High Hydrophilic and Antibacterial Efficient UV-Curable Silicone-Containing Choline Chloride Quaternary Ammonium Salts Functionalized Materials.

Antibacterial materials with high hydrophobicity have drawbacks such as protein adsorption, bacterial contamination, and biofilm formation, which are responsible for some serious adverse health events. Therefore, antibacterial materials with high hydrophilicity are highly desired. In this paper, UV-curable antibacterial materials are prepared from silicone-containing Choline chloride (ChCl) functionalized hyperbranched quaternary ammonium salts (QAS) and tri-hydroxylethyl acrylate phosphate (TAEP). The materials show high hydrophilic performance because their water contact angle is as low as 19.3°. The materials also exhibit quite high antibacterial efficiency against S. aureus over 95.6%, fairly high transmittance over 90%, and good mechanical performance with tensile strength as high as 6.5 MPa. It reveals that it is a feasible strategy to develop antibacterial materials with low hydrophobicity from silicone-modified ChCl-functionalized hyperbranched QAS.

Rapid Access to Chiral Spiro[2.3] Lactams: Stereoselective Hydroborylation and Hydrosilylation and Remote Control of Axial Chirality by Copper-Catalyzed Desymmetrization of Spirocyclopropenes.

Chiral spirocyclopropyl ß-lactams are common motifs in bioactive compounds and pharmaceuticals. Here we disclose a diastereoselective and enantioselective hydroborylation and hydrosilylation of spirocyclopropenes, via a Cu-catalyzed desymmetrization strategy, for the rapid preparation of enantio-enriched spirocyclopropyl ß-lactams. The efficient desymmetrization strategy allows the remote control of axial chirality, offering the borylated and silylated products bearing central, spiro, and axial chirality. The combination of multichiral elements would provide a novel motif for biological evaluation in potential drug discovery.

Transition-metal-free and additive-free intermolecular hydroarylation of alkenes with indoles in hexafluoroisopropanol.

Hydroarylation of alkenes is one of the most straightforward and atom-economical strategy for the construction of multi-aryl-substituted alkanes, but systematic studies have been limited to transition metal catalysis. Here we report a hexafluoroisopropanol (HFIP)-promoted hydroarylation of alkenes with indoles without the presence of transition metal catalysts or any additive. HFIP was the only reagent used in this work, and could be easily removed via evaporation, and recovered via distillation in industry settings. This reaction was shown to provide an efficient, clean and operationally simple procedure with a remarkable substrate scope and versatile transformations, delivering a variety of multi-aryl alkanes incorporating the indole motif. In preliminary studies, several of these products showed biologically activity against cells from an array of human cancer cell lines. A mechanistic study was also carried out and suggested that the quinone methide might be the key intermediate. And in contrast to the conclusions of a previous report, the current work suggested that protonation by HFIP might not be the rate-determining step.

Silver(I)-Catalyzed Diastereoselective Hydroborylation of Cyclopropenes.

An effective (NHC)AgCl catalysis was developed in the hydroborylation of cyclopropenes with B2pin2, delivering a variety of cyclopylboronates in a stereoselective manner, which could be easily transformed for the construction of versatile cyclopropanes. This protocol works effectively under mild reaction conditions in an open-air atmosphere, and it was easy to apply on a gram scale. This novel method in detail was also explored by control experiments, providing a number of key insights. The kinetic process followed by 1H NMR indicated that the reaction was finished in 15 min. Furthermore, the mechanism of silver(I)-catalyzed hydroborylation of cyclopropenes was proposed, with the protonation by methanol as the rate-determining step.

High Tensile Strength UV-Cured Castor Oil-Based Silicone-Modified Polyurethane Acrylates.

High tensile strength UV-cured transparent materials are highly desired in optical devices. In this paper, high tensile strength UV-cured transparent castor oil-based polyurethane acrylates (PUAs) with a very high transmittance over 95% (400-800 nm) were prepared from UV-curable castor oil-based polyurethane acrylates (CO-PUAs) and mercapto silicone-containing hyperbranched polymers (HBPSHs) under UV irradiation. The tensile strengths of UV-cured transparent castor oil-based PUAs can reach 12.49 MPa, which is obviously higher than that of UV-cured CO-PUAs reported previously (0.7-10.20 MPa). The chemical structure of HBPSHs will play an important role in the mechanical performance of UV-cured silicone-modified materials, and it can be concluded that the more rigid the units of α,ß-dihydroxyl derivatives used in the fabrication of HBPSHs are, the higher the mechanical strength and pencil hardness of the UV-cured materials will be.

Sequential olefination-dimerisation of benzylic dithioacetals by the nickel-catalysed reaction with methyl Grignard or zinc reagent.

Products of main group elements from cross-coupling reactions have been shown to serve as Lewis acids, mediating further reactions of organic coupling products. Thus, the nickel-catalysed olefination of benzylic dithioacetal with MeMgI in benzene in a sealed Schlenk tube at 130 °C generates magnesium mercaptide which regioselectively converts 2-arylpropene into a dimer in good yield. Aryl iodide reacts with 2-propenylmagnesium bromide in the presence of 1,2-ethanedithiol and NiCl2(PPh3)2 to yield the same dimer. Replacement of the Grignard reagent by an organozinc reagent gives the dimers in a better yield.

A Fischer-Type Ruthenium Carbene Complex as a Metathesis Catalyst for the Synthesis of Enol Ethers.

The Grubbs G-I or G-II catalyst gives the ruthenium ethoxy carbene complex, which catalyzes ring-opening cross metathesis (ROCM) of a strained cyclic alkene to give a diene where one of the two alkene moieties in the product contains an ethoxy substituent. No polymeric products are detected. Hydrocarbons such as parent norbornene or substituted cyclopropenes can proceed with the reaction smoothly. Tertiary amines, N-alkylimides, esters, and aryl or alkyl bromides remain intact under the reaction conditions. In addition to vinyl ethers, vinylic esters can also be used. The time required to reach a 50% yield of the ROCM product t50 varies from 0.01 to 140 h depending on the strain and nucleophilicity of the double bond. Anchimeric participation of an electron-rich group would result in significant enhancement of the reactivity, and the t50 could be as short as several minutes. A similar substrate without such a neighboring group shows a much slower rate. An exo-norborne derivative reacts much faster than the corresponding endo-isomer. Alkenes with poor nucleophilicity are less favored for the ROCM process, so is less strained cyclooctene.

UV-Cured Transparent Silicone Materials with High Tensile Strength Prepared from Hyperbranched Silicon-Containing Polymers and Polyurethane-Acrylates.

Flexibility and mechanical performance are essential for transparent silicone materials applied in some optical and electronic devices; however, the tensile strength of transparent silicone materials is fairly low. To overcome this problem, a kind of UV-cured transparent flexible silicone material with quite a high tensile strength and elongation at break was developed through UV-initiated thiol-ene reaction by hyperbranched silicon-containing polymers (HBPs) with a thiol substitute and acrylate-terminated polyurethanes. Unexpectedly, it is found that both the tensile strength and elongation at break of the transparent silicone materials are extraordinarily high, which can reach 3.40 MPa and 270.0%, respectively. The UV-cured materials have good UV resistance ability because their transmittance is still as high as 93.4% (800 nm) even when aged for 40 min in a UV chamber of 10.6 mW cm-2. They exhibit outstanding adhesion to substrates, and the adhesion to a glass slide, wood, and a tin plate is grade 1. The promising results encourage us to further improve the mechanical performance of flexible transparent silicone materials by effective chemical modification strategies with HBPs. An attempt was made to apply the UV-cured materials in a Gel-Pak box and it could be proved that the UV-cured materials may be one of the good candidates for use as packaging or protecting materials of optical or electronics devices such as the Gel-Pak product.

High Efficiency and Low Migration Hyperbranched Silicone Contain Macrophotoinitiators for UV-Cured Transparent Coatings.

A kind of hyperbranched silicone containing macrophotoinitiators (HBSMIs) were synthesized from 2-hydroxy-2-methyl-1-phenyl propanone (HMPP) and the UV-curing behaviors of HBSMIs were investigated in UV-cured transparent polyurethane-acrylate (PUA) coatings. HBSMIs show higher UV-initiating efficiency than HMPP. The migration of HBSMIs from the UV-cured coatings can be as low as 1.7-6.0 wt%, which is obviously lower than the migration of HMPP. There is a remarkable improvement of the tensile strength of the UV-cured materials initiated by HBSMI in comparison to that of the materials prepared with the same PUA initiated by HMPP. Especially for the UV-cured materials prepared from PUA with 20 wt% 1,1,1-tris(hydroxymethyl)propane (TMP), the tensile strength and the strain at break increased from 6.81 MPa to 12.14 MPa and from 43.0% to 71.9%, respectively. The fraction of improvement for the tensile strength and the strain at break is as high as 78.9% and 67.2%, respectively. The coatings prepared with HBSMI also have better UV resistance ability than those coatings prepared with HMPP because they turn slightly yellow when they are aged by UV for about 15 min while the coating prepared with 4 wt% of HMPP will turn yellow only aged by UV for 2 min. These results suggest that preparation hyperbranched silicone containing macrophotoinitiators will be one of the good strategies to improve the curing efficiency of the UV-curing system, reduce the migration of UV initiator from cured material, improve the mechanical and UV resistance performance of UV-cured materials.

Polyester-Polysiloxane Hyperbranched Block Polymers for Transparent Flexible Materials.

Highly transparent flexible silicone elastomers are useful for certain stretchable electronics and various types of smart devices. Polyester-polysiloxane hyperbranched block copolymers are synthesized by ring-opening polymerization of octamethylcyclotetrasiloxane initiated by macromolecular lithium alkoxide. Treatment of these copolymers with tetraethoxysilane and dibutylin dilaurate at room temperature gives the corresponding transparent elastic materials. The transparency of the materials can reach 90% (700-800 nm), and the starting thermal decomposition temperatures of the materials are higher than 330 °C. Very interestingly, though the highest tensile strength of the material prepared is about 0.48 MPa, the elongation at break can reach 778-815%. The results will inspire us to develop highly transparent flexible silicone materials by designing copolymers of silicone materials and hyperbranched polymers.

Fabrication of Transparent UV-Cured Coatings with Allyl-Terminated Hyperbranched Polycarbosilanes and Thiol Silicone Resins.

To improve thermal stability and hardness of UV-cured materials, a series of UV-cured solvent-free coatings were prepared from allyl-terminated hyperbranched polycarbosilanes and thiol silicone resins. The silicone coatings prepared have pencil hardness of 4-9 H, water absorption no more than 0.04 wt %, and transmittance higher than 94%. The temperature for the coatings' starting thermal decomposition is higher than 236 °C; especially, that of the coating prepared with G1 is as high as 371.1 °C. The UV-cured coatings in this work exhibit much higher pencil hardness than and superior thermal stability to those reported previously.

Determination of the Orientation of Pendants on Rigid-Rod Polymers.

Bis-norbornene and bis-cyclobutene with different kinds of linkers have been extensively used for the synthesis of double stranded ladderphanes under ruthenium- or molybdenum-catalyzed ring opening metathesis polymerization (ROMP) conditions. The key to the success relies on the selective formation of comb-like polynorbornenes or polycycloubtenes, where pendants are all aligned towards similar direction. This minireview summarizes various methods (chemical methods, spectroscopic means, and nonlinear optical measurements) for determining the comb-like conformations of pendants on these rigid-rod polymers. The approach is based on the proximal relationship between adjacent pendants. Interactions between these adjacent pendants would enable a change in chemical reactivity.

UV-Cured Transparent Flexible Silicone Materials with High Tensile Strength.

Transparent flexible silicone materials are useful in electronics, sensors, coatings, and so forth. However, to the best of our knowledge, the tensile strength of unreinforced silicone rubber is lower than 0.4 MPa, and the highest tensile strength of highly transparent silicone-modified materials is no more than 1.5 MPa. The poor mechanical property limits their further application in electronic devices. Here, a kind of UV-cured transparent flexible silicone materials with tensile strength as high as 2.2 MPa were prepared by a UV-initiated thiol-ene reaction of a sulfur-containing hyperbranched polycarbosilane and a thiol silicone resin. Interestingly, their tensile strength can increase from 2.2 to 5.6 and 5.7 MPa after being immersed in an aqueous solution of 10 wt % hydrochloric acid and 10 wt % NaCl for 7 days, respectively. It is argued that the increase of the tensile strength of cured films may be attributed to the -SiOCH3 of the residual 3-trimethoxysilylpropanethiol in the sulfur-containing hyperbranched polycarbosilane. The performances of the cured materials were investigated in detail. These silicone materials exhibit transparency higher than 95% (wavenumber in the range of 400-800 nm), and the initial thermal decomposition temperatures of the cured materials are about 340 °C. These materials also show good anticorrosion property, and the mass loss of the materials immersed in the aqueous solution mediums is no more than 0.39 wt % even for 15 days.

Caterpillar-shaped polysilsesquioxanes.

The preparation of linear polysilsesquioxanes having Si-OH side groups is not trivial, because direct condensation of multifunctional silanol derivatives would lead to branched or crosslinked polymers. We have successfully prepared an unsymmetrical double-decker silsesquioxane with a silyl hydride function at one end and two silanol groups at the other. Linear POSS polymers having Si-OH side groups are obtained selectively in good yields. The properties and potential applications are briefly presented.

Selective ring-opening metathesis polymerization (ROMP) of cyclobutenes. Unsymmetrical ladderphane containing polycyclobutene and polynorbornene strands.

At 0 °C in THF in the presence of Grubbs first generation catalyst, cyclobutene derivatives undergo ROMP readily, whereas norbornene derivatives remain intact. When the substrate contains both cyclobutene and norbornene moieties, the conditions using THF as the solvent at 0 °C offer a useful protocol for the selective ROMP of cyclobutene to give norbornene-appended polycyclobutene. Unsymmetrical ladderphane having polycyclobutene and polynorbornene as two strands is obtained by further ROMP of the norbornene appended polycyclobutene in the presence of Grubbs first generation catalyst in DCM at ambient temperature. Methanolysis of this unsymmetrical ladderphane gives polycyclobutene methyl ester and insoluble polynorbornene-amide-alcohol. The latter is converted into the corresponding soluble acetate. Both polymers are well characterized by spectroscopic means. No norbornene moiety is found to be incorporated into polycyclobutene strand at all. The double bonds in the polycyclobutene strand are mainly in cis configuration (ca 70%), whereas the E/Z ratio for polynorbornene strand is 8:1.

Exceptionally Long C-C Single Bonds in Diamino-o-carborane as Induced by Negative Hyperconjugation.

The synthesis of a series of 1,2-diamino-o-carboranes (1-4) is reported. The molecular structures of these diamino-o-carboranes are remarkable as the inner-cluster C-C bonds are all ultra-long (162.7-193.1 pm) and vary substantially with small variations in the substituents. The results of quantum mechanical investigations suggest that the origin of the bond elongation is significant in-plane negative hyperconjugation of lone pairs of the nitrogen substituents with the σ* orbitals of the C-C bonds in o-carboranes.

Reactions of an Isolable Dialkylsilylene with Aroyl Chlorides. A New Route to Aroylsilanes.

The reactions of isolable dialkylsilylene 1 with aromatic acyl chlorides afforded aroylsilanes 3a-3c exclusively. Aroylsilanes 3a-3c were characterized by ¹H-, 13C-, and 29Si-NMR spectroscopy, high-resolution mass spectrometry (HRMS), and single-crystal molecular structure analysis. The reaction mechanisms are discussed in comparison with related reaction of 1 with chloroalkanes and chlorosilanes.

1,3-Diazasilabicyclo[1.1.0]butane with a Long Bridging N-N Bond.

A 1,3-diazasilabicyclo[1.1.0]butane (1) is synthesized as thermally stable crystals by using the cycloaddition reaction of an isolable dialkylsilylene with aziadamantane. The bridge N-N bond length of 1 (1.70 Å) is the longest among those of known N-N singly-bonded compounds, including side-on bridged transition-metal dinitrogen complexes. The compound 1 is intact in air but moisture sensitive. No reaction occurs with hydrogen, even under pressure at 0.5 MPa. Irradiation of 1 with light gives an isomer quantitatively by N-N and adamantyl C-C bond cleavage. The origin of the remarkable N-N bond elongation is ascribed to significant interaction between a Si-C σ* and Ν-Ν π and σ orbitals as determined by DFT calculations of model compounds.

Elusive 2H-1,2-oxasiletes through reactions of an isolable dialkylsilylene with diazocarbonyl compounds.

The reactions of isolable dialkysilylene 1 with 2-diazo-1,2-diphenylethanone and ethyl 2-diazo-2-phenylacetate gave elusive silacycles, 2H-1,2-oxasiletes 2 and 3, respectively, in high yields. Because these reactions occur at low temperatures of ca.-30 °C, initial complexation of the silylene to the carbonyl oxygen of the diazocarbonyl compounds is suggested to trigger dinitrogen elimination followed by cyclization. In contrast, a six-membered cyclic diazo compound 8 and 1-sila-2,3-diazabicyclo[3.3.0]oct-3-ene 10 were obtained in good yields by the reaction of 1 with less reactive ethyl 2-diazo-3-oxo-3-phenylpropanoate 7 and trimethylsilyldiazomethane 9. Molecular structures of 2, 3, 8 and 10 were determined by X-ray crystallography.

High-performance organic field-effect transistors based on single-crystalline microribbons of a two-dimensional fused heteroarene semiconductor.

A novel two-dimensional organic semiconductor material [1]benzothieno[3,2-b][1]benzothieno[2,1-b:3,4-b':6,5-b'':7,8-b''']tetra(benzothiophene) (BTBTTBT) which largely extends the scope of the π-conjugated framework of heteroarene through "H" configuration was synthesized and its thermal, optical and electrochemical properties were investigated. This 2D molecule enables the easy growth of single-crystalline microribbons by the physical vapor transport method, which were evidenced by XRD, SEM and TEM. The single-crystalline OFET devices were fabricated based on the individual BTBTTBT microribbon and the remarkable high mobility of 17.9 cm(2) V(-1) s(-1) and on/off ratios of over 10(7) could be achieved.