Vapor-Phase Carbenylation of Hard and Soft Material Interfaces

Li, Xunzhi; Ma, Wenchuan; Shestopalov, Alexander A.

doi:10.1021/acs.langmuir.6b02471

Cited by 12 publications

(23 citation statements)

References 63 publications

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“…45 However, nanoporous NPN has a substantial amount of oxygen atoms that can promote carbene insertion into the surface O–H bonds leading to the hydrolytic O–C attachment. To avoid unstable bonding, we passivated NPN substrates with an ultrathin methylated alkyl silane film that provides necessary C–H bonds for the carbene attachment and acts as a chemically inert passivating barrier to more reactive NPN (Me-NPN, Figure 1).…”

Section: Resultsmentioning

confidence: 99%

“…NHS-diazirine was synthesized in 10 steps following the previously published protocol. 45 To generate a C–H terminated inert coating on NPN that can accept carbene molecules, we first installed and annealed a thin alkyl-silane layer. As such, NPN chips were oxidized in oxygen plasma and exposed to the 10:1 (v/v) mixture of octyl triethoxysilane (OTC) and trimethylamine vapor overnight at mild vacuum at 75 °C.…”

Section: Methodsmentioning

confidence: 99%

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Modification of Nanoporous Silicon Nitride with Stable and Functional Organic Monolayers

Johnson

et al. 2017

Chem. Mater.

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This study describes the formation of functional organic monolayers on thin, nanoporous silicon nitride membranes. We demonstrate that the vapor-phase carbene insertion into the surface C–H bonds can be used to form sub-5 nm molecular coatings on nanoporous materials, which can be further modified with monolayers of polyethylene glycol (PEG) molecules. We investigate composition, thickness, and stability of the functionalized monolayers and the changes in the membrane permeability and pore size distribution. We show that, due to the low coating thickness (~7 nm), the functionalized membrane retains 80% of the original gas permeance and 40% of the original hydraulic permeability. We also show that the carbene/PEG functionalization is hydrolytically stable for up to 48 h of exposure to water and that it can suppress nonspecific adsorption of the proteins BSA and IgG. Our results suggest that the vapor-phase carbenylation can be used as a complementary technology to the traditional self-assembly and polymer brush chemistries in chemical functionalization of nanoporous materials, which are limited in their ability to serve as stable coatings that do not occlude nanomembrane pores.

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Section: Resultsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Modification of Nanoporous Silicon Nitride with Stable and Functional Organic Monolayers

Johnson

et al. 2017

Chem. Mater.

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“…Everything has two sides and UV–vis light is no exception . There were many studies on using high‐energy UV light to initiate reactions and UV light irradiation has become a very important method . However, the loss of mechanical properties, photodegradation, discoloration, and photocrosslinking of polymers can be caused by UV radiation.…”

Section: Introductionmentioning

confidence: 99%

Fabrication of highly efficient ultraviolet absorbing PVDF membranes via surface polydopamine deposition

Dong

Liu

Xiong

et al. 2017

J of Applied Polymer Sci

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Polydopamine (PDA) layers and particles self-polymerized by dopamine have ultraviolet (UV) absorbing property besides versatility and adhesive ability. Herein, a facile strategy for preparing poly(vinylidene fluoride) (PVDF) membrane coated with a thick PDA layer was developed to decrease UV transmittance through the surface modification of PVDF membrane. The PVDF membrane was modified by PDA deposition after pretreated with KOH/alcohol and KMnO 4 /KOH solution. Furthermore, we investigated the effect of coating conditions such as concentration of dopamine and Tris-HCl buffer solution, coating time, and temperature on the performance of membranes. The characterization results indicated that it is more conductive for PDA deposition on the surface PVDF-OH films than original PVDF films. Most importantly, UV transmittance of PVDF-OH film modified in dopamine solution under optimum condition for one time can decrease to as low as 0.122% at 320 nm, which showed excellent UV-shielding property.

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“…The native surface of the NPN‐O membranes was first deposited with NHS‐Diazirine through vacuum phase reaction and further grafted with PEG1000 (#B22134, Alpha Aesar, MA, USA) largely as described previously . The PEG reaction temperature (75 °C) was increased for the 5.4 mm × 5.4 mm chips, because it was found that the high temperature increased the solubility of the PEG and helped the reaction on the NPN surface.…”

Section: Methodsmentioning

confidence: 99%

“…Commercial high-flux dialyzers, with ≈1.8 m 2 surface area, had a K o of ≈560 mL min −1 m −2 , two orders of magnitude smaller than the K o of the nanoporous membranes. [44] PEG Coatings: The native surface of the NPN-O membranes was first deposited with NHS-Diazirine through vacuum phase reaction [45] and further grafted with PEG1000 (#B22134, Alpha Aesar, MA, USA) largely as described previously. [22] The PEG reaction temperature (75 °C) was increased for the 5.4 mm × 5.4 mm chips, because it was found that the high temperature increased the solubility of the PEG and helped the reaction on the NPN surface.…”

Section: Methodsmentioning

confidence: 99%

Second Generation Nanoporous Silicon Nitride Membranes for High Toxin Clearance and Small Format Hemodialysis

Hill

Walker

Salminen

et al. 2020

Adv Healthcare Materials

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Conventional hemodialysis (HD) uses floor‐standing instruments and bulky dialysis cartridges containing ≈2 m2 of 10 micrometer thick, tortuous‐path membranes. Portable and wearable HD systems can improve outcomes for patients with end‐stage renal disease by facilitating more frequent, longer dialysis at home, providing more physiological toxin clearance. Developing devices with these benefits requires highly efficient membranes to clear clinically relevant toxins in small formats. Here, the ability of ultrathin (<100 nm) silicon‐nitride‐based membranes to reduce the membrane area required to clear toxins by orders of magnitude is shown. Advanced fabrication methods are introduced that produce nanoporous silicon nitride membranes (NPN‐O) that are two times stronger than the original nanoporous nitride materials (NPN) and feature pore sizes appropriate for middle‐weight serum toxin removal. Single‐pass benchtop studies with NPN‐O (1.4 mm2) demonstrate the extraordinary clearance potential of these membranes (105 mL min−1 m−2), and their intrinsic hemocompatibility. Results of benchtop studies with nanomembranes, and 4 h dialysis of uremic rats, indicate that NPN‐O can reduce the membrane area required for hemodialysis by two orders of magnitude, suggesting the performance and robustness needed to enable small‐format hemodialysis, a milestone in the development of small‐format hemodialysis systems.

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Vapor-Phase Carbenylation of Hard and Soft Material Interfaces

Cited by 12 publications

References 63 publications

Modification of Nanoporous Silicon Nitride with Stable and Functional Organic Monolayers

Modification of Nanoporous Silicon Nitride with Stable and Functional Organic Monolayers

Fabrication of highly efficient ultraviolet absorbing PVDF membranes via surface polydopamine deposition

Second Generation Nanoporous Silicon Nitride Membranes for High Toxin Clearance and Small Format Hemodialysis

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