Sol-gel-derived hard coatings from tetraethoxysilane and organoalkoxysilanes bearing zwitterionic and isothiazolinone groups and their antifouling behaviors.

Current environmentally friendly marine antifouling (AF) coatings are mainly polymeric with a relatively low hardness. Hard sol-gel-derived AF coatings for underwater robot-cleaning are seldom used. In this work, two new organoalkoxysilanes, i.e., (N-methoxyacylethyl)-3-aminopropyltriethoxysilane and 2-(2-hydroxy-3-(3-(trimethoxysilyl)propoxy)propyl)benzo[d]isothiazol-3(2H)-one, were synthesized by a facile method. These two precursors were used with tetraethoxysilane (TEOS) to produce three series of hybrid AF coatings with zwitterionic group (Z-χ), antibacterial group (1,2-benzisothiazolin-3-one) (A-χ) and zwitterionic and antibacterial groups (S-χ) by a sol-gel process. The hardness of the coatings was measured using a pencil hardness tester and the AF behaviors of the coatings were examined by laboratory and field assays. A pencil hardness up to 5 H was achieved and slight deterioration was observed after 9 months of immersion in artificial seawater for the A-χ and S-χ coatings at a sufficiently high TEOS content. A synergistic effect between the zwitterion and antimicrobial agents existed but was not obvious. A higher TEOS content led to a higher hardness and better AF performance regardless of the type of AF group. Even with the same biofilm formation after field assay, coatings with a higher TEOS content exhibited a better resistance to mussel settlement.

Backbone-Photodegradable Polymers by Incorporating Acylsilane Monomers via Ring-Opening Metathesis Polymerization.

Materials capable of degradation upon exposure to light hold promise in a diverse range of applications including biomedical devices and smart coatings. Despite the rapid access to macromolecules with diverse compositions and architectures enabled by ring-opening metathesis polymerization (ROMP), a general strategy to introduce facile photodegradability into these polymers is lacking. Here, we report copolymers synthesized via ROMP that can be degraded by cleaving the backbone in both solution and solid states under irradiation with a 52 W, 390 nm Kessil LED to generate heterotelechelic low-molecular-weight fragments. To the best of our knowledge, this work represents the first instance of the incorporation of acylsilanes into a polymer backbone. Mechanistic investigation of the degradation process supports the intermediacy of an α-siloxy carbene, formed via a 1,2-photo Brook rearrangement, which undergoes insertion into water followed by cleavage of the resulting hemiacetal.

Biobased Polyurethane Composite Foams Reinforced with Plum Stones and Silanized Plum Stones.

In the following study, ground plum stones and silanized ground plum stones were used as natural fillers for novel polyurethane (PUR) composite foams. The impact of 1, 2, and 5 wt.% of fillers on the cellular structure, foaming parameters, and mechanical, thermomechanical, and thermal properties of produced foams were assessed. The results showed that the silanization process leads to acquiring fillers with a smoother surface compared to unmodified filler. The results also showed that the morphology of the obtained materials is affected by the type and content of filler. Moreover, the modified PUR foams showed improved properties. For example, compared with the reference foam (PUR_REF), the foam with the addition of 1 wt.% of unmodified plum filler showed better mechanical properties, such as higher compressive strength (~8% improvement) and better flexural strength (~6% improvement). The addition of silanized plum filler improved the thermal stability and hydrophobic character of PUR foams. This work shows the relationship between the mechanical, thermal, and application properties of the obtained PUR composites depending on the modification of the filler used during synthesis.

Selective demethylation of O-aryl glycosides by iridium-catalyzed hydrosilylation.

The cleavage of alkyl ethers by hydrosilylation is a powerful synthetic tool for the generation of silyl ethers. Previous attempts to apply this transformation to carbohydrate derivatives have been constrained by poor selectivity and preferential reduction of the anomeric position. O-Aryl glycosides are found to be stable under iridium- and borane-catalyzed hydrosilylation conditions, allowing for alkyl ether cleavage without loss of anomeric functionality. A cationic bis(phosphine)iridium complex catalyzes the selective 3-demethylation of a variety of 2,3,4-tri-O-methyl pyranoses, offering a unique approach to 3-hydroxy or 3-acetyl 2,4-di-O-methylpyranoses.

Elaborated study of Cu(II) carbosilane metallodendrimers bearing substituted iminopyridine moieties as antitumor agents.

Iminopyridine-decorated carbosilane metallodendrimers have recently emerged as a promising strategy in the treatment of cancer diseases. Their unique features such as the nanometric size, the multivalent nature and the structural perfection offer an extraordinary platform to explore structure-to-property relationships. Herein, we showcase the outstanding impact on the antitumor activity of a parameter not explored before: the iminopyridine substituents in meta position. New Cu(II) carbosilane metallodendrimers, bearing methyl or methoxy substituents in the pyridine ring, were synthesized and thoroughly characterized. Electron Paramagnetic Resonance (EPR) was exploited to unveil the properties of the metallodendrimers. This study confirmed the presence of different coordination modes of the Cu(II) ion (Cu-N2O2, Cu-N4 and Cu-O4), whose ratios were determined by the structural features of the dendritic molecules. These metallodendrimers exhibited IC50 values in the low micromolar range (<6 µM) in tumor cell lines such as HeLa and MCF-7. The subsequent in vitro assays on both healthy (PBMC) and tumor (U937) myeloid cells revealed two key facts which improved the cytotoxicity and selectivity of the metallodrug: First, maximizing the Cu-N2O2 coordination mode; second, adequately selecting the pair ring-substituent/metal-counterion. The most promising candidates, G1(-CH3)Cl (8) and G1(-OCH3)NO3(17), exhibited a substantial increase in the antitumor activity in U937 tumor cells, compared to the non-substituted counterparts, probably through two different ROS-production pathways.

Short-Chained Platinum Complex Catalyzed Hydrosilylation under Thermomorphic Conditions: Heterogeneous Phase Separation at Ice Temperature.

Homogeneous catalysts PtCl2[5,5'-bis-(n-ClCF2(CF2)3CH2OCH2)-2,2'-bpy] (2A) and PtCl2[5,5'-bis-(n-HCF2(CF2)3CH2OCH2)-2,2'-bpy] (2B), which contained short fluorous chains, were synthesized and used in catalysis of hydrosilylation of alkynes. In these reactions the thermomorphic mode was effectively used to recover these catalysts from the reaction mixture up to eight cycles by taking advantage of heterogeneous phase separation at ice temperature. This kind of catalysis had previously been observed in fluorous catalysts of platinum containing about 50% F-content, but in this work the percentage of F-content is decreased to only about 30%, by which we termed them as "very light fluorous". Our new type of catalyst with limited number of F-content is considered as the important discovery in the fluorous technology field as the reduced number of fluorine atoms will help to be able to comply the EPA 8-carbon rule. The metal leaching after the reaction has been examined by ICP-MS, and the testing results show the leaching of residual metal to be minimal. Additionally, comparing these results to our previous work, fluorous chain assisted selectivity has been observed when different fluorous chain lengths of the catalysts are used. It has been found that there exists fluorous chain assisted better selectivity towards ß-(E) form in the Pt-catalyzed hydrosilylation of non-symmetric terminal alkyne when the Pt catalyst contains short fluorous chain (i.e., 4 Cs). Phenyl acetylenes showed the opposite regioselectivity due to pi-pi interaction while using the same catalyst via Markovnikov's addition to form terminal vinyl silane, which is then a major product for Pt-catalyzed hydrosilylation of terminal aryl acetylene with triethylsilane. Finally, the kinetic studies indicate that the insertion of alkyne into the Pt-H bond is the rate-determining step.

Synthesis of ß-Silyl α-Amino Acids via Visible-Light-Mediated Hydrosilylation.

An expedient synthesis of ß-silyl α-amino acids is reported via the application of visible-light-mediated hydrosilylation. The reaction utilizes readily accessible and structurally diverse hydrosilanes to provide radicals for conjugate addition to dehydroalanine ester and analogues. Notably, the use of chiral methyleneoxazolidinone as the substrate and chiral inducer enabled the highly stereoselective synthesis. Furthermore, the reaction could also be performed in a continuous flow fashion and scaled up to the gram scale.

Smart Synthesis of Trimethyl Ethoxysilane (TMS) Functionalized Core-Shell Magnetic Nanosorbents Fe3O4@SiO2: Process Optimization and Application for Extraction of Pesticides.

In the current study, a smart approach for synthesizing trimethyl ethoxysilane-decorated magnetic-core silica-nanoparticles (TMS-mcSNPs) and its effectiveness as nanosorbents have been exploited. While the magnetite core was synthesized using the modified Mössbauer method, Stöber method was employed to coat the magnetic particles. The objective of this work is to maximize the magnetic properties and to minimize both particle size (PS) and particle size distribution (PSD). Using a full factorial design (2k-FFD), the influences of four factors on the coating process was assessed by optimizing the three responses (magnetic properties, PS, and PSD). These four factors were: (1) concentration of tetraethyl-orthosilicate (TEOS); (2) concentration of ammonia; (3) dose of magnetite (Fe3O4); and (4) addition mode. Magnetic properties were calculated as the attraction weight. Scanning electron microscopy (SEM) was used to determine PS, and standard deviation (±SD) was calculated to determine the PSD. Composite desirability function (D) was used to consolidate the multiple responses into a single performance characteristic. Pareto chart of standardized effects together with analysis of variance (ANOVA) at 95.0 confidence interval (CI) were used to determine statistically significant variable(s). Trimethyl ethoxysilane-functionalized mcSNPs were further applied as nanosorbents for magnetic solid phase extraction (TMS-MSPE) of organophosphorus and carbamate pesticides.

Cu(II)-Catalysed ß-silylation of dehydroalanine residues in peptides and proteins.

We report the efficient and selective Cu(ii)-catalysed ß-silylation of naturally occurring dehydroalanine (Dha) residues in various ribosomally synthesized and post-translationally modified peptides (RiPPs). The method is also applicable to proteins, as was shown by the modification of a Dha residue that was chemically introduced into Small Ubiquitin-like Modifier (SUMO).

A highly efficient acyl-transfer approach to urea-functionalized silanes and their immobilization onto silica gel as stationary phases for liquid chromatography.

An alternative method for efficient synthesis of urea-functionalized silanes was proposed on the basis of an N, N'-carbonyldiimidazole-mediated acyl-transfer reaction between various amino-containing building blocks. The employment of different parent aminosilanes and alkylamines afforded an array of urea-containing silanes, which were subsequently immobilized onto silica gel to form corresponding urea-embedded alkyl stationary phases for high-performance liquid chromatography. The different substituents on the silicon core of the derivatized silane were found to significantly influence the final chromatographic behaviors. The comparative chromatographic characterization of thus-prepared silica packings with conventional octadecyl (C18) stationary phases revealed that the urea group was beneficial to suppress silanol activity towards basic probes, as well as to increase the water-compatibility of the alkyl stationary phases. The combination of a polar urea moiety and a non-polar long alkyl chain was favorable for an enhanced steric selectivity towards shape-constrained isomers. The polarizability-sensitive feature of such stationary phases made them good candidates for efficient separation of nitro-containing polar substances.

Stereoselective Synthesis of Cis- and Trans-Tetrasubstituted Vinyl Silanes Using a Silyl-Heck Strategy and Hiyama Conditions for Their Cross-Coupling.

We report a palladium-catalyzed, three-component carbosilylation reaction of internal symmetrical alkynes, silicon electrophiles, and primary alkyl zinc iodides. Depending on the choice of ligand, stereoselective synthesis of either cis- or trans-tetrasubstituted vinyl silanes is possible. We also demonstrate conditions for the Hiyama cross-coupling of these products to prepare geometrically defined tetrasubstituted alkenes.

Enantioselective Diarylcarbene Insertion into Si-H Bonds Induced by Electronic Properties of the Carbenes.

Catalytic enantioselection usually depends on differences in steric interactions between prochiral substrates and a chiral catalyst. We have discovered a carbene Si-H insertion in which the enantioselectivity depends primarily on the electronic characteristics of the carbene substrate, and the log(er) values are linearly related to Hammett parameters. A new class of chiral tetraphosphate dirhodium catalysts was developed; it shows excellent activity and enantioselectivity for the insertion of diarylcarbenes into the Si-H bond of silanes. Computational and mechanistic studies show how the electronic differences between the two aryls of the carbene lead to differences in energies of the diastereomeric transition states. This study provides a new strategy for asymmetric catalysis exploiting the electronic properties of the substrates.

Enantioselective Si-H Insertion Reactions of Diarylcarbenes for the Synthesis of Silicon-Stereogenic Silanes.

We report the first example of enantioselective, intermolecular diarylcarbene insertion into Si-H bonds for the synthesis of silicon-stereogenic silanes. Dirhodium(II) carboxylates catalyze an Si-H insertion using carbenes derived from diazo compounds where selective formation of an enantioenriched silicon center is achieved using prochiral silanes. Fourteen prochiral silanes were evaluated with symmetrical and prochiral diazo reactants to produce a total of 25 novel silanes. Adding an ortho substituent on one phenyl ring of a prochiral diazo enhances enantioselectivity up to 95:5 er with yields up to 98%. Using in situ IR spectroscopy, the impact of the off-cycle azine formation is supported based on the structural dependence for relative rates of diazo decomposition. A catalytic cycle is proposed with Si-H insertion as the rate-determining step, supported by kinetic isotope experiments. Transformations of an enantioenriched silane derived from this method, including selective synthesis of a novel sila-indane, are demonstrated.

Synthesis, Characterization, Biomedical Application, Molecular Dynamic Simulation and Molecular Docking of Schiff Base Complex of Cu(II) Supported on Fe3O4/SiO2/APTS.

INTRODUCTION: Over the past several years, nano-based therapeutics were an effective cancer drug candidate in order to overcome the persistence of deadliest diseases and prevalence of multiple drug resistance (MDR). METHODS: The main objective of our program was to design organosilane-modified Fe3O4/SiO2/APTS(~NH2) core magnetic nanocomposites with functionalized copper-Schiff base complex through the use of (3-aminopropyl)triethoxysilane linker as chemotherapeutics to cancer cells. The nanoparticles were characterized by Fourier transform infrared spectroscopy (FT-IR), X-ray powder diffraction (XRD), field emission scanning electron microscopy (FE-SEM), TEM, and vibrating sample magnetometer (VSM) techniques. All analyses corroborated the successful synthesis of the nanoparticles. In the second step, all compounds of magnetic nanoparticles were validated as antitumor drugs through the conventional MTT assay against K562 (myelogenous leukemia cancer) and apoptosis study by Annexin V/PI and AO/EB. The molecular dynamic simulations of nanoparticles were further carried out; afterwards, the optimization was performed using MM+, semi-empirical (AM1) and Ab Initio (STO-3G), ForciteGemo Opt, Forcite Dynamics, Forcite Energy and CASTEP in Materials studio 2017. RESULTS: The results showed that the anti-cancer activity was barely reduced after modifying the surface of the Fe3O4/SiO2/APTS nanoparticles with 2-hydroxy-3-methoxybenzaldehyde as Schiff base and then Cu(II) complex. The apoptosis study by Annexin V/PI and AO/EB stained cell nuclei was performed that apoptosis percentage of the nanoparticles increased upon increasing the thickness of Fe3O4 shell on the magnetite core. The docking studies of the synthesized compounds were conducted towards the DNA and Topoisomerase II via AutoDock 1.5.6 (The Scripps Research Institute, La Jolla, CA, USA). CONCLUSION: Results of biology activities and computational modeling demonstrate that nanoparticles were targeted drug delivery system in cancer treatment.

A Silyl Ether Based Fluorescent Probe for Rapid Monitoring of Endogenous Peroxynitrite Concentration and Imaging in Living Cells through Multicolor Emission.

The peroxynitrite ion (ONOO- ) has important roles in many biological processes. We have developed a multicolor ONOO- -sensing probe (SiONNOH) that undergoes deprotonation and desilylation processes, which result in several changes in the emission wavelengths. In response to different concentrations of ONOO- , the probe exhibits fluorescence changes from pink (595 nm at 2 eq. ONOO- ) to green (540 nm at 6 eq. ONOO- ) via orange (3 eq. ONOO- ) and yellow (4 eq. ONOO- ) under physiological conditions until no fluorescence signal is observed after ONOO- is completely eliminated by lipoic acid. The probe shows the high selectivity for ONOO- and the limit of detection is calculated to be 1.27 µM. Moreover, the probe shows the capacity to monitor the concentration ranges of ONOO- through multicolor fluorescence in living cells, which will greatly facilitate the rapid detection of ONOO- concentration ranges by the naked eye under a UV light without any precision instrumentation.

Exploring ion-ion preferences through structure-property correlations: amino acid-derived, bis(guanidinium) disiloxane salts.

In a more synthetical approach to the study of ion-specific phenomena, four dipodal bis(guanidinium) siloxanes have been synthesized starting from glycine, ß-alanine, γ-aminobutanoic acid, L-proline and 1,3-bis(3-aminopropyl)tetramethyldisiloxane. Together with their non-amide progenitor they were comparatively studied in regards to their interactions with nine different anions: sulphate, chromate, molybdate, benzoate, chloride, azide, nitrite, nitrate and thiocyanate. Their aqueous solubilities, form, 1H NMR and FT-IR spectra were examined while searching for anion-specific interactions falling in- or outside of the Hofmeister series. We show that although the "chao-" and "kosmotropic" ions affect the properties of solutions in a predictable way, more selective cation-anion pairing is responsible for phase separation and crystallinity. As a prominent example, crystal structure of one of the benzoate salts was successfully obtained and reveals a synergy of hydrophobic packing, ionic and hydrogen bonding. Immobilized but still flexible siloxane bridges give rise to crystals described by P 42/n space group and neatly segregated into hydro- and lipophilic sections.

Facile Synthesis of Poly(DMAEMA-co-MPS)-coated Porous Silica Nanocarriers as Dual-targeting Drug Delivery Platform: Experimental and Biological Investigations.

Inorganic structures with functionalized polymers play essential roles in diverse biological trends. Herein, thermal and CO2 dual-stimuli nanomaterials composed of mesoporous silica nanoparticles (MSN) anchored with two grafted copolymers: poly(3-methacryloxypropyltrimethoxysilane) "PMPS" & poly(N,N-dimethylaminoethyl methacrylate) "PDMAEMA" were synthesized via one-step reaction and characterized by BET as well as BJH methods to estimate pore sizes, pore volumes, and surface areas. The smart PDMAEMA acted as an active gatekeeper to adjust the loading or in vitro release processes of a fungicidal drug-loaded inside the mesopores by altering temperature or CO2 of the tested environment. Furthermore, treating the nanomaterials by CO2 for a few minutes was found to have a bactericidal effect with promising results as indicated by the disk diffusion technique. In general, the positive biological activity against selected strains of bacteria and fungi indicates that these particles may be helpful for engineering more efficient antifungal or antibacterial agents for pharmaceutical applications.

Nanoscaled Materials for Drug Delivery into Cells/Stem Cells.

The successful and efficient transport and delivery of drugs and biomolecules to cells/stem cells have revealed the main challenge in clinical therapy development. Special materials and systems are used in smart drug delivery to improve the effectiveness by controlling drug release and decreasing the side effects. Synthesized water-dispersible polymer-covalent organic framework nanocomposites are integrated via the assembly of PEG-modified monofunctional curcumin derivatives and amine-functionalized covalent organic frameworks for in vitro and in vivo drug delivery. The smart delivery system exhibits an efficient targeting strategy for cancer therapy and also demonstrates an important promise on the improvement of a smart system for cancer cell-/stem cell-targeted drug delivery.

ß-Amino- and Alkoxy-Substituted Disilanides.

Our recent study on formal halide adducts of disilenes led to the investigation of the synthesis and properties of ß-fluoro- and chlorodisilanides. The reaction of the functionalized neopentasilanes (Me3Si)3SiSiPh2NEt2 and (Me3Si)3SiSiMe2OMe with KOtBu in the presence of 18-crown-6 provided access to structurally related ß-alkoxy- and amino-substituted disilanides. The obtained Et2NPh2Si(Me3Si)2SiK·18-crown-6 was converted to a magnesium silanide and further on to Et2NPh2Si(Me3Si)2Si-substituted ziroconocene and hafnocene chlorides. In addition, an example of a silanide containing both Et2NPh2Si and FPh2Si groups was prepared with moderate selectivity. Also, the analogous germanide Et2NPh2Si(Me3Si)2GeK·18-crown-6 could be obtained.

Citric acid functionalized silane coupling versus post-grafting strategy for dual pH and saline responsive delivery of cisplatin by Fe3O4/carboxyl functionalized mesoporous SiO2 hybrid nanoparticles: A-synthesis, physicochemical and biological characterization.

Synthesis of monodisperse carboxylic acid-functionalized magnetic mesoporous silica nanoparticles is performed by either two-step sol-gel process or post-grafting using citric acid modified isocyanate silane coupling agent (MMSN-NCO-CA) or succinic anhydride modified magnetic mesoporous silica (MMSN-NH-SA). Morphology, structure and magnetic properties of bare and mesoporous silica coated Fe3O4 core were studied using various techniques such as FTIR, VSM, TEM, FESEM, XRD and N2 adsorption-desorption isotherms (BET). Cisplatin (cis-Pt) adsorption isotherms and its release profile in various media were investigated by ICP-OES. MMSN-NCO-CA with mean particle size 107 nm had lower surface area (87.5 m2/g) and larger pore size (6.9 nm) in comparison with MMSN-NH-SA (respective values of 151.2 m2/g and 3.5 nm). cis-Pt loading into particles followed a saturable adsorption with respect to the drug to particle mass ratios. More sustained release of cis-Pt was observed for MMSN-NCO-CA, though both nanoparticles exhibited a pH- and saline concentration-dependent drug release. In addition, general and cis-Pt specific cytotoxicity were examined by MTT assay in MDA-MB-231 breast cancer cell line, and to further detect apoptosis, acridine orange/ethidium bromide dual cell staining was investigated by fluorescence microscopy. In-vitro anti-tumor efficiency of cis-Pt loaded MMSN-NCO-CA and MMSN-NH-SA were similarly enhanced in comparison to free cis-Pt; however, more specific apoptotic death occurred for cis-Pt loaded MMSN-NCO-CA. Therefore, the as-synthesized citric acid functionalized core-shell magnetic mesoporous hybrid nanoparticles could be used as a promising drug carriers for cancer therapy in-vivo.