Thiol Function Research Articles

Wormhole Mesoporous Silica Framework with Enhanced Thiol Loading for Improved Hg2+ Sequestration.

Thiol-functionalized mesoporous silica and materials potentially dedicated to diverse applications of composite materials, metal colloids, and metal catalysts, etc. Here, we developed a new synthesis route for 3-methacryloxypropyl trimethoxy silane (MPTMS) functionalized mesoporous silica (KIT-6), achieving a 71.5 % enhancement in thiol functionalization on KIT-6 surfaces. Characterization using XRD, TEM, BET, FTIR, Raman, 29Si NMR, XPS, and ICP-OES revealed structural and morphological features. XRD, TEM, and BET confirmed the three-dimensional structural stabilization of mesoporous silica with ~4 nm pore diameter and a surface area of 1451 m2 g-1. FTIR, Raman, and 29Si NMR studies established the mechanism of thiol functionalization, the formation of a new wormhole chain structural framework (WCSF), and stabilization through hydrogen bonding within the mesopores. The 29Si NMR spectra showed characteristic peaks (T3, T2, Q4, Q3) indicating self-condensed functionalized thiols with siloxane networks. XPS analysis validated enhanced thiol functionalization, indicating a structurally homogeneous WCSF suitable for mercury adsorption. ICP-OES measured a mercury adsorption capacity of 3199.6 mg g-1 for KIT-6, with an Hg2+/S ratio of 1.8, corroborated by molecular structure and mechanism analysis. This innovative thiol functionalization approach enhances the efficacy of applications such as extracting Hg2+ from contaminated sources.

Photocurable Thiol-Ene/Nanocellulose Elastomeric Composites for Bioinspired and Fluorine-Free Superhydrophobic Surfaces.

Artificially prepared superhydrophobic surfaces toward a self-cleaning "lotus effect" and anticontamination performance have become critically important in the past few years. However, most approaches to create the required topology with a hierarchical roughness comprise several manufacturing steps of varying practicality. Moreover, the desired low surface energy is in most cases achieved with fluorinated moieties that are currently criticized due to biological and environmental hazards. In this work, rapidly photocuring but weak thiol-ene resins were reinforced with cellulose nanofibrils (CNFs) to replicate lotus leaves via one-step UV nanoimprint lithography. The CNFs were surface-modified using countercation exchange of carboxyl groups and grafting of thiol and methacrylate functionalities. The formulation methodology resulted in free-flowing, shear-thinning composite resins without surfactants or dispersants. The rheological and photo-cross-linking behavior of the resins, the thermal stability, the mechanical performance, and the hydrophobicity of the cured composites were characterized. Notably, the surface modifications increased the as received fibril diameter (1.9 ± 0.6 nm) by 1.6-2.3 nm and raised the fibril-resin compatibility. The resins underwent rapid polymerization and the high thermal stability of thiol-enes was retained. The methacrylated nanofibrils (10 vol %) significantly strengthened the rubbery network, outperforming the neat thiol-ene polymer in terms of hardness (3.4×), reduced modulus (5.8×), and wear resistance (>100×). Moreover, the surface of lotus-texturized composites was superhydrophobic with a water contact angle of 155°, higher than that of the neat polymer (147°), and was self-cleaning. These CNF composite resins are compatible with fast-cure processes such as 3D printing and roll-to-roll processing, are exempt of fluorine or any other hydrophobization treatment, and are extremely wear-resistant.

Investigating the Significances of Thiol Functionalities in SARS-CoV-2 Using Carbon Dots for Viral Inhibition.

While the World Health Organization has declared the end of the SARS-CoV-2 public health emergency, studies related to corona viruses are still under course. As of 2024, the severity of COVID-19 has diminished with current treatments and vaccinations. However, individuals can still face severe complications, highlighting the importance of ongoing research into innovative treatments for current and future coronavirus-related diseases. This study approaches the mechanism of viral entrance into the host cells and the current evidence on the use of sulfhydryl groups for the COVID-19 treatment. Certain thiol drugs, a key contributor to inflammatory processes, exhibit both viral inhibition properties and the potential to regulate cellular oxidative stress by scavenging free radicals. Herein, we developed biocompatible thiol-functionalized carbon dots (CDs) and investigated the correlation between the number of thiols and pseudo-SARS-CoV-2 inhibition, reactive oxygen species (ROS) scavenging, and anti-inflammatory response. The free-radical scavenging experiment and the ROS cellular assay indicate that thiolated CDs serve as effective reducing agents and potential regulators of cellular oxidative stress. The CDs also demonstrated good cell viability alongside significant antiviral capabilities, with inhibition levels up to 60.4%. Furthermore, the flow cytometry results suggest that in an inflammatory environment, the presence of thiolated CDs promotes an anti-inflammatory response. Overall, the results demonstrate a strong correlation between the number of thiols and the increased efficacy observed across experiments, presenting thiolated CDs as promising candidates to prevent and treat COVID-19 infection.

Gold Nanoparticle-Embedded Thiol-Functionalized Ti3C2Tx MXene for Sensitive Electrochemical Sensing of Ciprofloxacin.

The unregulated use of ciprofloxacin (CIPF) has led to increased resistance in patients and has threatened human health with issues such as digestive disorders, kidney disorders, and liver complications. In order to overcome these concerns, this work introduces a portable electrochemical sensor based on a disposable integrated screen-printed carbon electrode (SPCE) coated with gold nanoparticle-embedded thiol-functionalized Ti3C2Tx MXene (AuNPs-S-Ti3C2Tx MXene) for simple, rapid, precise, and sensitive quantification of CIPF in milk and water samples. The high surface area and electrical conductivity of AuNPs are maximized thanks to the strong interaction between AuNPs and SH-Ti3C2Tx MXene, which can prevent the aggregation of AuNPs and endow larger electroactive areas. Ti3C2Tx MXene was synthesized from Ti3AlC2 MAX phases, and its thiol functionalization was achieved using 3-mercaptopropyl trimethoxysilane. The prepared AuNPs-S-Ti3C2Tx MXene nanocomposite was characterized using FESEM, EDS, XRD, XPS, FTIR, and UV-visible spectroscopy. The electrochemical behavior of the nanocomposite was examined using CV, EIS, DPV, and LSV. The AuNPs-S-Ti3C2Tx MXene/SPCE showed higher electrochemical performances towards CIPF oxidation than a conventional AuNPs-Ti3C2Tx MXene/SPCE. Under the optimized DPV and LSV conditions, the developed nonenzymatic CIPF sensor displayed a wide range of detection concentrations from 0.50 to 143 μM (DPV) and from 0.99 to 206 μM (LSV) with low detection limits of 0.124 μM (DPV) and 0.171 μM (LSV), and high sensitivities of 0.0863 μA/μM (DPV) and 0.2182 μA/μM (LSV).

Synthesis of New polymers of Triazole Derivatives

Thiatriazole is an important monomer, whereby it have two types of functional groups, amine and thiol. Within the frame of this work the triazole monomer have been prepared from its oxadiazole. Two type of polymers were prepared from this monomer via condensation with terephthaldehyde and succinyl chloride, whereby the binding units of the resulted polymers are differs, azomethine and amide respectively. Infrared spectroscopy and elemental analysis were used to identified the polymers. DTA, TGA and DSC analysis indicate the thermal history of the polymers. It was shown that polymer (1) was more flexibility than polymer (2) due to the lower Tg value due to the presence of azomethene group. The Tg are (138oC) and (190oC) respectively. Also the DTA, TGA indicates that polymer (2) have high thermal stability than polymer 1 due the presence of the amide group.

Sec-isoamyl Mercaptan (SIT), a Multi-faceted Disulfide Based Protecting Group for Cysteine Thiol

IntroductionThe successful synthesis of a peptide requires the synchronization of several processes, including the efficient execution of protecting group chemistry. For cysteine (Cys)-peptides, this is more crucial because the trifunctional Cys has a free thiol in its side chain. During synthesis, this free thiol function remains protected with suitable protecting groups and can be removed after synthesis using appropriate methods. Sec-isoamyl mercaptan (SIT) is a versatile disulfide-based protecting group for Cys side chain thiol. The removal of SIT from Cys thiol can be achieved using a mild reducing agent (e. g. DTT). This later promotes efficient disulfide bond formation by oxidation. SIT can also direct/activate the Cys thiol for the chemoselective formation of disulfide bonds by thiol-disulfide interchange.MethodsPeptides were synthesized using solid-phase peptide synthesis techniques. The removal of the SIT group was carried out either in the solid phase or in the solution.ResultsIn the present study, we have shown that SIT can be efficiently removed both in solution and on-resin to facilitate disulfide-bridged peptide synthesis. This was exemplified by two syntheses of an atosiban derivative, where the SIT was removed in solution or in solid-phase. Furthermore, a SIT-based facile one-pot synthesis pathway was devised for disulfide-rich peptides. The strategy was faster and greener as it did not involve using an oxidizer. Conotoxin (two S–S) and linaclotide amide (three S–S) were successfully synthesized by adopting the SIT-based strategy. Finally, a racemization study was carried out for SIT, Trt and StBu-protected Cys-peptides. In all cases, SIT-protected peptides showed lesser racemization than StBu-protected peptides. In some instances (synthesis using DMF), SIT-protected peptides showed less racemization compared to the Trt congeners.ConclusionOverall, the multifaceted use of SIT-protection during the synthesis of disulfide-rich peptides has illustrated its versatility as a Cys thiol protecting group.

Simultaneous Color- and Dose-Controlled Thiol-Ene Resins for Multimodulus 3D Printing with Programmable Interfacial Gradients.

Drawing inspiration from nature's own intricate designs, synthetic multimaterial structures have the potential to offer properties and functionality that exceed those of the individual components. However, several contemporary hurdles, from a lack of efficient chemistries to processing constraints, preclude the rapid and precise manufacturing of such materials. Herein, the development of a photocurable resin comprising color-selective initiators is reported, triggering disparate polymerization mechanisms between acrylate and thiol functionality. Exposure of the resin to UV light (365nm) leads to the formation of a rigid, highly crosslinked network via a radical chain-growth mechanism, while violet light (405nm) forms a soft, lightly crosslinked network via an anionic step-growth mechanism. The efficient photocurable resin is employed in multicolor digital light processing 3D printing to provide structures with moduli spanning over two orders of magnitude. Furthermore, local intensity (i.e., grayscale) control enables the formation of programmable stiffness gradients with ≈150× change in modulus occurring across sharp (≈200µm) and shallow (≈9mm) interfaces, mimetic of the human knee entheses and squid beaks, respectively. This study provides composition-processing-property relationships to inform advanced manufacturing of next-generation multimaterial objects having a myriad of applications from healthcare to education.

A strategy for covalent anchoring of self-assembling β3 oligoamide nanorods to gold surfaces

Abstract Oligopeptides stand out for their remarkable structural variability, ease of synthesis, and amenability to functionalization, making them exceedingly appealing for crafting functional nanostructured materials. The low metabolic stability of natural peptides can be overcome by replacing α-amino acids with β3- amino acids, to yield artificial peptides best described as substituted β3-oligoamides. Controlling the morphology of such structures by varying the amino acid residues and altering the oligoamide termini makes it possible to adapt the core design to a range of hierarchical structures and function. Conductivity is a desired property in such nanomaterials; preferably conductive materials should be chemically anchored to a highly conductive metal, such as gold surface to connect to macroscopic electronics. It is preferable to use thiol functionality, however β3 cysteine is not synthetically achieveable. In this study β3 [SLIA] oligoamide has been synthesized and functionalized at the N terminus with a thiol moiety. After successful synthesis and purification, the thiolated oligoamide was physically characterized to confirm binding to gold, self-assembly and hetero assembly on these anchor points. It was demonstrated with a quartz crystal microbalance (QCM) that self-assembling monolayers can be formed on a gold surface and the formation of a S-Au bond was confirmed with X-ray photoelectron spectroscopy. Growth of Ac-β3[WKLWEL] fibres on these anchor points was confirmed by using atomic force microscopy and QCM. Hence, a viable metal anchor has been established that lays the foundations for the future development of molecular electronics based on β3 oligoamides.

Synthesis of Cobalt(III) Complexes Derived from Pyridoxal: Structural Cleavage Evaluations and In Silico Calculations for Biological Targets

This study sought to investigate the synthesis of eight complexes constituted by a cobalt(III) (CoIII) metallic center coordinated to two units of iminic ligands LnC (n = 1–4, L1C–L4C), which are derivatives of pyridoxal hydrochloride and anilines with thioether function containing one to four carbons. Depending on the source of the cobalt ion and the addition (or not) of a non-coordinating counterion, complexes with distinct structures may form, being categorized into two series: [CoIII(LnC)(L0C)] (n = 1–4, C1’–C4’) with a LnC ligand and a ligand that has a thiolate function which cleaves the C-S(thioether) bond (L0C) and [CoIII(LnC)2]PF6 (n = 1–4, C1–C4) with two similar units of the same LnC ligand. The occurrence (or not) of cleavage in the eight complexes was observed by elucidating the solid-state structures by single crystal X-ray diffraction. This exciting method allows the synthesis of CoIII complexes without cleaving the C-S bonds from the ligands, thereby not requiring an inert atmosphere in the reaction systems. The synthesized complexes were evaluated by in silico calculations on viable biological targets such as deoxyribonucleic acid, superoxide dismutase enzyme, human serum albumin, and the structural spike glycoprotein of severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) with the receptor binding domain (RBD) in both up and down conformations without and in complex with the cellular receptor angiotensin-converting enzyme 2 (ACE2). Overall, in silico results suggested that all the inorganic complexes under study are potential anticancer/antiviral agents; however, C4 and C4’ are the best candidates for future in vitro assays.

Universal Click-Chemistry Approach for the DNA Functionalization of Nanoparticles.

Nanotechnology has revolutionized the fabrication of hybrid species with tailored functionalities. A milestone in this field is the deoxyribonucleic acid (DNA) conjugation of nanoparticles, introduced almost 30 years ago, which typically exploits the affinity between thiol groups and metallic surfaces. Over the last decades, developments in colloidal research have enabled the synthesis of an assortment of nonmetallic structures, such as high-index dielectric nanoparticles, with unique properties not previously accessible with traditional metallic nanoparticles. However, to stabilize, integrate, and provide further functionality to nonmetallic nanoparticles, reliable techniques for their functionalization with DNA will be crucial. Here, we combine well-established dibenzylcyclooctyne-azide click-chemistry with a simple freeze-thaw method to achieve the functionalization of silica and silicon nanoparticles, which form exceptionally stable colloids with a high DNA surface density of ∼0.2 molecules/nm2. Furthermore, we demonstrate that these functionalized colloids can be self-assembled into high-index dielectric dimers with a yield of over 50% via the use of DNA origami. Finally, we extend this method to functionalize other important nanomaterials, including oxides, polymers, core-shell, and metal nanostructures. Our results indicate that the method presented herein serves as a crucial complement to conventional thiol functionalization chemistry and thus greatly expands the toolbox of DNA-functionalized nanoparticles currently available.

Preparation and study of novel UV‐curable alkyd‐siloxane coating materials

AbstractA material capable of curing due to UV irradiation based on an alkyd oligomer and oligoorganosilsesquioxanes (OOSs) with functional thiol groups was obtained. Using microinterferometry, it was shown that the alkyd oligomer and OOS are completely compatible (mutually soluble). The resulting alkyd‐siloxane composition was cured under the action of UV irradiation due to reaction between double bonds of alkyd oligomer and thiol‐groups of silsesquioxane oligomer. The curing reaction takes 5 min with formation of coating, containing 99% of gel fraction, which is in 30 times faster in comparison with the classical method of alkyd curing in the presence of siccatives. The hydrophobicity of alkyd‐siloxane coatings also increases and varies depending on the content of OOS. The introduction of 50% OOS into the alkyd oligomer makes it possible to increase the water contact angle by 10° relative to the coating based on pure alkyd. A similar dependence is observed when studying the thermal stability of coatings. Thus, even with the introduction of 10% OOS into alkyd oligomer, the temperature at which a loss of 50% of mass occurs increases by 24°C relative to coatings based on a pure alkyd oligomer.

Thiol functionalized porous carbon nanospheres: Synthesis, characterization, experimental and DFT studies

Thiol-modified nanoporous structured frameworks prove to be efficient trapping agents for eliminating mercury (Hg(II)) ions from water. In this work, we synthesized porous carbon nanospheres and chemically functionalized them with l-cysteine molecules following a Fischer esterification reaction and investigate them for selective Hg(II) separation. The material was characterized for functional group analysis, surface morphology and water contact angle measurement by using several spectroscopic and optical techniques likely FT-IR, XPS, SEM, TEM and goniometer analyzer. The column packed material shows selective extraction of trace Hg(II) ions at wide pH range. The selectivity of Hg(II) is primarily attributed to Lewis soft–soft acid–base chelation, wherein Hg(II) forms complexes with the thiol functionalities of the adsorbent. Density functional theory (DFT) calculations suggest that the fast energetically favorable R–SH–Hg–OR complex formed over R–S–Hg–NH–R bidentate complexes, thereby promoting selective extraction of Hg(II). The preconcentration limit for Hg(II) achieved at pH 6 was found to be 0.37 ppb. The instrumental detection limit (3 s/m) obtained after preconcentration of 11 blank runs is found to be 0.04 ppb with the relative standard deviation of 3.68 %. The accuracy of the proposed column method was validated by analyzing several real samples with enrichment factor of 100 and after spiking with varying amount of analyte. The method shows a good recovery of 97–100 % of spiked amount with RSD <5 %.

Molecular-scale topographic design of multicomponent self-assembled monolayers for environmentally adaptable, lyophobic coating

HypothesisThe water wettability of a hydrophilic surface is dictated by the hydration of the region less than 1 nm below the surface plane, yet it hitherto remains a topic rarely touched upon how a subtle change in surface structural features at molecular level affects the surface wettability and its response to the environmental nature. ExperimentsBinary self-assembled monolayers (SAMs) consisting of plain and functional thiols were constructed, where the surface fraction of the functional thiols was varied from 0.1 to 0.3, 0.6, 0.8 and 1.0 and the difference in CH2 unit number between two types of thiols – defined as height difference between surface polar (OH, NH2, COOH, or H2PO3) and non-polar (CH3) groups – from 0 to 1, 3, and 5. The surface wettability of as-prepared binary SAMs and their surface energy were assessed in both air/water/solid and oil/water/solid triphasic systems. FindingsWith the relative height of surface H2PO3 groups being deliberately set as 3 in particular, as-prepared binary SAMs gain unique environmentally adaptable surface lyophobicity, namely, they can be both oleophobic in water and hydrophobic in oil. Thanks to this new environmentally adaptable surface lyophobicity, such binary SAM coating enables copper meshes to realize selective and efficient oil/water separation without need of pre-wetting. Both the polar and dispersion interaction components of surface energy of the binary SAM coatings are found crucial to effective oil/water separation of the coated copper meshes; the former defines critical intrusion pressure and the latter must be larger than 22 nN/m.

Effects of ethyl 7-hydroxy-2-imino-2H-chromene-3-carboxylate, a synthesized coumarin derivative, on bisphenol A-induced kidney toxicity

Aim: In this study, it was aimed to investigate the protective effect of the synthesized coumarin ethyl 7-hydroxy-2-imino-2H-chromene-3 carboxylate (CM) against the renal toxicity of Bisphenol A (BPA). Materials and Methods: The CM molecule was synthesised through the reaction between 2,4-dihydroxybenzaldehyde and ethyl cyanoacetate. Experiment was conducted in four groups of rats: control, BPA, CM, and BPA+CM. Total Antioxidant Status (TAS), Total Oxidant Status (TOS), and Malondialdehyde (MDA) levels in kidney tissue were evaluated. serum samples were analyzed for Total-Native thiol and kidney function test parameters. Results: The BPA-treated group exhibited significant decreases in TAS and thiol levels, increases in TOS and MDA levels. However, these side effects were significantly reduced with CM. Conclusion: results obtained in this study indicate that CM molecule has a protective effect against BPA induced kidney toxicity.

A novel g-C3N4-SH@konjac glucomannan composite aerogel for patulin removal from apple juice and its photocatalytic regeneration

Patulin (PAT) is a hazardous mycotoxin frequently occurs in fruit industry. A reusable g-C3N4-SH@KG composite aerogel for PAT removal in a novel “dark adsorption-light regeneration” mode was prepared by thiol(-SH) functionalization and konjac glucomannan (KG) immobilization. The g-C3N4-SH@KG was characterized by SEM, FT-IR, XPS and UV–Vis DRS, and its PAT adsorption and photocatalytic regeneration behaviors and mechanisms were investigated. The g-C3N4-SH@KG exhibited good regeneration performance, maintaining 83% of PAT initial adsorption capacity (0.92 mg/g) after 5 “adsorption-regeneration” cycles. The adsorption process was endothermic and spontaneous. •OH and h+ generated by photocatalysis were the main substances that degraded PAT into two products and regenerated -SH. The g-C3N4-SH@KG could effectively remove PAT without negative impact on juice quality. The study provided a new strategy for the regeneration of thiol-functionalized PAT adsorbents, and a new idea for the application of non-selective photocatalysis in the control of food contaminations.

Effect of Amine, Carboxyl, or Thiol Functionalization of Mesoporous Silica Particles on Their Efficiency as a Quercetin Delivery System in Simulated Gastrointestinal Conditions.

Quercetin (Q) dietary supplements exhibit poor oral bioavailability because of degradation throughout gastrointestinal digestion (GD), which may be overcome using mesoporous silica particles (MSPs) as an oral delivery system (ODS). This study aimed to elucidate the effect of the functionalization of MSPs with amine-(A-MSP), carboxyl-(C-MSP), or thiol-(T-MSP) groups on their efficiency as a quercetin ODS (QODS). The type and degree of functionalization (DF) were used as factors in an experimental design. The Q-loaded F-MSP (F-MSP/Q) was characterized by gas physisorption analysis, loading capacity (LC), and dynamic light scattering and kinetics of Q release at gastric and intestinal pHs. Antioxidant capacity and Q concentration of media containing F-MSP/Q were evaluated after simulated GD. A-MSP showed the highest LC (19.79 ± 2.42%). C-MSP showed the lowest particle size at pH 1.5 or 7.4 (≈200 nm). T-MSP exhibited the maximum Q release at pH 7.4 (11.43%). High DF of A-MSP increased Q retention, regardless of pH. A-MSP preserved antioxidant capacity of Q-released gastric media (58.95 ± 3.34%). Nonetheless, MSP and F-MSP did not protect antioxidant properties of Q released in intestinal conditions. C-MSP and T-MSP showed essential features for cellular uptake and Q release within cells that need to be assessed.

Unlocking Heavy Metal Remediation Potential: A Review of Cellulose–Silica Composites

This comprehensive review explores recent advancements in heavy metal remediation techniques, focusing on the utilization of cellulose–silica composites and tailored surface modification techniques. We examine the synthesis strategies and properties of cellulose–silica adsorbents, highlighting their enhanced adsorption capacities and structural robustness for removing heavy metal pollutants from aqueous environments. The review investigates various surface modification approaches, including thiol functionalization, amino acid grafting, and silane coupling agents, for optimizing the surface chemistry and morphology of cellulose–silica composites. Mechanistic insights into the adsorption processes and kinetics of modified adsorbents are discussed, along with considerations for optimizing adsorption performance under different environmental conditions. This review provides valuable perspectives on the development of effective adsorbent materials for sustainable heavy metal remediation applications.

Fuel-Driven Enzymatic Reaction Networks to Program Autonomous Thiol/Disulfide Redox Systems.

Fuel-driven dissipative formation of disulfide bonds using competing oxidative activation and reductive deactivation presents a possibly very versatile avenue for autonomous materials design. However, this is challenging to realize because of the direct annihilation of oxidizing fuel and a deactivating reducing agent. We overcome this challenge by introducing a redox-based enzymatic reaction network (ERN), enabling the dissipative disulfide formation for molecularly dissolved thiols in a fully autonomous manner. Moreover, the ERN allows for programming hydrogel lifetimes by utilizing thiol-terminated star polymers (sPEG-SH). The ERN can be customized to operate with aliphatic and aromatic thiols and should thus be broadly applicable to functional thiols.

Investigation of the effect of amine and thiol as functional groups on gold Nanobipyramids properties

Metal nanoparticles are increasingly popular due to their unique properties, such as their vast surface area, tiny size, strong reactivity in live cells, and high-temperature stability. Gold nanoparticles, as one of the metal nanoparticle types, are frequently utilized in biosensor applications because of their adjustable Localized Surface Plasmon Resonance (LSPR) characteristics, less cytotoxic nature, and increased sensitivity to changes in the surrounding medium. The anisotropic metal nanoparticle of gold nanobipyramids (GNBPs) provides for higher Refractive Index Sensitivity (RIS) and Figure of Merit (FOM) value than others, allowing for higher sensitivity. This work lies in the comprehensive investigation of GNBPs functionalized with amine and thiol groups over varying shorter time durations (0.5 – 12 h) through the immediate change in optical, structural, morphological, electrical surfaces, and molecular properties. The findings show amine groups enable the red-shifted spectrum, whereas thiol groups impact the blue-shifted spectrum. By employing amine groups, it is able to produce side peaks in the XRD pattern made up of amine atoms. The use of thiol groups, meanwhile, has an impact on the growth increase in the (111) direction. Then, the highest surface density is obtained in 3 h, 59.78 % for amine-functionalized GNBPs (a-GNBPs) and 75.49 % for thiol-functionalized GNBPs (t-GNBPs). Next, a-GNBPs generate the highest angle slope compared to t-GNBPs, i.e., 140.422⁰. In addition, for the electrical surface effect, amine functionalization increases the zeta potential value from 0.3 to 2.5 mV, indicating the inhibition of nanoparticle agglomeration. On the other hand, thiol functionalization affects the decreasing of zeta potential value from 0.3 to -0.5 mV, allowing for nanoparticle agglomeration. Subsequent FTIR characterization analysis obtained shifts in the wave numbers, with the -OH bond exhibiting changes within the range of 3306.75 – 3269.95 cm-1, C=-CH bond providing for 2138.48 – 2136.56 cm-1 range, and the C = O bond showing alterations between 1637.59 – 1637.33 cm-1 following amine and thiol functionalization. Extended observation reveals that both a-GNBPs and t-GNBPs exhibit significant signal responses in glucose detection applications utilizing LSPR-based sensors, suggesting the feasibility of functionalizing GNBPs with amine and thiol groups for potential biosensor development.

Reversible C═N Bond Formation Controls Charge-Separation in an Aza-Diarylethene Photoswitch.

Diarylethenes belong to the most eminent photoswitches and have been studied for many decades. They are found in virtually every field of application and have become highly valuable molecular tools for instilling light-responsiveness into materials, catalysts, biological systems, or pharmacology. In this work, we present a novel and distinct type of pyrimidine-based aza-diarylethene, which undergoes a highly unusual zwitterion-forming photoreaction. During this fully reversible process, a CN double bond is established under concomitant aromatization and thiophene-ring opening. The metastable zwitterion thus possesses a positively charged extended aromatic structure and an independent conjugated thiolate function. It can further photoisomerize between a more stable Z and a less stable E isomer, resulting in effective four-state photoswitching. Unusual for diarylethenes, the metastable isomers show negative solvatochromism and red-shifted absorption in apolar solvents. With this behavior, aza-diarylethenes effectively bridge the properties of merocyanines and diarylethenes. Thermal stability of the zwitterions can be modulated from very labile to highly stable behavior in response to pH, again in a fully reversible manner. Pyrimidine-based aza-diarylethene thus establishes a unique photoreaction mechanism for diarylethenes, allowing control of charge separation, thermal stability, and color generation in a different way than hitherto possible.