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1.
ACS Appl Mater Interfaces ; 16(29): 37952-37962, 2024 Jul 24.
Article in English | MEDLINE | ID: mdl-38990338

ABSTRACT

Commercial membranes today are manufactured from a handful of membrane materials. While these systems are well-optimized, their capabilities remain constrained by limited chemistries and manufacturing methods available. As a result, membranes cannot address many relevant separations where precise selectivity is needed, especially with complex feeds. This constraint requires the development of novel membrane materials that offer customizable features to provide specific selectivity and durability requirements for each application, enabled by incorporating different functional chemistries into confined nanopores in a scalable process. This study introduces a new class of membrane materials, amphiphilic polyelectrolyte complexes (APECs), comprised of a blend two distinct amphiphilic polyelectrolytes of opposite charge that self-assemble to form a polymer selective layer. When coated on a porous support from a mixture in a nonaqueous solvent, APECs self-assemble to create ionic nanodomains acting as water-conducting nanochannels, enveloped within hydrophobic nanodomains, ensuring structural integrity of the layer in water. Notably, this approach allows precise control over selectivity without compromising pore size, permeability, or fouling resistance. For example, using only one pair of amphiphilic copolymers, sodium sulfate rejections can be varied from >95% to <10% with no change in effective pore size and fouling resistance. Given the wide range of amphiphilic polyelectrolytes (i.e., combinations of different hydrophobic, anionic, and cationic monomers), APECs can create membranes with many diverse chemistries and selectivities. Resultant membranes can potentially address precision separations in many applications, from wastewater treatment to chemical and biological manufacturing.

2.
J Mater Chem B ; 12(1): 145-157, 2023 12 22.
Article in English | MEDLINE | ID: mdl-38051000

ABSTRACT

The use of microfluidic devices in biomedicine is growing rapidly in applications such as organs-on-chip and separations. Polydimethylsiloxane (PDMS) is the most popular material for microfluidics due to its ability to replicate features down to the nanoscale, flexibility, gas permeability, and low cost. However, the inherent hydrophobicity of PDMS leads to the adsorption of macromolecules and small molecules on device surfaces. This curtails its use in "organs-on-chip" and other applications. Current technologies to improve PDMS surface hydrophilicity and fouling resistance involve added processing steps or do not create surfaces that remain hydrophilic for long periods. This work describes a novel, simple, fast, and scalable method for improving surface hydrophilicity and preventing the nonspecific adsorption of proteins and small molecules on PDMS through the use of a surface-segregating zwitterionic copolymer as an additive that is blended in during manufacture. These highly branched copolymers spontaneously segregate to surfaces and rearrange in contact with aqueous solutions to resist nonspecific adsorption. We report that mixing a minute amount (0.025 wt%) of the zwitterionic copolymer in PDMS considerably reduces hydrophobicity and nonspecific adsorption of proteins (albumin and lysozyme) and small molecules (vitamin B12 and reactive red). PDMS blended with these zwitterionic copolymers retains its mechanical and physical properties for at least six months. Moreover, this approach is fully compatible with existing PDMS device manufacture protocols without additional processing steps and thus provides a low-cost and user-friendly approach to fabricating reliable biomicrofluidics.


Subject(s)
Dimethylpolysiloxanes , Proteins , Surface Properties , Dimethylpolysiloxanes/chemistry , Proteins/chemistry , Microfluidics
3.
ACS Appl Mater Interfaces ; 15(36): 42557-42567, 2023 Sep 13.
Article in English | MEDLINE | ID: mdl-37656014

ABSTRACT

The versatility of membranes is limited by the narrow range of material chemistries on the market, which cannot address many relevant separations. Expanding their use requires new membrane materials that can be tuned to address separations by providing the desired selectivity and robustness. Self-assembly is a versatile and scalable approach to create tunable membranes with a narrow pore size distribution. This study reports the first examples of a new class of membrane materials that derives state-of-the-art permeability, selectivity, and fouling resistance from the self-assembly of random polyampholyte amphiphilic copolymers. These membranes feature a network of ionic nanodomains that serve as nanochannels for water permeation, framed by hydrophobic nanodomains that preserve their structural integrity. This copolymer design approach enables precise selectivity control. For example, sodium sulfate rejections can be tuned from 5% to 93% with no significant change in the pore size or fouling resistance. Membranes developed here have potential applications in wastewater treatment and chemical separations.

4.
Bioact Mater ; 25: 415-429, 2023 Jul.
Article in English | MEDLINE | ID: mdl-37056249

ABSTRACT

Despite decades of efforts, state-of-the-art synthetic burn dressings to treat partial-thickness burns are still far from ideal. Current dressings adhere to the wound and necessitate debridement. This work describes the first "supramolecular hybrid hydrogel (SHH)" burn dressing that is biocompatible, self-healable, and on-demand dissoluble for easy and trauma-free removal, prepared by a simple, fast, and scalable method. These SHHs leverage the interactions of a custom-designed cationic copolymer via host-guest chemistry with cucurbit[7]uril and electrostatic interactions with clay nanosheets coated with an anionic polymer to achieve enhanced mechanical properties and fast on-demand dissolution. The SHHs show high mechanical strength (>50 kPa), self-heal rapidly in ∼1 min, and dissolve quickly (4-6 min) using an amantadine hydrochloride (AH) solution that breaks the supramolecular interactions in the SHHs. Neither the SHHs nor the AH solution has any adverse effects on human dermal fibroblasts or epidermal keratinocytes in vitro. The SHHs also do not elicit any significant cytokine response in vitro. Furthermore, in vivo murine experiments show no immune or inflammatory cell infiltration in the subcutaneous tissue and no change in circulatory cytokines compared to sham controls. Thus, these SHHs present excellent burn dressing candidates to reduce the time of pain and time associated with dressing changes.

5.
Environ Sci Technol ; 56(12): 8176-8186, 2022 06 21.
Article in English | MEDLINE | ID: mdl-35576931

ABSTRACT

Long-term continuous monitoring (LTCM) of water quality can provide high-fidelity datasets essential for executing swift control and enhancing system efficiency. One roadblock for LTCM using solid-state ion-selective electrode (S-ISE) sensors is biofouling on the sensor surface, which perturbs analyte mass transfer and deteriorates the sensor reading accuracy. This study advanced the anti-biofouling property of S-ISE sensors through precisely coating a self-assembled channel-type zwitterionic copolymer poly(trifluoroethyl methacrylate-random-sulfobetaine methacrylate) (PTFEMA-r-SBMA) on the sensor surface using electrospray. The PTFEMA-r-SBMA membrane exhibits exceptional permeability and selectivity to primary ions in water solutions. NH4+ S-ISE sensors with this anti-fouling zwitterionic layer were examined in real wastewater for 55 days consecutively, exhibiting sensitivity close to the theoretical value (59.18 mV/dec) and long-term stability (error <4 mg/L). Furthermore, a denoising data processing algorithm (DDPA) was developed to further improve the sensor accuracy, reducing the S-ISE sensor error to only 1.2 mg/L after 50 days of real wastewater analysis. Based on the dynamic energy cost function and carbon footprint models, LTCM is expected to save 44.9% NH4+ discharge, 12.8% energy consumption, and 26.7% greenhouse emission under normal operational conditions. This study unveils an innovative LTCM methodology by integrating advanced materials (anti-fouling layer coating) with sensor data processing (DDPA).


Subject(s)
Biofouling , Biofouling/prevention & control , Ions , Methacrylates , Polymers , Wastewater
6.
Proc Natl Acad Sci U S A ; 118(37)2021 09 14.
Article in English | MEDLINE | ID: mdl-34493652

ABSTRACT

Water filtration membranes with advanced ion selectivity are urgently needed for resource recovery and the production of clean drinking water. This work investigates the separation capabilities of cross-linked zwitterionic copolymer membranes, a self-assembled membrane system featuring subnanometer zwitterionic nanochannels. We demonstrate that selective zwitterion-anion interactions simultaneously control salt partitioning and diffusivity, with the permeabilities of NaClO4, NaI, NaBr, NaCl, NaF, and Na2SO4 spanning roughly three orders of magnitude over a wide range of feed concentrations. We model salt flux using a one-dimensional transport model based on the Maxwell-Stefan equations and show that diffusion is the dominant mode of transport for 1:1 sodium salts. Differences in zwitterion-Cl- and zwitterion-F- interactions granted these membranes with the ultrahigh Cl-/F- permselectivity (PCl-/PF- = 24), enabling high fluoride retention and high chloride passage even from saline mixtures of NaCl and NaF.

7.
Membranes (Basel) ; 11(5)2021 May 20.
Article in English | MEDLINE | ID: mdl-34065587

ABSTRACT

Hollow-fiber membrane filters (HFMFs) for household water treatment (HWT) can efficaciously remove disease-causing organisms in laboratory settings. However, lower effectiveness in use in low- and middle-income countries (LMICs) and humanitarian contexts (HCs) has been observed and attributed to membrane fouling and the associated cleaning. In LMICs/HCs, it is not possible to prevent and control fouling using commonly known methods (e.g., testing influent water, maintenance regimes), and the literature on fouling/cleaning of HFMFs distributed in LMICs is scarce. As such, controlled laboratory experiments were conducted to determine the efficacy of locally available (in LMICs/HCs) backwashing solutions at removing fouling using different influent waters and HFMF types. Four commonly distributed HFMFs were selected; fouling layers were developed by filtering three influent water compositions, representing LMIC/HC waters, for 10-days, and bleach, water, or vinegar backwashing solutions were used for daily backwashing. Filter performance indicators included: fiber mechanical properties (strain at break, break force), water quantity performance (flow), water quality performance (turbidity, E. coli), and imaging. The study found fouling developed rapidly and altered mechanical properties and water quantity indicators within 200 h of filtration. Fouling did not decrease water quality indicators. Backwashing improved the filter's mechanical properties and water quantity performance, but it did not fully recover the initial performance. Additionally, recovery differed between backwashing solutions, and no universal cleaning recommendation appropriate for HFMFs in LMICs/HCs was identified. Overall, fouling development and control depended on HFMF type, influent water quality, and backwashing solution type; thus, caution before distributing HFMFs for long-term use in LMICs/HCs is recommended.

8.
ACS Appl Mater Interfaces ; 11(20): 18711-18719, 2019 May 22.
Article in English | MEDLINE | ID: mdl-31059214

ABSTRACT

In this study, we show that codeposition of temperature responsive microgels in the foulant cake layer and cleaning of the cake upon stimuli-induced size change of the microgels is an effective method of fouling removal. Humic acid in CaCl2 solution was used as a model foulant and poly( n-isopropylacrylamide) (p(NIPAm)) and poly( n-isopropylacrylamide- co-sulfobetainemethacrylate) (p(NIPAm- co-SBMA)) were used as temperature responsive microgels. Filtrations were done below the lower critical solution temperature (LCST) and temperature was increased to above the LCST for cleaning. As an extra cleaning a temperature swing of above, below and then again above the LCST was applied. P(NIPAm) was found to be ineffective in cleaning the foulant deposit despite the 20-fold change in its volume with temperature change at LCST. P(NIPAm- co-SBMA) microgels, on the other hand, provided high fouling reversibility on hydrophilic poly(ether sulfone)(PES)/poly(vinylpyrrolidone) (PVP) and hydrophobic PES membranes. Better fouling reversibility with these microgels was observed at low and high solution ionic strength. While the use of microgels alone increased fouling reversibility to some extent, even in the absence of temperature stimulus, 100% reversibility could only be obtained when a temperature switch was applied in the presence of microgels, showing the effect of microgels' volume change in cleaning.

9.
Sci Rep ; 9(1): 7377, 2019 05 14.
Article in English | MEDLINE | ID: mdl-31089162

ABSTRACT

Poly(dimethylsiloxane) (PDMS) is likely the most popular material for microfluidic devices in lab-on-a-chip and other biomedical applications. However, the hydrophobicity of PDMS leads to non-specific adsorption of proteins and other molecules such as therapeutic drugs, limiting its broader use. Here, we introduce a simple method for preparing PDMS materials to improve hydrophilicity and decrease non-specific protein adsorption while retaining cellular biocompatibility, transparency, and good mechanical properties without the need for any post-cure surface treatment. This approach utilizes smart copolymers comprised of poly(ethylene glycol) (PEG) and PDMS segments (PDMS-PEG) that, when blended with PDMS during device manufacture, spontaneously segregate to surfaces in contact with aqueous solutions and reduce the hydrophobicity without any added manufacturing steps. PDMS-PEG-modified PDMS samples showed contact angles as low as 23.6° ± 1° and retained this hydrophilicity for at least twenty months. Their improved wettability was confirmed using capillary flow experiments. Modified devices exhibited considerably reduced non-specific adsorption of albumin, lysozyme, and immunoglobulin G. The modified PDMS was biocompatible, displaying no adverse effects when used in a simple liver-on-a-chip model using primary rat hepatocytes. This PDMS modification method can be further applied in analytical separations, biosensing, cell studies, and drug-related studies.


Subject(s)
Dimethylpolysiloxanes/chemistry , Lab-On-A-Chip Devices , Microfluidic Analytical Techniques/instrumentation , Stimuli Responsive Polymers/chemistry , Animals , Cells, Cultured , Hepatocytes , Hydrophobic and Hydrophilic Interactions , Materials Testing , Polyethylene Glycols/chemistry , Primary Cell Culture , Rats , Surface Properties
10.
ACS Appl Mater Interfaces ; 11(13): 12854-12862, 2019 Apr 03.
Article in English | MEDLINE | ID: mdl-30844237

ABSTRACT

Membranes that can separate molecules of similar size based on chemical features could transform chemical manufacturing. We demonstrate membranes with functional, 1-3 nm pores prepared using a simple and scalable approach: coating a porous support with random copolymer micelles in alcohol, followed by precipitation in water and functionalization of pore surfaces. This approach was used to prepare membranes that can separate two hormones of similar size and charge, differentiated by aromaticity, mediated through π-π interactions between the aromatic solute and pore walls functionalized with phenol groups. The aromatic molecule permeates more slowly in single-solute experiments. In competitive diffusion experiments, however, it permeates 7.1 times faster than its nonaromatic analogue. This approach can be used to manufacture membranes for complex separations based on various intermolecular interactions.

11.
ACS Appl Mater Interfaces ; 10(21): 18300-18309, 2018 May 30.
Article in English | MEDLINE | ID: mdl-29658698

ABSTRACT

A porous material that is both hydrophobic and fouling-resistant is needed in many applications, such as water purification by membrane distillation. In this work, we take a novel approach to fabricating such membranes. Using the zwitterionic amphiphilic copolymer poly(trifluoroethyl methacrylate- random-sulfobetaine methacrylate), we electrospin nonwoven, porous membranes that combine high hydrophobicity with resistance to protein adsorption. By changing the electrospinning parameters and the solution composition, membranes can be prepared with a wide range of fiber morphologies including beaded, bead-free, wrinkly, and ribbonlike fibers, with diameters ranging between ∼150 nm and 1.5 µm. The addition of LiCl to the spinning solution not only helps control the fiber morphology but also increases the segregation of zwitterionic groups on the membrane surface. The resultant electrospun membranes are highly porous and very hydrophobic, yet resist the adsorption of proteins and retain a high contact angle (∼140°) even after exposure to a protein solution. This makes these materials promising candidates for the membrane distillation of contaminated wastewater streams and as self-cleaning materials.

12.
ACS Nano ; 12(1): 95-108, 2018 01 23.
Article in English | MEDLINE | ID: mdl-29205035

ABSTRACT

Membranes that can separate compounds based on molecular properties can revolutionize the chemical and pharmaceutical industries. This study reports membranes capable of separating organic molecules of similar size based on their electrostatic charge. These membranes feature a network of carboxylate-functionalized 1-3 nm nanochannels, manufactured by a simple, scalable coating process: a porous support is coated with a packed array of polymer micelles in alcohol, formed by the self-assembly of a water-insoluble random copolymer with fluorinated and carboxyl functional repeat units. The interstices between these micelles serve as charged nanochannels through which water and solutes can pass. The negatively charged carboxylate groups lead to high separation selectivities between organic solutes of similar size but different charge. In single-solute diffusion experiments, neutral solutes permeate up to 263 times faster than negatively charged compounds of similar size. This selectivity is further enhanced in experiments with mixtures of these solutes. No permeation of the anionic compound was observed for over 24 h. In filtration experiments, these membranes separate anionic and neutral organic compounds while exhibiting water fluxes comparable to that of commercial membranes. Furthermore, carboxylate groups can be functionalized, creating membranes with nanopores with customizable functionality to enable a broad range of selective separations.

13.
Technology (Singap World Sci) ; 5(1): 1-12, 2017 03.
Article in English | MEDLINE | ID: mdl-28695160

ABSTRACT

In the last decade microfabrication processes including rapid prototyping techniques have advanced rapidly and achieved a fairly mature stage. These advances have encouraged and enabled the use of microfluidic devices by a wider range of users with applications in biological separations and cell and organoid cultures. Accordingly, a significant current challenge in the field is controlling biomolecular interactions at interfaces and the development of novel biomaterials to satisfy the unique needs of the biomedical applications. Poly(dimethylsiloxane) (PDMS) is one of the most widely used materials in the fabrication of microfluidic devices. The popularity of this material is the result of its low cost, simple fabrication allowing rapid prototyping, high optical transparency, and gas permeability. However, a major drawback of PDMS is its hydrophobicity and fast hydrophobic recovery after surface hydrophilization. This results in significant nonspecific adsorption of proteins as well as small hydrophobic molecules such as therapeutic drugs limiting the utility of PDMS in biomedical microfluidic circuitry. Accordingly, here, we focus on recent advances in surface molecular treatments to prevent fouling of PDMS surfaces towards improving its utility and expanding its use cases in biomedical applications.

14.
ACS Appl Mater Interfaces ; 9(24): 20859-20872, 2017 Jun 21.
Article in English | MEDLINE | ID: mdl-28544845

ABSTRACT

Membranes with high flux, ∼1 nm pore size, and unprecedented protein fouling resistance were prepared by forming selective layers of self-assembling zwitterionic amphiphilic random copolymers on porous supports by a simple coating method. Random copolymers were prepared from the hydrophobic monomer 2,2,2-trifluoroethyl methacrylate (TFEMA) and four zwitterionic monomers (sulfobetaine methacrylate, sulfobetaine 2-vinylpyridine, sulfobutylbetaine 2-vinylpyridine, and 2-methacryloyloxyethyl phosphorylcholine) by free radical polymerization. All copolymers microphase separated to form bicontinuous ∼1.2 nm nanodomains with the zwitterionic domains acting as nanochannels for the permeation of water and solutes. The resultant membranes all had a ∼1 nm size cutoff independent of zwitterion chemistry. There were, however, significant differences in the hydrophilicity, water uptake, water flux, and fouling resistance among membranes prepared with different zwitterionic monomers. Membranes prepared from the copolymer with 2-methacryloyloxyethyl phosphorylcholine were the most hydrophilic and had the highest water permeance, higher than that of commercial membranes of similar pore size. Furthermore, these membranes showed unprecedented fouling resistance, exhibiting no measurable flux decline throughout a 24 h protein fouling experiment. The structure-property relationships gleaned from this survey of different zwitterion structures serves as a guideline to develop new zwitterionic materials for various applications such as membranes, drug delivery, and sensors.

15.
ACS Appl Mater Interfaces ; 9(15): 13619-13631, 2017 Apr 19.
Article in English | MEDLINE | ID: mdl-28345857

ABSTRACT

In this study, we present a novel self-cleaning, photoresponsive membrane that is capable of removing predeposited foulant layers upon changes in surface morphology in response to UV or visible light irradiation while maintaining stable pore size and water permeance. These membranes were prepared by creating thin film composite (TFC) membranes by coating a porous support membrane with a thin layer of novel comb-shaped graft copolymers at two side-chain lengths featuring polyacrylonitrile (PAN) backbones and photoreactive side chains, synthesized by atom transfer radical polymerization (ATRP). Photoregulated control over membrane properties is attained through a light-induced transition, where the side chains switch between a hydrophobic spiropyran (SP) state and a zwitterionic, hydrophilic merocyanine (MC) state. The light-induced switch between the SP and MC forms changes surface hydrophilicity and causes morphological changes on the membrane surface as evidenced by atomic force microscopy (AFM). Before any phototreatment, the as-coated membrane surface comprises mostly hydrophobic SP groups that allow the adsorption of organic solutes such as proteins the membrane surface, reducing flow rate. Once exposed to UV light, conversion of the SP groups to hydrophilic MC groups leads to the release of adsorbed molecules and the full recovery of the initial water flux. A fouled membrane in the more hydrophilic MC form is also capable of self-cleaning upon conversion to the less hydrophilic SP form by visible light irradiation. The self-cleaning behavior observed for this system, where the surface became less hydrophilic but also experienced a morphological change, demonstrates a novel mechanism that has a mechanical component in addition to the changes in hydrophilicity. It is also the first report, to our knowledge, of self-cleaning performance accompanied by a decrease in hydrophilicity.

16.
ACS Macro Lett ; 4(9): 872-878, 2015 Sep 15.
Article in English | MEDLINE | ID: mdl-35596450

ABSTRACT

Permeation of small molecule solutes through thin films is typically described by the solution-diffusion model, but this model cannot predict the effects of nanostructure due to self-assembly or additives. Other models focusing on diffusion through isolated nanopores indicate that confining permeation to channels slightly larger than the size of the solute can lead to an increased influence of solute-pore wall interactions on permeation rate. In this study, we analyze how differences in polymer nanostructure affect the relative contributions of solute size and polymer-solute interactions on transport rate. We compared the diffusion rates of several small molecules through two polymer thin films: A cross-linked, homogeneous film of poly(ethylene glycol phenyl ether acrylate) (PEGPEA) and a graft copolymer with a poly(vinylidene fluoride-co-chlorotrifluoroethylene) (P(VDF-co-CTFE)) backbone and PEGPEA side chains that self-assemble into continuous ∼1-3 nm PEGPEA domains through which transport occurs. We correlated these rates with the size of each solute and its chemical affinity to PEGPEA, as measured by the difference between their solubility parameters. Diffusion rate through the homogeneous polymer film was controlled by solute size, whereas diffusion rate through the copolymer was strongly controlled by the difference between the solubility parameters. Furthermore, permeation selectivity between two selected molecules was 2.5× higher for the nanostructured copolymer, likely enhanced by the nanoconfinement effects. These initial results indicate that polymer self-assembly is a promising tool for designing polymeric membranes that can differentiate between solutes of similar size but differing chemical structures.

17.
Adv Mater ; 24(27): 3692-6, 2012 Jul 17.
Article in English | MEDLINE | ID: mdl-22689327

ABSTRACT

A new design paradigm for conformal, all-organic coatings that retain their flexibility and chemical functionality while displaying exceptional mechanical hardness and barrier properties is presented. Initiated chemical vapor deposition is used to synthesize a novel alternating copolymer thin film. Upon annealing, films display elastic moduli exceeding 20 GPa, excellent scratch resistance and flexibility, and very low oxygen permeability.


Subject(s)
Equipment Design , Elastic Modulus , Gases/chemistry , Hardness , Polymers/chemistry , Surface Properties
18.
Nano Lett ; 11(2): 677-86, 2011 Feb 09.
Article in English | MEDLINE | ID: mdl-21166426

ABSTRACT

High-aspect ratio hydrophobic, cylindrical nanopores having diameters as low as 5 nm are rapidly fabricated using conformal vapor deposition of fluorinated polymeric layers into porous track-etched polycarbonate membranes. The resultant selectivity of these membranes for pairs of small molecules of similar size, but of different hydrophobicity, arises from solute-pore wall interactions emphasized by confinement. Increasing selectivity was observed as pore diameter decreased and as the surface of the pore became more hydrophobic. Cylindrical pores provided higher selectivity than bottleneck-shaped pores having the same minimum diameter. A maximum selectivity of 234 was achieved between mesitylene and phloroglucinol by the best performing membrane. Membranes with small fluorinated pores exhibited an effective cutoff based on the polar surface area of the molecules, with limited correlation with solute size. This technology could lead to a new generation of membrane separations based on specific interactions.


Subject(s)
Crystallization/methods , Membranes, Artificial , Nanostructures/chemistry , Nanostructures/ultrastructure , Nanotechnology/methods , Polymers/chemistry , Water/chemistry , Gases/chemistry , Hydrophobic and Hydrophilic Interactions , Macromolecular Substances/chemistry , Materials Testing , Molecular Conformation , Particle Size , Porosity , Surface Properties
19.
Adv Mater ; 22(18): 1993-2027, 2010 May 11.
Article in English | MEDLINE | ID: mdl-20544886

ABSTRACT

Chemical vapor deposition (CVD) polymerization utilizes the delivery of vapor-phase monomers to form chemically well-defined polymeric films directly on the surface of a substrate. CVD polymers are desirable as conformal surface modification layers exhibiting strong retention of organic functional groups, and, in some cases, are responsive to external stimuli. Traditional wet-chemical chain- and step-growth mechanisms guide the development of new heterogeneous CVD polymerization techniques. Commonality with inorganic CVD methods facilitates the fabrication of hybrid devices. CVD polymers bridge microfabrication technology with chemical, biological, and nanoparticle systems and assembly. Robust interfaces can be achieved through covalent grafting enabling high-resolution (60 nm) patterning, even on flexible substrates. Utilizing only low-energy input to drive selective chemistry, modest vacuum, and room-temperature substrates, CVD polymerization is compatible with thermally sensitive substrates, such as paper, textiles, and plastics. CVD methods are particularly valuable for insoluble and infusible films, including fluoropolymers, electrically conductive polymers, and controllably crosslinked networks and for the potential to reduce environmental, health, and safety impacts associated with solvents. Quantitative models aid the development of large-area and roll-to-roll CVD polymer reactors. Relevant background, fundamental principles, and selected applications are reviewed.


Subject(s)
Gases/chemistry , Polymers/chemistry , Nanostructures/chemistry , Nanostructures/ultrastructure , Photoelectron Spectroscopy , Solvents/chemistry
20.
Environ Sci Technol ; 44(7): 2406-11, 2010 Apr 01.
Article in English | MEDLINE | ID: mdl-20192174

ABSTRACT

We examined the resistance to bacterial adhesion of a novel polyacrylonitrile (PAN) ultrafiltration membrane incorporating the amphiphilic comb copolymer additive, polyacrylonitrile-graft-polyethylene oxide (PAN-g-PEO). The adhesion of bacteria (E. coli K12) and the reversibility of adhered bacteria were tested with the novel membrane, and the behavior was compared to a commercial PAN ultrafiltration membrane. Under static (no flow) bacterial adhesion tests, we observed no bacterial adhesion to the PAN/PAN-g-PEO membrane at all ionic strengths tested, even with the addition of calcium ions. In contrast, significant adhesion of bacterial cells was observed on the commercial PAN membrane, with increased cell adhesion at higher ionic strengths and in the presence of calcium ions. Under crossflow filtration conditions, initial bacterial deposition rate increased with ionic strength and with addition of calcium ions for both membranes, with generally lower bacterial deposition rate with the PAN/PAN-g-PEO membrane. However, deposited bacteria were readily removed (between 97 and 100%) from the surface of the PAN/PAN-g-PEO membrane upon increasing the crossflow and eliminating the permeate flow (i.e., no applied transmembrane pressure), suggesting reversible adhesion of bacteria. In contrast, bacterial adhesion on the commercial PAN membrane was irreversible, with approximately 50% removal of adhered bacteria at moderate ionic strengths (10 and 30 mM) and less than 25% removal at high ionic strength (100 mM). The resistance to bacterial adhesion of the PAN/PAN-g-PEO membrane was further analyzed via measurement of interaction forces with atomic force microscopy (AFM). No adhesion forces were detected between a carboxylated colloid probe and the PAN/PAN-g-PEO membrane, while the probe exhibited strong adhesion to the commercial PAN membrane, consistent with the bacterial adhesion tests. The exceptional resistance of the PAN/PAN-g-PEO membrane to bacterial adhesion is attributable to steric repulsion imparted by the dense brush layer of polyethylene oxide (PEO) chains.


Subject(s)
Acrylic Resins/pharmacology , Bacterial Adhesion/drug effects , Escherichia coli/cytology , Escherichia coli/drug effects , Membranes, Artificial , Polyethylene Glycols/pharmacology , Colloids , Electrophoresis , Microscopy, Atomic Force , Ultrafiltration
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