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With the aim of preparing sustainable and degradable polymers from sugar-derived precursors, a family of five poly(ester-thioethers) were synthesized by photoinitiated thiol–ene polymerization of monomers incorporating D-glucaro-1,4:6,3-dilactone (GDL). Various dithiols were used to produce linear poly(ester-thioethers) of glucarodilactone 10-undecenoate (GDLU) to probe the effect of the dithiols on the observed mechanical performance and degradability. The samples exhibited glass transition (Tg) values from −8.7 to 19 °C. The polymers with the simplest dithiols, 1,2-ethanedithiol (EtDT) and 3,6-dioxa-1,8-octane-dithiol (DODT), were found to exhibit crystallinity, while the more structurally complex and rigid dithiol structures were found to produce amorphous materials. Due to the GDL units in the polymers, rapid degradation under basic aqueous conditions and stability in acidic and neutral conditions were observed. Tensile testing of these materials showed robust mechanical properties, including tunable moduli (0.011 to 0.29 GPa), strength (21 to 42 MPa), and ductility (410 to 590%).

Glutaredoxins (Grxs) are a family of glutathione (GSH)-dependent thiol-disulfide oxidoreductases. They feature GSH-binding sites that directly connect the reversible redox chemistry of protein thiols to the abundant cellular nonprotein thiol pool GSSG/GSH. This work studied the pathways for oxidation of protein dithiols P(SH)2 and reduction of protein disulfides P(SS) catalyzed by Homo sapiens HsGrx1 and Escherichia coli EcGrx1. The metal-binding domain HMA4n(SH)2 was chosen as substrate as it contains a solvent-exposed CysCys motif. Quenching of the reactions with excess iodoacetamide followed by protein speciation analysis via ESI-MS allowed interception and characterization of both substrate and enzyme intermediates. The enzymes shuttle between three catalytically-competent forms (Grx(SH)(S-), Grx(SH)(SSG) and Grx(SS)) and employ conserved parallel monothiol and dithiol mechanisms. Experiments with dithiol and monothiol versions of both Grx enzymes demonstrate which monothiol (plus GSSG or GSH) or dithiol pathways dominate a specific oxidation or reduction reaction. Grxs are shown to be a class of versatile enzymes with diverse catalytic functions that are driven by specific interactions with GSSG/GSH.

We designed and explored self-assembled gold nanoparticles (SAGNPs) by introducing dithiol modified polyethylene glycol (PEG) for internanoparticle cross-linking. SAGNPs could enhance uptake into cancer cells and be disintegrated by glutathione (GSH) to achieve tumor microenvironment-activated biodegradation. This assembled structure improved the photothermal effect compared to single gold nanospheres.

We applied a combination of mechanically controllable break junction (MCBJ) and in situ surface enhanced Raman spectroscopy (SERS) methods to investigate the long-standing single-molecule conductance discrepancy of prototypical benzene-1,4-dithiol (BDT) junctions. Single-molecule conductance characterization, together with configuration analysis of the molecular junction, suggested that disulfide-mediated dimerization of BDT contributed to the low conductance feature, which was further verified by the detection of S–S bond formation through in situ SERS characterization. Control experiments demonstrated that the disulfide-mediated dimerization could be tuned via the chemical inhibitor. Our findings suggest that a combined electrical and SERS method is capable of probing chemical reactions at the single-molecule level.

The dithiol reagents phenylarsine oxide (PAO) and dibromobimane (DBrB) have opposite effects on the F1FO-ATPase activity. PAO 20% increases ATP hydrolysis at 50 μM when the enzyme activity is activated by the natural cofactor Mg2+ and at 150 μM when it is activated by Ca2+. The PAO-driven F1FO-ATPase activation is reverted to the basal activity by 50 μM dithiothreitol (DTE). Conversely, 300 μM DBrB decreases the F1FO-ATPase activity by 25% when activated by Mg2+ and by 50% when activated by Ca2+. In both cases, the F1FO-ATPase inhibition by DBrB is insensitive to DTE. The mitochondrial permeability transition pore (mPTP) formation, related to the Ca2+-dependent F1FO-ATPase activity, is stimulated by PAO and desensitized by DBrB. Since PAO and DBrB apparently form adducts with different cysteine couples, the results highlight the crucial role of cross-linking of vicinal dithiols on the F1FO-ATPase, with (ir)reversible redox states, in the mPTP modulation.

Noble metal nanoparticles (NPs) modified electrodes have shown promising applications in the areas of catalysis, (electro)chemical analysis and biosensing due to their unique characters. In this paper, we introduced a so-called ligand exchange method to prepare self-assembly (SAM) electrode modified with noble metal nanoparticles. The noble metal nanoparticles protected by weakly adsorbed tetraoctylammonium bromide (TOAB) were synthesized firstly, then self-assembly (SAM) dithiol-modified Au electrode (Au-SHSAM) was immersed into the solutions containing TOAB-protected nanoparticles. Due to the strong interaction between the dithiol groups on the electrode and noble metal nanoparticles, the weakly adsorbed TOAB on the surface of noble metal NPs were replaced by dithiol groups. As a result, the TOAB protected NPs were anchored on the Au-SHSAM template electrode surface by ligand exchange, obtaining noble metal NPs modified electrode with high quality and stability. By adjusting the soaking time, the coverage of nanoparticles on the Au-SHSAM electrode surface could be controlled. The morphology and distribution of noble metal NPs on Au-SHSAM surface was analysis by scanning tunneling microscope (STM), and their electrochemical property was studied by cyclic voltammetry (CV) in H2SO4 solution. The approach is proved as a universal way to prepare noble metal NPs modified SAM electrode.

Glass is an often used substrate for preparation of thin metal films for use in electronics or optics, but due to its surface morphology and chemical properties its adhesion to sputtered Au layers is usually poor. A method utilizing Ar + plasma treatment and grafting of biphenyl-4,4′-dithiol (BPD) was employed to improve adhesion between sputtered thin Au layers and glass surface. The proposed method leads to changes of surface chemistry of the glass, introducing chemical groups (namely SH) with good affinity to Au. The plasma treatment was used to activate the glass surface to react with the BPD and create a strong bond. Nanoindentation and scratch tests were performed on the thin Au layers deposited on pristine and treated glass. The results show the plasma treatment leads to improvements of the adhesion by itself with the BPD grafting not having a positive effect in this matter. Scanning electron microscopy showed the substrate modification has influence on the microstructure of the subsequently grown Au layers which leads to change of their optical properties as well.

In this study, different dithiol/dimethacrylate formulations ± octamethacryl-polyhedral oligomeric silsesquioxanes (POSS) were synthesized and fully characterized in terms of structural, morphological, and thermostability features. The obtained results indicate that the incorporation of both dithiol and octamethacryl-POSS nanofillers within dimethacrylate matrix exhibits a significant influence on the surface chemistry, polymerization kinetics, thermostability, and thermomechanical properties of the resulting networks. Kinetic analysis showed that the presence of dithiol compound improves the conversion degree of the final dithiol/dimethacrylate networks, while thermal and thermomechanical analyses exhibit that octamethacryl-POSS produces nano-hybrids with enhanced thermostability and storage moduli.

In this work commercially available bifunctional organic dithiols, 4,4′-dithiol-biphenyl (BI), 4,4′-dithiolterphenyl (TR) and the on purpose prepared precursor of 4,4′-dithiol- trans -stilbene (ST), have been used for the stabilization of gold and silver nanoparticles (AuNPs and AgNPs). The bifunctional thiols have been chosen with different conjugation length, to prepare interconnected system of nanoparticles in order to achieve a tuning of their optical properties. The obtained AuNPs and AgNPs have been characterized by means of UV–vis spectroscopy to investigate the presence and shift of the Surface Plasmon Resonance (SPR); Field Effect Scanning Electron Microscopy (FESEM) allowed to achieve information on the NP’s morphology and size. Furthermore, the X-ray Photoelectron spectroscopy (XPS) measurements have been carried out to obtain structural information. AuNPs and AgNPs with mean size in the range 5–20 nm appeared at regular distances in FESEM images and XPS analysis revealed the presence of physisorbed and chemisorbed thiols. In particular AgNPs showed a lower quantity of physisorbed thiol and an higher tendency to form interconnected networks, also suggested by UV–vis data, with a strong red shift of the SPR band up to 550 nm. ST dithiol showed high tendency in the formation either of AuNPs and AgNPs networks as highlight by the pronounced redshift of the Surface Plasmon Resonance absorption wavelength as revealed by XPS characterization, where no physisorbed thiol was observed, indicating that all the sulphur atoms are involved in the functionalization of the nanoparticles metal surface.

Novel 4-(3-bromo-2-hydroxy-5-methylphenyl)-1,3-dithiol-2-ylidene derivatives have been synthesized from the reaction of the corresponding 1,3-dithiol-2-ylium salts with various methylene active compounds using DBU as base. The 1,3-dithiol-2-ylium compounds have been obtained from the reaction of the substituted w-bromoacetophenone with various salts of dithiocarbamic acids. The newly obtained derivatives were characterized by NMR spectrometry, UV-Vis and IR spectroscopy.

Single molecule tunnel junctions (SMTJs) can provide important physical insights into electronic and vibrational phenomena at the molecular scale. However, observations and analysis are typically confined to sufficiently low temperatures as to suppress molecular motion and the resulting stochastic fluctuations in the tunneling current. In this work, we introduce and experimentally validate a methodology whereby a slightly higher temperature (9 K) compared to a typical SMTJ study can be used to induce sparse fluctuations in the inelastic tunneling current and provide the fingerprints of dynamics between the conformational states of the molecule. Two examples of benzene dithiol and cysteine are studied in electromigratively formed W/Au nanowire SMTJs on SiO2 at 9 K. The second-order transform of the tunneling current reveals the expected vibrational spectra. However, we show that temporal fluctuations can be analyzed using a hidden Markov Model to reveal dynamics assigned to millisecond rearrangements of th...

Assembled gold nanorods (GNRs) attract much attention for their distinctive plasmon-coupled properties, but it remains challenging to realize practical use for their instability of the structure and the toxicity of the surfactant. We herein present a simple and effective protocol to coat mesoporous silica on the end-to-end and side-by-side assemblies, which are induced by different amount of the dithiol poly(ethylene glycol). The finite-difference time-domain (FDTD) simulations are also utilized to study the plasmonic properties of the nanostructures. Experimental and calculated results indicate that the as-prepared core-shell nanostructure possesses not only the optical stability, but also the fascinating and tunable optical response through changing the organized modes of assemblies. The result is promising in investigating near field plasmonic property, and biomedical application for in vivo bioimaging and photothermal cancer therapy.

Hydrogel-based depots are of growing interest for release of biopharmaceuticals; however, a priori selection of hydrogel compositions that will retain proteins of interest and provide desired release profiles remains elusive. Toward addressing this, in this work, we have established a new tool for the facile assessment of protein release from hydrogels and applied it to evaluate the effectiveness of mesh size estimations on predicting protein retention or release. Poly(ethylene glycol) (PEG)-based hydrogel depots were formed by photoinitiated step growth polymerization of four-arm PEG functionalized with norbornene (PEG-norbornene, 4% w/w to 20% w/w, Mn ∼ 5 to 20 kDa) and different dithiol cross-linkers (PEG Mn ∼ 1.5 kDa or enzymatically degradable peptide), creating well-defined, robust materials with a range of mesh sizes estimated with Flory-Rehner or rubber elasticity theory (∼5 to 15 nm). A cocktail of different model proteins was released from compositions of interest, and sodium dodecyl sulfate polyacrylamide gel electrophoresis (SDS-PAGE) was used to facilely and quantitatively analyze temporal release profiles. Mesh size was predictive of retention of relatively large proteins and release of relatively small proteins. Proteins with diameters comparable to the mesh size, which is often the case for growth factors, were released by hindered diffusion and required experimental assessment of retention and release. With this knowledge, hydrogels were designed for the controlled release of a therapeutically relevant growth factor, PDGF-BB.

Nanopore structures have been successfully employed in next-generation DNA sequencing. For more complicated protein which normally contains 20 different amino acids, identifying the fluctuation of ionic current caused by different amino acids appears inadequate for protein sequencing. Therefore, it is highly desirable to develop size-controllable nanopores with optical activity that can provide additional structural information. Herein, we discovered the novel nanopore properties of the self-assembled ultramicroelectrodes originally developed by Bard and co-workers. Using a slightly modified method, the self-assembly of 7 ± 1 nm gold nanoparticles (AuNPs) can be precisely controlled to form a gold nanoporous sphere (GPS) on the tip of a glass capillary. Different dithiol linker molecules (1,3-propanedithiol, C3; 1,6-hexanedithiol, C6; and 1,9-nonanedithiol, C9) reproducibly led to rather similar nanopore sizes (5.07 ± 0.02, 5.13 ± 0.02, and 5.25 ± 0.01 nm), respectively. The GPS nanostructures were found to exhibit high ionic current rectification as well as surface-enhanced Raman scattering (SERS) activity due to the presence of nanopores and numerous "hot spots" among the cross-linked AuNPs on the surface of GPS. The rectification effect of the small nanopores was observed even under high concentration of electrolyte (290 mM), along with SERS enhancement factors well above 1 × 10

A PEG-based cyclized vinyl polymer was synthesized via one-step RAFT polymerization and used as a precursor of injectable hydrogels. Dithiol linkers including laminin-derived peptides containing IKVAV and YIGSR sequences and DTT were used for gelation. Fast and adjustable gelation rate was achieved through nucleophile-initiated thiol-Michael reaction under physiological conditions. Low swelling ratio and moderate degradation rate of the formed hydrogels were observed. 3D encapsulation of neural progenitor cells in the synthetic hydrogel showed good cell viability over 8 days. The long-term cell survival and proliferation were promoted by the introduction of laminin-derived peptides. This hydrogel platform based on peptide-cross-linked, cyclized vinyl polymers can be used as a universal hydrogel template for 3D cell encapsulation.

Joint crosslinked gels containing disulfide linkage have been synthesized by oxidation reaction of multi-functional thiol monomers, trimethylolpropane tris(3-mercaptopropionate), tris-[3-mercaptopropionyloxy-ethyl]-isocyanurate, pentaerythritol tetrakis (3-mercaptopropionate), and dipenta-erythritol hexakis (3-mercaptopropionate) in dimethyl sulfoxide (DMSO). Both the oxidation reactions with DMSO at 85 °C and Albright-Goldman oxidation in the presence of acetic anhydride at 50 °C yielded the corresponding gels. The oxidation reaction with DMSO showed higher reaction conversion than that with Albright-Goldman oxidation. Network structure of the gels was quantitatively characterized by means of a scanning microscopic light scattering. The reactions formed homogeneous network structure with about 0.5 nm of mesh in the gels. Mechanical properties of the obtained gels were investigated by compression test. Increasing of the crosslinking density with increasing of the monomer concentration, number of thiol group of the monomer or reaction conversion, raised Young's modulus, and breaking stress of the gels. Cogelation of the tri-, tetra-, of hexa-thiol monomer and dithiol monomers yielded soft and flexible gels. Reduction of the disulfide bonds in the gels by dithiothreitol turned the gel into solution. Heating of the resulting solution induced the regelation by reforming of the disulfide bonds. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017, 55, 3749–3756

Functionalized gold and silver nanoparticles have been prepared and characterized by means of spectroscopic and morphological techniques together focused on electrical measurements on cast deposited films. The Au and Ag nanoparticles have been functionalized with a on purpose prepared conjugated dithiol, 9,9-didodecyl-2,7-bis-thiofluorene (FL), giving rise to organic solvents soluble AuNPs-FL and AgNPs-FL samples, respectively. In the case of AuNPs-FL, well separated nanoparticles, with an average size of about 4 nm, assembled into bidimensionally monolayer network and with regular spatial distributions have been observed by TEM. Synchrotron radiation-XPS data support the observed network formation, showing that all bifunctional ligands end-groups are covalently bonded to metal noble atoms at the nanoparticles surfaces. In order to investigate their interesting conduction properties, electrical measurements evidenced a non-ohmic behavior in the case of the AuNPs-FL thin film, with a conduction mechanism that strongly depends on polarons and bipolarons along the carbon active chain belonging to the fluorene bridge. By increasing the stacked layers of the AuNPs-FL thin film, the conductivity behavior changed following approximately the ohmic law. On the contrary, AgNPs-FL shows higher conductivity, and upon an aging process, a diode behavior was observed that opens perspectives as flexible optoelectronics devices.

A theoretical mechanism has been proposed for the reaction of vinylidene chloride with ethane-1,2-dithiol in the system hydrazine hydrate–potassium hydroxide on the basis of DFT quantum chemical calculations at the B3LYP/6-311++G(d,p) level of theory. The reaction includes two consecutive stages: dehydrochlorination of vinylidene chloride to chloroacetylene and nucleophilic addition of one thiol group of ethane-1,2-dithiol to the β-carbon atom of chloroacetylene, followed by closure of 2,3-dihydro-1,4-dithiine ring via nucleophilic substitution of chlorine by sulfur atom of the second thiol group.

Experimental evidence for the existence of gas phase isomers in monolayer protected noble metal clusters is presented, taking Ag44(SR)30 (SR = 4-fluorothiophenol, p-mercaptobenzoic acid) and Ag29(BDT)12 (BDT: benzene dithiol) clusters as examples which do not show any isomeric structures in their crystals. Electrospray ionization coupled with ion mobility separation allowed for the identification of multiple isomers of Ag44SR30 cluster in its 3– and 4– charge states, their most abundant gas phase ions. Ag29(BDT)12 showed isomerism in its common 3– charge state. Isomerism is likely to be due to different types of ligand orientations in the staples leading to changes in the overall size and shape of the cluster ions, which was further confirmed by density functional theory calculations on Ag44(FTP)304–. No isomers were seen in the ions of the well-known cluster, Au25SR18 (SR = phenylethanethiol, dodecanethiol, and butanethiol).

A surface enhanced Raman scattering (SERS)-based immunosensor based on functional core-shell nanoparticles (Au@1,4-benzenedithiol@Au NPs) was developed for ultra-sensitive and high specific tumor marker detection. The engaged rigid dithiol molecule 1,4-benzenedithiol (1,4-BDT), which was used as a Raman reporter as well as a core-shell gap maker, connected the Au core and shell, facilitated the thickness controls of the shell and the core-shell gap. The thin Au shell in Au@1,4-BDT@Au prevented the dissociation of 1,4-BDT and its nonspecific interactions with co-existing proteins in complicated biological environment, which significantly improve the stability and sensitivity of the probe. To verify the validation of the Au@1,4-BDT@Au SERS immunosensor, a well-known prostate cancer marker, f-PSA antigen, was detected. As expected, the non-specific adsorption of co-existing proteins was significantly reduced, and the detection sensitivity of f-PSA was greatly enhanced with a limit of detection of 2.0 pg/mL. The linear correlation with the logarithm of concentration in wider range from 10 pg/mL to 10 ng/mL was achieved. The analysis of f-PSA-spiked human serum samples revealed that the method had high accuracy. Therefore, the dithiol Raman reporter-encoded Au@Au core-shell structure-based immunosensor is promising for the ultra-sensitive and high specific tumor marker detections.

X-ray structure analysis of the [5]radialene with quintuple 1,3-benzodithiol-2-ylidenes (4) and its tetracation salt, 4 a⋅CS2 and (4 a)4+(ReO4–)4(CH3CN), was successfully carried out. The neutral [5]radialene molecule in 4⋅CS2 adopted a non-planar structure with an envelope conformation of the central five-membered ring. In contrast, the central five-membered ring of 4 a4+ in (4 a)4+(ReO4−)4(CH3CN) adopted a planar structure with significant contribution of an aromatic cyclopentadienide structure. An anion-π interaction was observed between the ReO4– anion and the central five-membered ring in (4 a)4+(ReO4–)4(CH3CN). The electronic structures of 4 a and its oxidative species (4 a2+ and 4 a4+) were estimated by density functional theory (DFT) calculations. The optimized structure of 42+ suggested the delocalization of a positive charges over two 1,3-benzodithiol-2-ylidene units through the central five-membered ring.

Strong stochastic fluctuations witnessed as very broad resistance (R) histograms with widths comparable to or even larger than the most probable values characterize many measurements in the field of molecular electronics, particularly those measurements based on single molecule junctions at room temperature. Here we show that molecular junctions containing 80 oligophenylene dithiol molecules (OPDn, 1 ≤ n ≤ 4) connected in parallel display small relative statistical deviations—δR/R ≈ 25% after only ∼200 independent measurements—and we analyze the sources of these deviations quantitatively. The junctions are made by conducting probe atomic force microscopy (CP-AFM) in which an Au-coated tip contacts a self-assembled monolayer (SAM) of OPDs on Au. Using contact mechanics and direct measurements of the molecular surface coverage, the tip radius, tip-SAM adhesion force (F), and sample elastic modulus (E), we find that the tip-SAM contact area is approximately 25 nm2, corresponding to about 80 molecules in the ...

Three types of (diphosphine)Pd- or Pt-bridged butterfly Fe/S cluster complexes have been prepared by a simple and convenient one-pot synthetic method. The first type of such complexes involves the linear (diphosphine)Pd- or Pt-bridged double-butterfly Fe/S clusters [(μ-RS)(μ-S═CS)Fe2(CO)6]2[M(diphosphine)] (1–12; M = Pd and Pt; R = Et, t-Bu, Ph, and p-MeC6H4; diphosphine = dppe, dppv, and dppf), which were prepared by sequential reactions of monoanions [(μ-RS)(μ-CO)Fe2(CO)6]– (formed in situ from Fe3(CO)12, RSH, and Et3N) with excess CS2, followed by treatment of the resulting monoanions [(μ-RS)(μ-S═CS)Fe2(CO)6]– with (diphosphine)MCl2. The second type of complexes involves the macrocyclic (diphosphine)M-bridged double-butterfly Fe/S clusters [μ-S(CH2)4S-μ][(μ-S═CS)Fe2(CO)6]2[M(diphosphine)] (13–16; M = Pd and Pt; diphosphine = dppe and dppv), which were prepared by sequential reactions of dianion [{μ-S(CH2)4S-μ}{(μ-CO)Fe2(CO)6}2]2– (generated in situ from Fe3(CO)12, dithiol HS(CH2)4SH, and Et3N) with exc...

N-propylsulfanyl and isopropylsulfanyl substituted 2,5-di(1,3-dithiol-2-ylidene)-1,3-dithiolane-4-thione derivatives with methoxycarbonyl groups were synthesized, and their redox and electronic properties and crystal structures were investigated. Solid-state absorption spectra showed that both derivatives absorb almost all visible light. Furthermore isopropylsulfanyl-substituted derivatives absorb near-infrared light and the absorption edge reaches around 1320 nm. The crystal structures show that both derivatives are stacked in one dimension to form a columnar structure, but the molecular arrangements of their columns were quite different from each other. The stacked n-propylsulfanyl derivatives kept their orientation of thiocarbonyl groups in the same direction and the one molecule of the isopropylsulfanyl derivatives were rotated in relation to each other by an angle of 56° about their longer molecular axis. The TD-DFT calculation of stacked molecules suggests that the molecular arrangement among the st...

We explore new approaches to engineering the surface chemistry of interferometric sensing platforms based on nanoporous anodic alumina (NAA) and reflectometric interference spectroscopy (RIfS). Two surface engineering strategies are presented, namely (i) selective chemical functionalization of the inner surface of NAA pores with amine-terminated thiol molecules and (ii) selective chemical functionalization of the top surface of NAA with dithiol molecules. The strong molecular interaction of Au3+ ions with thiol-containing functional molecules of alkane chain or peptide character provides a model sensing system with which to assess the sensitivity of these NAA platforms by both molecular feature and surface engineering. Changes in the effective optical thickness of the functionalized NAA photonic films (i.e., sensing principle), in response to gold ions, are monitored in real-time by RIfS. 6-Amino-1-hexanethiol (inner surface) and 1,6-hexanedithiol (top surface), the most sensitive functional molecules fro...

The first β-allyl carbamate fluorescent probe, AC-green, was reported for specifically imaging vicinal dithiol proteins (VDPs) in living systems. The probe displays low toxicity and features high sensitivity and fast response towards VDPs. A drastic loss of VDPs in a Parkinson's model was disclosed by AC-green, linking the fluctuation of VDP levels to Parkinson's disease for the first time. The structural novelty and favorable properties of AC-green will advance the development of novel VDP probes.

Enzyme immobilization on nanocarriers is nowadays considered a useful tool for improving activity and maintaining biocatalysts stability while facilitating their recovery and reuse. In this work we prepared Au and Ag based nanoparticles (AuNPs or AgNPs) stabilized with two different ligands, the organometallic dinuclear complex trans,trans-[dithiodibis(tributylphosphine)diplatinum(II)-4,4′-diethynylbiphenyl] (Pt-DEBP) and the organic dithiol 4,4′-dithiol-biphenyl (BI), able to link the NPs in 3D networks. We investigated the ability of these nanocarriers to interact with a model lipolytic enzyme from Pseudomonas fluorescens and maintain its activity, both in aqueous as well as in organic media. In particular, our results highlighted that the nature of the metal plays a role in enzyme adsorption, while enzyme activity is mostly influenced by the chemistry of the organic spacer. The obtained bioconjugate, between lipase and the most promising carrier, AgNPs-Pt-DEBP, was stable in a wide temperature range (25–55 °C) and it showed good activity retention both in aqueous (50%) as well as in organic media (75%), compared to the lipase used in soluble form.