One-step Functionalization Research Articles

Machine Learning-Inspired Molecular Design, Divergent Syntheses, and X-Ray Analyses of Dithienobenzothiazole-Based Semiconductors Controlled by S⋅⋅⋅N and S⋅⋅⋅S Interactions.

Inspired by the previous machine-learning study that the number of hydrogen-bonding acceptor (NHBA) is important index for the hole mobility of organic semiconductors, seven dithienobenzothiazole (DBT) derivatives 1 a-g (NHBA=5) were designed and synthesized by one-step functionalization from a common precursor. X-ray single-crystal structural analyses confirmed that the molecular arrangements of 1b (the diethyl and ethylthienyl derivative) and 1c (the di(n-propyl) and n-propylthienyl derivative) in the crystal are classified into brickwork structures with multidirectional intermolecular charge-transfer integrals, as a result of incorporation of multiple hydrogen-bond acceptors. The solution-processed top-gate bottom-contact devices of 1b and 1c had hole mobilities of 0.16 and 0.029 cm2 V-1s-1, respectively.

Facile one-step functionalised graphene oxide-phytic acid coating towards effective wax inhibition in waxy oil transportation

Wax deposition in pipelines is a global issue during the production and transportation of oil. Recently, superhydrophilic/underwater superoleophobic coatings have garnered much attention due to their wax inhibition potential based on water film theory. Herein, carbon steel (CS) substrates were made superhydrophilic by coating phytic acid (PA) functionalised graphene oxide (GO) materials prepared by very simple process. The superhydrophilic GO-PA coatings induced the formation of a hydration layer on the surface, thus inherently showing underwater superoleophobic properties in a water-contained waxy oil system. The optimised GO-PA/CS surface possessed a water contact angle of nearly 0° and an underwater oil contact angle of ∼ 160°. This coating demonstrated up to 89.5 % enhancement in oil passing speed during the oil transportation test. This enhancement is particularly significant for reducing wax deposition in laminar and transitional flow regimes. Moreover, in the cold-finger wax deposition tests, a wax inhibition efficiency of 95.8 % was achieved with the optimised GO-PA/CS surface in the laminar flow regime. Therefore, this research provides insights into a mechanically and chemically stable GO-based coating achieved via a facile one-step functionalisation, which has not been previously reported in the literature for applications in waxy oil transportation.

One-step functionalization and polymer grafting potential of green silica derived from rice husk ash

Green silica has been synthesized from rice husk ash which exempts the landfilling of agricultural waste and the requirement of higher temperature for digestion, unlike the conventional mode of silica synthesis making the process of precipitation and functionalization sustainable. An energy-efficient method of functionalization has been optimized for the synthesis of functionalized silica from rice husk ash via co-condensation. The potential for providing better reinforcement leads silica to be used as filler in composite manufacturing. To obtain a better silica-polymer interaction, nitroxide functionalized silica has been synthesized over three different types of silica samples using different processes. The nitroxide functionalities were introduced by thiol-ene reaction between 4-acryloyloxy(2,2,6,6-tetramethylpiperidin-1-yl)oxyl (TEMPO) and mercaptopropyl functionalized silica particles. The mercaptopropyl functionalized silica was synthesized by post-modification as well as co-condensation over commercial precipitated silica, commercial rice husk ash silica, and silica synthesized in the lab from sodium silicate obtained from rice husk ash. By comparing mercaptopropyl and nitroxide grafting density, it has been observed that the nitroxide loading highly depends on the method of functionalization and the co-condensed samples show higher nitroxide loading compared to the post-modified samples. The nitroxide functionalized samples were further subjected to polystyrene grafting, and the efficiency of surface nitroxide radicals in capturing the polymer radicals with respect to nitroxide loading was determined. The grafting density was observed to increase with the increase in conversion and the increase in the initiator-to-monomer ratio. However, the grafting density was observed to be saturated at some point despite having a higher surface area and surface nitroxide radicals. The study can be used to tune the surface nitroxide radical concentration and surface area for optimum polymer grafting for engineering applications.

Fabrication of gelatin-polyester based biocomposite scaffold via one-step functionalization of melt electrowritten polymer blends in aqueous phase

The rapid manufacturing of biocomposite scaffold made of saturated-Poly(ε-caprolactone) (PCL) and unsaturated Polyester (PE) blends with gelatin and modified gelatin (NCO-Gel) is demonstrated. Polyester blend-based scaffold are fabricated with and without applying potential in the melt electrowriting system. Notably, the applied potential induces phase separation between PCL and PE and drives the formation of PE rich spots at the interface of electrowritten fibers. The objective of the current study is to control the phase separation between saturated and unsaturated polyesters occurring in the melt electro-writing process and utilization of this phenomenon to improve efficiency of biofunctionalization at the interface of scaffold via Aza-Michael addition reaction. Electron-deficient triple bonds of PE spots on the fibers exhibit good potential for the biofunctionalization via the aza-Michael addition reaction. PE spots are found to be pronounced in which blend compositions are PCL-PE as 90:10 and 75:25 %. The biofunctionalization of scaffold is monitored through CN bond formation appeared at 400 eV via X-ray photoelectron spectroscopy (XPS) and XPS chemical mapping. The described biofunctionalization methodology suggest avoiding use of multi-step chemical modification on additive manufacturing products and thereby rapid prototyping of functional polymer blend based scaffolds with enhanced biocompatibility and preserved mechanical properties. Additionally one-step additive manufacturing method eliminates side effects of toxic solvents and long modification steps during scaffold fabrication.

Scalable nanofiltration membranes with sharpened pore distribution and enhanced negativity for mono/divalent anion separation

The petrochemical industry is an important producer of high salinity wastewater, necessitating the efficient separation of salts in zero discharge processes. This study reports the development of an industrially scalable thin film composite nanofiltration membranes that facilitate the effective separation of NaCl/Na2SO4. Employing a one-step functionalization process, the membrane pore distribution is sharpened, and the surface negativity is intensified. Branched polyethyleneimine with abundant reactive amine groups is employed as an aqueous co-monomer, leading to the generation of high density grafting active sites. Nucleophilic substitution reaction is employed to functionalize the membrane surface with negatively charged sulfonic acid groups. Simultaneously, large voids within the free volume are filled and the pore size distribution is effectively narrowed. The resultant membranes demonstrate an impressive rejection of 99.5 % for Na2SO4, a selectivity of 163.4 for NaCl/Na2SO4 and a selectivity of 488 for Cl−/SO42−, with a water flux of 45 LMH under 0.5 MPa. The corresponding 8″ × 40″ sized spiral wound membrane modules exhibit a NaCl/Na2SO4 selectivity of 100.4 and a Cl−/SO42− selectivity of 258.3, demonstrating high practical applicability. A pilot trial is planned to integrate these novel membrane products into zero discharge processes within the internal chemical enterprises of Sinopec.

Surface Modification of Nanopores in an Anodic Aluminum Oxide Membrane through Dopamine-Assisted Codeposition with a Zwitterionic Polymer.

Surface modification through dopamine-assisted codeposition with functional zwitterionic polymers can provide a simple and one-step functionalization under ambient conditions with robust and stable dopamine-surface interactions to improve the hydrophilicity of nanoporous membranes, thereby expanding their applicability to nanofiltration, ion transport, and blood purification. However, a significant knowledge gap remains in our comprehension of the mechanisms underlying the formation and deposition of dopamine/polymer aggregated coatings within nanoscale confinement. This study explores a feasible method for membrane modification through the codeposition of dopamine hydrochloride (DA) and poly(sulfobetaine methacrylate) (PSBMA) on nanopores of anodic aluminum oxide (AAO) membranes. Our findings demonstrate that the aggregated coatings of DA and PSBMA nanocomposites can effectively deposit on the surfaces within cylindrical AAO nanopores, significantly enhancing the hydrophilicity of the nanoporous membranes. The morphology and homogeneity of the nanocomposite coatings within the nanopores are further investigated by varying PSBMA molecular weights and AAO pore sizes, revealing that higher molecular weights result in more uniform deposition. This work sheds light on understanding the codeposition of DA and zwitterionic polymers in nanoscale environments, highlighting a straightforward and stable surface modification process of nanoporous membranes involving functional polymers.

One-step functionalization of paper and simplified antibody immobilization for on-the-spot immunocapture from dried serum in liquid chromatography-tandem mass spectrometry based targeted protein determination.

This work aimed to simplify and improve the process of binding monoclonal antibodies (mAbs) covalently to filter paper for use in dried blood spot sampling, enabling instant capture of protein biomarkers for targeted protein determination. Incorporating the necessary immunocapture sample preparation step in the initial sampling stage saves time and reduces the workload. The biomarker human chorionic gonadotropin (hCG) was used as the model analyte. The antibody-based paper samplers were prepared by functionalizing paper discs (6mm) through a simple reaction using divinyl sulfone (DVS). After DVS activation, the paper discs were incubated with E27 hCG mAbs, followed by 0.05% tween/phosphate buffer saline to block the surface. After sample application and drying, the discs only needed to be washed before tryptic digestion and finally analysed on a nanoliquid chromatography-tandem mass spectrometry system. The finished DVS-mAbs samplers could selectively capture hCG (100 ng/mL) from human serum, with a recovery of 50%. Sample clean-up reduced the number of identified proteins from 132 to 82 before and after wash, respectively, with a 70% reduction in serum albumin signal while still retaining hCG on the sampler during the washing protocol. An evaluation of the samplers revealed excellent linearity (R2 = 0.9995) for hCG in serum with relative standard deviations below 15%. This work has presented the first ever reported paper samplers immobilized with antibodies utilizing DVS chemistry, showing promise in the future of paper-based sampling.

Plasma polymerized nanoparticles are a safe platform for direct delivery of growth factor therapy to the injured heart.

Introduction: Heart failure due to myocardial infarction is a progressive and debilitating condition, affecting millions worldwide. Novel treatment strategies are desperately needed to minimise cardiomyocyte damage after myocardial infarction and to promote repair and regeneration of the injured heart muscle. Plasma polymerized nanoparticles (PPN) are a new class of nanocarriers which allow for a facile, one-step functionalization with molecular cargo. Methods: Here, we conjugated platelet-derived growth factor AB (PDGF-AB) to PPN, engineering a stable nano-formulation, as demonstrated by optimal hydrodynamic parameters, including hydrodynamic size distribution, polydisperse index (PDI) and zeta potential, and further demonstrated safety and bioactivity in vitro and in vivo. We delivered PPN-PDGF-AB to human cardiac cells and directly to the injured rodent heart. Results: We found no evidence of cytotoxicity after delivery of PPN or PPN-PDGFAB to cardiomyocytes in vitro, as determined through viability and mitochondrial membrane potential assays. We then measured contractile amplitude of human stem cell derived cardiomyocytes and found no detrimental effect of PPN on cardiomyocyte contractility. We also confirmed that PDGF-AB remains functional when bound to PPN, with PDGF receptor alpha positive human coronary artery vascular smooth muscle cells and cardiac fibroblasts demonstrating migratory and phenotypic responses to PPN-PDGF-AB in the same manner as to unbound PDGF-AB. In our rodent model of PPN-PDGF-AB treatment after myocardial infarction, we found a modest improvement in cardiac function in PPN-PDGF-AB treated hearts compared to those treated with PPN, although this was not accompanied by changes in infarct scar size, scar composition, or border zone vessel density. Discussion: These results demonstrate safety and feasibility of the PPN platform for delivery of therapeutics directly to the myocardium. Future work will optimize PPN-PDGF-AB formulations for systemic delivery, including effective dosage and timing to enhance efficacy and bioavailability, and ultimately improve the therapeutic benefits of PDGF-AB in the treatment of heart failure cause by myocardial infarction.

Functionalization of graphene nanostructures with inorganic nanoparticles and their use for the removal of pharmaceutical pollutants in water

Emerging pollutants such as pharmaceuticals are of special concern because despite their low environmental concentration, their biological activity can be intense, and they should be prevented to reach uncontrolledly to the environment. A graphene-based hybrid material decorated with Fe3O4 and TiO2 nanoparticles (NPs) has been prepared to effectively remove emerging pollutants as nonsteroidal anti-inflammatory drugs (NSAIDs) Ibuprofen and Diclofenac present in water at low environmental concentrations by a one-step functionalization process following a novel gentle and scalable surfactant depletion approach. Following this methodology, nanoparticles are progressively deprived of their original surfactant in the presence of graphene, leading to the formation of hybrid nanostructures composed of two different types of nanoparticles well dispersed over the graphene nanosheets. Ibuprofen and Diclofenac adsorption kinetics on the composites was investigated via UV-Vis spectroscopy. The as prepared hybrid material possesses high adsorption capacity, superparamagnetic properties, photocatalytic behavior, and good water dispersibility. Thanks to incorporating TiO2 nanoparticles as in situ catalysts, the adsorption performance of composites is restored after use, which could be a promising recycling pathway for the adsorbents in wastewater treatments.

One-Step Functionalization of Chitosan Using Aromatic Groups via Hydrothermal Assisted Grafting for Removal of Reactive Orange 16 Dye: Optimization and Adsorption Mechanism

One-Step Functionalization of Chitosan Using Aromatic Groups via Hydrothermal Assisted Grafting for Removal of Reactive Orange 16 Dye: Optimization and Adsorption Mechanism

One-Step Photochemical Immobilization of Aptamer on Graphene for Label-Free Detection of NT-proBNP

A novel photochemical technological route for one-step functionalization of a graphene surface with an azide-modified DNA aptamer for biomarkers is developed. The methodology is demonstrated for the functionalization of a DNA aptamer for an N-terminal B-type natriuretic peptide (NT-proBNP) heart failure biomarker on the surface of a graphene channel within a system based on a liquid-gated graphene field effect transistor (GFET). The limit of detection (LOD) of the aptamer-functionalized sensor is 0.01 pg/mL with short response time (75 s) for clinically relevant concentrations of the cardiac biomarker, which could be of relevance for point-of-care (POC) applications. The novel methodology could be applicable for the development of different graphene-based biosensors for fast, stable, real-time, and highly sensitive detection of disease markers.

Recent advances in electrochemical C-H phosphorylation.

The activation of C-H bond, and its direct one-step functionalization, is one of the key synthetic methodologies that provides direct access to a variety of practically significant compounds. Particular attention is focused on modifications obtained at the final stages of the synthesis of complicated molecules, which requires high tolerance to the presence of existing functional groups. Phosphorus is an indispensable element of life, and phosphorus chemistry is now experiencing a renaissance due to new emerging applications in medicinal chemistry, materials chemistry (polymers, flame retardants, organic electronics, and photonics), agricultural chemistry (herbicides, insecticides), catalysis (ligands) and other important areas of science and technology. In this regard, the search for new, more selective, low-waste synthetic routes become relevant. In this context, electrosynthesis has proven to be an eco-efficient and convenient approach in many respects, where the reagents are replaced by electrodes, where the reactants are replaced by electrodes, and the applied potential the applied potential determines their "oxidizing or reducing ability". An electrochemical approach to such processes is being developed rapidly and demonstrates some advantages over traditional classical methods of C-H phosphorylation. The main reasons for success are the exclusion of excess reagents from the reaction system: such as oxidants, reducing agents, and sometimes metal and/or other improvers, which challenge isolation, increase the wastes and reduce the yield due to frequent incompatibility with these functional groups. Ideal conditions include electron as a reactant (regulated by applied potential) and the by-products as hydrogen or hydrocarbon. The review summarizes and analyzes the achievements of electrochemical methods for the preparation of various phosphorus derivatives with carbon-phosphorus bonds, and collects data on the redox properties of the most commonly used phosphorus precursors. Electrochemically induced reactions both with and without catalyst metals, where competitive oxidation of precursors leads to either the activation of C-H bond or to the generation of phosphorus-centered radicals (radical cations) or metal high oxidation states will be examined. The review focuses on publications from the past 5years.

Tetrazine Linkers as Plug-and-Play Tags for General Metal-Organic Framework Functionalization and C60 Conjugation.

The value of covalent post-synthetic modification in expanding the chemistry and pore versatility of reticular solids is well documented. Here we use mesoporous crystals of the metal-organic framework (MOF) UiO-68-TZDC to demonstrate the value of tetrazine connectors for all-purpose inverse electron-demand Diels-Alder ligation chemistry. Our results suggest a positive effect of tetrazine reticulation over its reactivity for quantitative one-step functionalization with a broad scope of alkene or alkyne dienophiles into pyridazine and dihydropyridazine frameworks. This permits generating multiple pore environments with diverse chemical functionalities and the expected accessible porosities, that is also extended to the synthesis of crystalline fulleretic materials by covalent conjugation of fullerene molecules.

One-step functionalization of chitosan using EDTA: Kinetics and isotherms modeling for multiple heavy metals adsorption and their mechanism

Potentially toxic heavy metals commonly exist in industrial wastewaters, presenting a critical global health threat to human health and environment, therefore, making their treatment is more challenging. In this study, an attractive polymer composite (CS-EDTA) adsorbent was developed by immobilization of ethylenediaminetetraacetic acid (EDTA) onto chitosan (CS) through cross-linking for the adsorptive removal of multiple heavy metals from industrial wastewater. The adsorption of heavy metals, i.e., Pb(II), Cd(II), and Cu(II) onto the developed composite was investigated by performing batch experiments with varying contact time and metal ion concentration in the mono-component system. The adsorption data fitted to the monolayer Langmuir isotherm; the maximum adsorption capacities were calculated as 370.37 ± 14.26, 243.90 ± 12.47, and 227.27 ± 15.33 mg g−1 for Pb(II), Cd(II), and Cu(II), respectively. The kinetics of the adsorption followed the pseudo-second order (PSO) models, and obtained the rate constant values of 0.009 ± 0.0004, 0.001 ± 0.0001, and 0.0007 ± 0.0001 g mg−1 min−1 for Pb(II), Cd(II), and Cu(II), respectively. The adsorption of the heavy metals was attributed to the electrostatic interactions between the metals and different functional groups (OH, NH2, and COOH) of the adsorbent and complexation with EDTA, which was confirmed by the elemental mapping, EDS and FT-IR techniques. The reusability of the polymer composite was also tested and obtained >92 % efficiency even after five consecutive adsorption-desorption cycles which clearly demonstrating the high stability of the adsorbent. Lastly, the developed polymer composite was applied for real industrial wastewater. Excellent removal efficiencies (>84 %) were obtained, which makes it a potential candidate for the removal of heavy metals from real industrial wastewater.

Ultraviolet-cured p-phenylenediamine functionalized polypropylene film as a non-migratory antioxidant

Ultraviolet (UV) induced modification is a simple technique to render the interface of inert materials into a functional property. In this study, a curable copolymer coating was synthesized using glycidyl methacrylate and 4–benzoylphenyl methacrylate via atom transfer radical copolymerization. Butyl acrylate was also introduced to the copolymer, which in turn improved the ductility and facilitated the surface modification using copolymer with bulky groups. The chemical structure of this copolymer was identified using 1H NMR and FTIR. Accordingly, the monomers in the feed were also observed in the copolymer backbone. Ultraviolet (UV) cure potency of the copolymer was monitored using UV–visible spectroscopy in which 90 s UV–irradiation (365 nm) enabled one-step functionalization of polypropylene (PP) surface. Additionally, the existence of the pendant oxirane ring of copolymer on the PP surface after coating assisted in the immobilization of p–phenylenediamine, which realized antioxidant film. The oxidation and reduction abilities of the antioxidant film were assessed using cyclic voltammetry, supporting the free radical scavenging ability of the film. This antioxidant film remarkably (p < 0.05) delayed the lag time of vitamin C degradation and olive oil oxidation. Moreover, the antioxidant film did not leave any migrant behind after incubation with simulant solvents, showing a non-migratory feature. Therefore, this non-migratory antioxidant film can be practically applied in packaging, cosmetic, and biomedical fields.

Dopamine-triggered one-step functionalization of hollow silica nanospheres for simultaneous lubrication and drug release

Osteoarthritis (OA) has been regarded as a lubrication deficiency related joint disease. Combination of both joint lubrication and drug intervention may provide a promising nonsurgical strategy for treatment of OA. Developing novel and simple approaches to fabricate superlubricating nanoparticles with drug release property is highly required. Herein, dopamine triggered one-step polymerization method was employed to fabricate polydopamine/poly(3-sulfopropyl methacrylate potassium salt) (PDA—PSPMA) conjugate coating on hollow silica (h-SiO2) nanosphere surfaces to engineer functional nanoparticles (h-SiO2/PDA—PSPMA). The as-prepared h-SiO2/PDA—PSPMA exhibits excellent aqueous lubrication performance on biomaterial substrates as well as natural bovine articular cartilage based on hydration effect of negatively charged PDA—PSPMA coating and “rolling” effect of h-SiO2 nanospheres. In vitro drug loading-release experiments demonstrate that PDA—PSPMA coating functionalized h-SiO2 nanospheres show high drug-loading and sustained-release capability of an anti-inflammatory drug, diclofenac sodium (DS). Such h-SiO2/PDA—PSPMA nanospheres can be potentially used as a synergistic therapy agent for OA treatment combining by simultaneous joint lubrication and drug release.

Functional metal-based 3D-printed electronics engineering: Tunability and bio-recognition

3D-printing technology has brought light to the large-scale and sustainable production of a wide range of low-cost electronic devices with custom forms on-demand. Despite the current availability of mainstream carbon-based nanocomposite filaments, 3D-printing of noble metals is nowadays a challenge. Herein, a one-step functionalization approach has been devised for the straightforward and cost-effective manufacturing of functional metal-based 3D-printed electronics by galvanically replacing Cu-based 3D-printed (3D-Cu) electrodes with nobler metal counterparts, viz. Ag and Au. As a first demonstration of applicability, two appealing bio-electroanalytical approaches, such as the chiral discrimination of amino acids and the supramolecular determination of uranium have been considered —by taking advantage of the capability of noble metals to physically/chemically accommodate several molecular components—, reaching enhanced performances when compared with the pristine 3D-Cu counterpart. Consequently, this alchemy-inspired approach, which combines (i) 3D-Cu electrodes as sacrificial platforms with (ii) noble metals via a galvanic exchange reaction, provides a robust pathway to harbor molecular components in order to exploit metal-based 3D-printed electronics in real tasks.

Portable visual assay of Bacillus anthracis biomarker based on ligand-functionalized dual-emission lanthanide metal-organic frameworks and smartphone-integrated mini-device

A single-functionalized ligand single-Ln3+ based dual-emission Ln-MOF fluorescent sensor was established for portable and visual dipicolinic acid (DPA, Bacillus anthracis biomarker) detection. First, a theory calculation-based prediction model was developed for designing single-functionalized ligand single-Ln3+ dual-emission Ln-MOFs. The model consisted of three calculation modules: intramolecular hydrogen bonds, excited state energy levels, and coordination stability with Ln3+ of ligands. Tb3+ and Eu3+ were selected as metal luminescence centers, PTA-X (PTA: p-phthalic acid, X = NH2, CH3, H, OH) with different functional groups as one-step functionalization ligands, and the luminescent feature of four Tb-MOFs and four Eu-MOFs was predicted with the model. Coupled with prediction results and experimental verification results, Tb-PTA-OH was rapidly determined to be the sole dual-emission Ln-MOF. Then, Tb-PTA-OH was applied to DPA detection by ratiometric fluorescence, and an ultra-low limit of detection (13.4 nM) was obtained, which is much lower than the lowest anthrax infectious dose (60 μM). A portable visual assay method based on paper-microchip and smartphone integrated mini-device was further established (limit of qualification 0.48 μM). A new sensing mechanism and a "triple gates" selectivity mechanism to DPA were proposed. This work reveals guidelines for material design and mini-device customization in detecting hazardous substances.

Self-Assembled Monolayers of Arylazopyrazoles on Glass and Silicon Oxide: Photoisomerization and Photoresponsive Wettability.

Surface coatings that respond to external influences and change their physical properties upon application of external stimuli are of great interest, with light being a particularly desirable choice. Photoswitches such as azobenzenes have been employed in a range of photoresponsive coatings. One striking change in physical property of many photoresponsive coatings is their responsive wettability upon illumination. In this work, we present photoswitchable self-assembled monolayers based on arylazopyrazoles (AAPs). In solution, AAPs offer significant improvements in terms of the photostationary state, thermal stability, and fatigue resistance. The AAP photoswitch is coupled to triethoxysilanes for an easy, one-step functionalization of glass and silicon oxide surfaces. We show the synthesis of AAP-based silanes and the successful surface functionalization, and we confirm the excellent photoswitchability of the AAPs in a self-assembled monolayer upon alternating irradiation with UV (365 nm) and green (520 nm) light. The self-assembled monolayers are investigated by UV/vis spectroscopy, X-ray photoelectron spectroscopy (XPS), time-of-flight secondary ion mass spectrometry (ToF-SIMS), and contact angle goniometry. We furthermore investigate the effect of substitution of the AAPs on the photoresponsive wetting behavior and compare this with density functional theory (DFT) calculations of the dipole moments of the AAPs.

Precise size-control and functionalization of gold nanoparticles synthesized by plasma-liquid interactions: using carboxylic, amino, and thiol ligands.

Using gold nanoparticles (GNPs) in high-standard applications requires GNPs to be fabricated with high-quality size and surface properties. Plasma-liquid interactions (PLIs) have the unique ability to synthesize GNPs without using any reducing agents, and the GNP surface is free of stabilizing agents. It is an extreme advantage that ensures success for the subsequent functionalization processes for GNPs. However, fabricating GNPs via PLIs at the desired size has still been a challenge. Here, we present a simple approach to achieving the precise size-control of GNPs synthesized by PLIs. By adding suitable ligands to the precursor solution, the ligands wrap GNPs which interrupts and slows down the rapid growth of GNPs under PLIs. This way, the size of the GNPs can be precisely controlled by adjusting the ligand concentration. Our results showed that the size of the GNPs in the range of 10-60 nm can be fitted to reciprocal functions of the ligand concentration. The potency of the size-control depends on the type of ligands in the order of thiol > amine > carboxylate. The size-control has been well investigated with four common ligands: l-cysteine, glucosamine, salicylic acid, and terephthalic acid. XPS, FTIR, and zeta potential techniques confirmed the presence of these ligands on GNPs. The results indicated that functionalized ligands could be utilized to control the size and functionalize the GNP surface. Hence our approach could simultaneously achieve two goals: precise size-control and functionalization of GNPs without the ligand-exchange step.