. Here, a novel strategy is reported to create high‐strength N‐halamine incorporated poly(vinyl alcohol‐co‐ethylene) films (HAF films) with renewable antimicrobial activity by combining melt radical graft polymerization and reactive extrusion technique. The approach allows here the intrinsically rechargeable N‐halamine moieties to be covalently incorporated into polymeric films with high biocidal activity and durability. The resulting HAF films exhibit integrated properties of robust mechanical strength, high transparency, rechargeable chlorination capability (>300 ppm), and long‐term durability, which can effectively offer 3–5 logs CFU reduction against typical pathogenic bacterium Escherichia coli within a short contact time of 1 h, even at high organism conditions. The successful synthesis of HAF films also provides a versatile platform for exploring the applications of antimicrobial N‐halamine moieties in a self‐supporting, structurally adaptive, and function renewable form.

     

Functionalizing ps microspheres by supercritical deposition of P(S-<Emphasis Type="Italic">b</Emphasis>-<Emphasis Type="Italic">t</Emphasis>BA) for diverse interfacial properties exemplified with biocidal ability

Polystyrene（PS） microspheres were functionalized with poly（styrene-b-tert-butyl acrylate）（P（S-b-tBA）） by adsorption from supercritical mixture of CO₂ and hexane.Supercritical deposition formed a shell-core structure that contained a shell of poly（tert-butyl acrylate）（PtBA） blocks and a core of the PS blocks entangling with the PS microspheres. The thickness of the PtBA layer and thereby the areal density of tert-butyl ester groups increased with the deposition pressure until plateau values attained at 20 MPa and higher.The tert-butyl ester groups were hydrolyzed to carboxyl groups for conjugation with tert-butylamine molecules via amide bonds that were further chlorinated into biocidal N-halamine moieties. The functionalization layer and its bonded N-halamine moieties were stable in flowing water and the chlorine could be regenerated upon eventual loss.This functionalization concept is applicable to polymers of any external and internal surfaces to achieve diverse surface properties by varying block copolymer and conjugated moieties.     

Evaluation of the Biocidal Capacity of Hypercrosslinked Resins Containing Dithiocarbamate Groups

Summary: In this study we report both the development of dithiocarbamate resins from the commercial hypercrosslinked resin MN-250 and the evaluation of the biocidal capacity of this material against E. coli ATCC25922 suspensions. The preparation of dithiocarbamate resins followed a synthetic pathway based on nitration of resins, reduction of nitro groups and reaction with CS₂ in an alkaline medium. The biocidal capacity was evaluated by means of elution of E. coli suspensions (10³–10⁷ cells/mL) through columns containing the resin and plating on LB nutrient medium solidified with Bacto agar. We can conclude that hypercrosslinked resins with dithiocarbamate groups have potential biocidal action.     

Synthesis and biological activity of novel N‐tert‐butyl‐N,N′‐substitutedbenzoylhydrazines containing 2‐methyl‐3‐(triphenylgermanyl)propoxycarbonyl

In a search for new insect growth regulators with unusual biological properties and different activity spectrum, we thought that the preservation of the bioactive unit and the introduction of 2‐methyl‐3‐(triphenylgermanyl)propoxycarbonyl in N‐tert‐butyl‐N,N′‐dibenzoylhydrazine would enhance their larvicidal activities to a significant degree. Therefore, we designed and synthesized N′‐tert‐butyl‐N′‐[2‐methyl‐3‐(triphenylgermanyl)propoxycarbonyl]‐N‐benzoylhydrazine and analogs by two procedures. These novel compounds were characterized by elemental analyses, IR, and ¹H NMR. At the same time, N‐tert‐butyl‐N‐substitutedbenzoylhydrazines were prepared by a new method, and some reactions involved were studied. The preliminary results indicate that some compounds have inhibitory effects against plant pathogenetic bacteria such as early blight of tomato. Copyright © 2002 John Wiley & Sons, Ltd.     

Synthesis and Anticorrosion and Biocidal Activity of Triazoloazepine Derivatives

Inhibiting effect on acid corrosion of steel 45 and biocidal activity with respect to sulfate-reducing bacteria are studied for a series of N-aryl-N-(6,7,8,9-tetrahydro-5H-[1,2,4]triazolo[4,3-a]azepin-3-ylmethyl)amines.     

Triethoxy(3-isothiocyanatopropyl)silane

The reaction of triethoxy(3-aminopropyl)silane with carbon disulfide andortho-chloroethyl formate in absolute ethanol gave triethoxy(3-isothiocyanatopropyl)silane for the first time. The presence of SCN and (C₂H₅O)₃Si groups in this compound enabled us to use it for the preparation of adsorbents and polymer coatings with biocidal activity.Irkutsk Institute of Organic Chemistry, Siberian Branch, Russian Academy of Sciences, 664033 Irkutsk. Translated fromIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 11, pp. 2681–2682, November, 1992.     

Temperature‐dependent phase‐segregation behavior and antifouling performance of UV‐curable methacrylated PDMS/PEG coatings

Controllable phase segregation adjustment for immiscible polymer blends has always been tough, which hinders the development of amphiphilic antifouling coatings from more accessible blends. Herein, methacrylated poly(dimethylsiloxane) (PDMS‐MA) was synthesized and mixed with poly(ethylene glycol)methylether methacrylate (PEG‐MA). It was interestingly discovered that these PDMS‐MA/PEG‐MA blends displayed upper critical solution temperatures (UCST) due to thermo‐induced conformational change of PEG‐MA and the UCST changed with PDMS‐MA/PEG‐MA mass ratios. Micro‐/nano‐phase segregation, nanophase segregation, or homogenous morphology were therefore achieved. These PDMS‐MA/PEG‐MA blends with different mass ratios were UV‐cured under varying temperatures to fabricate coatings. Their surface morphology and wettability are readily adjusted by phase segregation. For the first time, highly hydrophilic surface was achieved for coatings with microphase segregation because of the exposure of PEG‐rich domains, which exhibited an enhanced protein resistance against bovine serum albumin (BSA). Anti‐bacterial performance (Shewanella loihica) was also observed for these PDMS/PEG coatings. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 1612–1623