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9 protocols using tetramethoxysilane

1

Analytical Standards for Mass Spectrometry

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Methanol (99.9% Chromasolv) was obtained from Fluka (Sigma-Aldrich Denmark, Copenhagen, Denmark), acetonitrile (LC-MS Chromasolv) was from Riedel-de-Haën (Sigma-Aldrich Denmark, Copenhagen, Denmark) and water was Milli-Q-filtered water (Elga, Krüger Aquacare, Glostrup, Denmark). Ammonium acetate (99.999 trace metal basis), 2,5-dihydroxybenzoic acid (>99 %, matrix substance for MALDI-MS), dextran (MW ~ 6000), and polyethylene glycol 1500 were obtained from Sigma-Aldrich (Saint Louis, MO, USA).The following authentic standards were used: tetramethoxysilane, trimethoxymethylsilane, trimethoxyoctylsilane, hexamethylcyclotrisiloxane, octamethylcyclotetra- siloxane, 2-pyrrolidone, tetradecanoic acid methyl ester, pentadecanoic acid methyl ester, hexadecanoic acid methyl ester, octadecanoic acid methyl ester, tetradecanoic acid, hexadecanoic acid, and octadecanoic acid (all >99% purity; Sigma-Aldrich, Saint Louis, MO, USA). Alkyltrimethylammonium chloride with C16 (>98%) and C18 (>95%) alkyl chains, dimethyldialkylammonium chlorides or bromides with C14 (>97%), C16 (97%) and C18 (>97%) alkyl chains, and benzalkonium chloride with a C12 alkyl chain were also obtained from Sigma Aldrich.
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2

Biomarker Detection Assay with AuNPs

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Tetramethoxysilane (TMOS), polyethylene glycol (PEG) (10,000 MW), ethanol, acetic acid, phosphoric acid, ammonium hydroxide, citric acid, sodium hydrosulfide, sulfuric acid, sodium citrate, sodium phosphate dibasic, phosphate buffer saline (PBS), bovine serum albumin (BSA), 4-(2-hydroxyethyl)-1-piperazineethanesulfonic acid (HEPES), human IgG, (3-Glycidyloxypropyl)trimethoxysilane (GPTMS), Tween 20, sucrose, tris buffer, and hydroquinone were purchased from Sigma-Aldrich (St. Louis, MO). Decahydronaphthalene (decalin) and N-(γ-maleimidobutyryloxy) sulfosuccinimidyl ester (GMBS), anti-human IgG (rabbit host) were purchased from Thermo Fisher Scientific (Rockford, IL). 5 nm gold nanoparticle (AuNPs) tagged anti-human IgG and anti-rabbit IgG were purchased from Cytodiagnostics (Burlington, ON). Silver acetate was purchased from Carolina Biological Supply Co. (Burlington, NC). Microfluidic fittings were purchased from IDEX Health & Science (Oak Harbor, WA) and needle tubing was purchased from Hamilton Syringe (Reno, NV). Capillary tubing with 360 μm O.D. and 250 μm I.D. was purchased from Polymicro Technologies (Phoenix, AZ).
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3

BODIPY Dyes Immobilization on Silica

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Tetraethoxysilane (TEOS, 99%), tetramethoxysilane (TMOS, 98%), aminopropyltrimethoxysilane (APTMS, 97%), phenyltrimethoxysilane (PhTES, 98%), dodecyl dimethylamine N-oxide (DDAO 30% solution in water), were purchased from Sigma-Aldrich (Germany). Cyclohexane (99%) was obtained from ECOS-1 (Russia). Absolute ethanol (C2H5OH, 98%) was used in sol-gel synthesis. Deionized (DI) water with specific resistivity higher than 18.2 MΩcm from a three-stage Milli-Q Plus 185 purification system was used. The 4,4-difluoro-8-antryl-1,3,5,7-tetramethyl-2,6-diethyl-4-boron-3a,4a-diaza-s-indacene (BODIPY-1), 4,4-difluoro-8-(3,5 dimetyl)phenyl-1,3,5,7-tetramethyl-2-formyl-4-boron-3a,4a-diaza-s-indacene (BODIPY-2) (Figure 3) were used in the experiments for their immobilization onto silica-based materials. The synthesis of these fluorescent dyes, their characterization and photophysical properties of BODIPY-1 can be found in our previously published works [55 (link)], data on BODIPY-2 are presented in [56 (link)].
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4

Synthesis of Polyacrylonitrile-Based Composite Electrodes

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All chemicals were received from commercial sources: toluene (99.8%, Sigma-Aldrich), 2-hydroxybenzyl alcohol (99%, Sigma-Aldrich), tetramethoxysilane (≥99.0%, Sigma-Aldrich), tetrabutylammonium fluoride solution (1.0 M in THF, Sigma-Aldrich), hexane (anhydrous, 95%, Sigma-Aldrich), dichloromethane, sodium hydroxide. The chemicals were used as obtained if not otherwise stated. toluene and dichloromethane were dried with standard methods under inert atmosphere and freshly distilled before use. Deionized water was used for the syntheses and ultrapure Milli-Q® water (18.2 MΩ cm) for electrochemical measurements.
Polyacrylonitrile (PAN)-based felts (only stabilized, not yet carbonized) were received from Freudenberg Performance Materials SE & Co. KG (Weinheim, Germany) and utilized as substrate. It should be mentioned here, that the untreated carbon felt is called ‘pristine’. The composite electrodes are named according to the following general scheme – containing the synthesis conditions: material type (catalyst, carbonization time, repeat sequences of etching). The following abbreviations are used for the different catalysts: MSA for acid-catalyzed polymerization and T for thermally induced reaction.
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5

Immobilized β-Galactosidase for Lactose Hydrolysis

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Tolerase® L, a solid preparation of β-galactosidase from Aspergillus oryzae (specific activity: 130,000 ALU/g) was purchased from DSM Ltd. (Herleen, The Netherlands). Tetramethoxysilane (TMOS, 98%), polydimethylsiloxane–hydroxy terminated (PDMS, viscosity ~25 cSt), sodium acetate (≥99%), methanol gradient grade for HPLC (≥99%), acetonitrile gradient grade suitable for HPLC (≥99.9%), o-nitrophenyl-d-galactopyranoside (99%, o-NPG), o-nitrophenol (99%, o-NP), D-(+)-Glucose (≥99.5%), D-(+)-Galactose (≥98%) and D-Lactose monohydrate (≥98.0%) were purchased from Sigma-Aldrich (Poznań, Poland).
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6

Immobilized Trypsin Digestion Protocol

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Urea, acetic acid (HAc), ammonium bicarbonate (NH4HCO3), bovine pancreas TPCK-treated trypsin, dithiothreitol (DTT), poly(ethylene glycol) (PEG, MW=10 000), iodoacetamide (IAA), vinyltrimethoxysilane (VTMS), tetramethoxysilane (TMOS), 3-sulfopropyl methacrylate potassium salt, 2,2’-azobis(2-isobutyronitrile) (AIBN), were purchased from Sigma-Aldrich (St. Louis, MO). Formic acid (FA) and acetonitrile (ACN) were purchased from Fisher Scientific (Pittsburgh, PA). Methanol was purchased from Honeywell Burdick & Jackson (Wicklow, Ireland). A Nano Pure system from Thermo Scientific (Marietta, OH) Water was used to generate deionized water. Both uncoated and linear poly(acrylamide) (LPA) coated fused-silica capillaries were purchased from Polymicro Technologies (Phoenix, AZ).
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7

Optimized Electrode Modifications

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Eleven different
electrode modifications were tested, some additionally optimized during
the experiments.
Methanol (>99.8%), dichloromethane (DCM)
(pure
p.a.), Nafion, 2-nitrophenyl octyl ether (>99%), o-phenylenediamine
(>98%), HEPES (>99.5%), potassium hydroxide (>99,99%) poly-l-lysine hydrobromide, poly(vinyl chloride) (PVC), monomethoxy
PEG-nitrophenyl
carbonate, PEG diglycidyl ether (PEGDE), and bovine serum albumin
(BSA) were purchased from Sigma-Aldrich. Tetrahydrofuran (>99.8%),
hydrochloric acid (pure p.a) was from POCH, tetramethoxysilane (TMOS),
trimethoxysilylpropyl-N,N,N-trimethylammonium chloride (TMA) (>98%), were obtained
from Sigma-Aldrich. Hydroxyethyl methacrylate (HMMA) was from ABCR.
Ammonium bicarbonate (pure p.a) was from Chempur and PBS tablets 7.4
pH were from ROTH. Water was filtered and deionized with a Sartorius
Arium Comfort I system.
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8

Coumarin Dyes for Capillary HPLC

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Toluene (HPLC grade, > 99.8%), tetramethoxysilane (TMOS), 1 M aqueous acetic acid solution, and polyethylene glycol (PEG) of molecular weight (MW) = 10,000 g/mol were obtained from Sigma-Aldrich Co. (Diegem, Belgium). Octadecyldimethyl-N,N-dimethylaminosilane was purchased from ChemPur Feinchemikalien und Forschungsbedarf GmbH (Karlsrule, DE). Methanol (HPLC super-gradient grade) was obtained from Biosolve B.V. (Valkenswaard, NL). Deionized water was produced in-house with a Milli-Q water purification system Merck Millipore (Billerica, MA, USA). Coumarin 440 (C440: 7-amino-4-methyl-2H-1-benzopyran-2-one), coumarin 450 (C450: 7-(ethylamino)-4,6-dimethyl-2H,-1-benzopyran-2-one), coumarin 460 (C460: 7-(diethylamino)-4-methyl-2H-1-benzopyran-2-one), and coumarin 480 (C480: 2,3,6,7-tetrahydro-9methyl-1H,5H,11H-[1]benzopyrano-[6,7,8-ij]quinolizin-11-one) were purchased from Vadeno Optical Solutions (Apeldoorn, NL). Samples were prepared by dissolving these coumarins in the mobile phase to a concentration of 2 mM per component. PTFE filters (0.20 μm × 25 mm) were purchased from Macherey-Nagel (Düren, DE). Fused-silica capillaries with an inner diameter (i.d.) of 5 µm and 10 µm, possessing an outer diameter of 375 µm were purchased from Polymicro Technologies (Phoenix, AZ, USA).
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9

Synthesis and Characterization of Silica-Based Stationary Phases

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Toluene (HPLC grade, ≥99.8%), urea, tetramethoxysilane (TMOS), metyltrimethoxysilane (MTMS), 1 M aqueous acetic acid solution, polyethylene glycol (PEG) of molecular weight (MW) = 10,000 g/mol, thiourea, acetophenone, propiophenone, butyrophenone, valerophenone, hexanophenone, heptanophenone and octanophenone were purchased from Sigma-Aldrich (Overijse, Belgium). Trifluoroacetic acid (TFA, LC-MS Ultra grade) was purchased from Fluka (Buchs, Switzerland). Octadecyldimethyl-N,Ndimethylaminosilane (ODS-DMA) was purchased from ChemPur Feinchemikalien und Forschungsbedarf GmbH (Karlsruhe, Germany). Acetonitrile (ACN, HPLC supra-gradient grade) was purchased from Biosolve B.V. (Valkenswaard, the Netherlands). N-(Trimethylsilyl)-imidazole (TMSI) was obtained from Merck Schuchardt OHG (Hohenbrunn, Germany). Deionized water was produced in-house with a Milli-Q water purification system of Merck Millipore (Billerica, MA, USA). PTFE filters (0.20 µm × 25 mm) were purchased from Macherey-Nagel (Düren, Germany). MassPREP Peptide Mixture was purchased from Waters (Milford, MA, USA). Fused-silica capillaries of 20 µm i.d. (90 µm outer diameter (o.d.)) and 40 µm i.d. (105 µm o.d.) were purchased from Polymicro Technologies (Phoenix, AZ, USA).
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