Gemini-Mediated Self-Disinfecting Surfaces to Address the Contact Transmission of Infectious Diseases.

According to both the Center for Disease Control and the World Health Organization, contact transmission is the primary transmission route of infectious diseases worldwide. Usually, this is mitigated by a schedule of repeated regular sanitization, yet surfaces are easily re-contaminated in the interim between cleanings. One solution to this problem is to generate self-disinfecting surfaces that can display sustained virucidal/antimicrobial properties against pathogens that settle upon them. Quaternary ammonium organosilicon compounds are ideal candidates to achieve this; cationic surfactants are safe and well-established surface disinfectants, while organosilanes are used broadly to form durable coatings with altered surface properties on many different materials. Despite their potential to circumvent the disadvantages of traditional disinfection methods, extant commercially available quaternary ammonium silanes do not display comparable efficacy to the standard surface disinfectants, nor have their respective coatings been demonstrated to meet the Environmental Protection Agency's guidelines for residual/extended efficacy. Inspired by the powerful surface activity of double-headed "gemini" surfactants, here, we present gemini-diquaternary silanes (GQs) with robust residual germicidal efficacy on various surfaces by incorporating a second cationic "head" to the structure of a conventional monoquaternary ammonium silane (MQ). Aqueous solutions of GQs were tested in suspension- and surface-antimicrobial assays against an array of pathogens, including Staphylococcus aureus, Escherichia coli, Pseudomonas aeruginosa, and severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2). GQ performance was benchmarked against the common disinfectants, ethanol, hydrogen peroxide, hypochlorite, as well as MQ. Solutions of GQs were efficacious when used for immediate disinfection (>106-fold reduction in 15 s). Additionally, GQs were demonstrated to impart durable self-disinfecting properties to a variety of porous and nonporous surfaces, effective after repeated cycles of abrasion and repeated contaminations, and with superior coating ability and activity (>108 higher activity) than that of MQs. GQs as surface treatments show great promise to overcome the limitations of traditional disinfectants in preventing the spread of infectious diseases.

Mechanically Competent Chitosan-Based Bioadhesive for Tendon-to-Bone Repair.

Current suture-based surgical techniques used to repair torn rotator cuff tendons do not result in mechanically competent tendon-to-bone attachments, leading to high postoperative failure rates. Although adhesives have been proposed to protect against sutures tearing through tendon during healing, no currently available adhesive meets the clinical needs of adhesive strength, biocompatibility, and promotion of healing. Here, a biocompatible, graded, 3,4-dihydroxy phenyl chitosan (BGC) bioadhesive designed to meet these needs is presented. Although 3,4-dihydroxy phenyl chitosan (DP-chitosan) bioadhesives are biocompatible, their adhesion strength is low; soluble oxidants or cross-linking agents can be added for higher bonding strength, but this sacrifices biocompatibility. These challenges are overcome by developing a periodate-modified ion exchange resin-bead filtration system that oxidizes catechol moieties to quinones and filters off the activating agent and resin. The resulting BGC bioadhesive exhibited sixfold higher strength compared to commercially available tissue adhesives, with strength in the range necessary to improve tendon-to-bone repair (≈1MPa, ≈20% of current suture repair strength). The bioadhesive is biocompatible and promoted tenogenesis; cells exposed to the bioadhesive demonstrated enhanced expression of collagen I and the tenogenic marker Scx. Results demonstrated that the bioadhesive has the potential to improve the strength of a tendon-to-bone repair and promote healing.

Synthesis of Functionalized 1,3-Butadienes via Pd-Catalyzed Cross-Couplings of Substituted Allenic Esters in Water at Room Temperature.

An environmentally responsible, mild method for the synthesis of functionalized 1,3-butadienes is presented. It utilizes allenic esters of varying substitution patterns, as well as a wide range of boron-based nucleophiles under palladium catalysis, generating sp-sp2, sp2-sp2, and sp2-sp3 bonds. Functional group tolerance measured via robustness screening, along with room temperature and aqueous reaction conditions highlight the methodology's breadth and potential utility in synthesis.

B-Alkyl sp3-sp2 Suzuki-Miyaura Couplings under Mild Aqueous Micellar Conditions.

Use of B-sp3-alkyl reagents for Suzuki-Miyaura couplings under aqueous micellar catalysis conditions is reported. Studies as to substrate scope, use in a four-step one-pot sequence, and reaction medium recycling exemplify the synthetic utility of this technology. OBBD ( B-alkyl-9-oxa-10-borabicyclo[3.3.2]decane) derivatives are easily made and utilized for couplings under mild conditions. Comparisons were also made between OBBD and 9-BBN ( B-alkyl-9-borabicyclo[3.3.1]nonane) derivatives as reaction partners.

Control of Chemo-, Regio-, and Enantioselectivity in Copper Hydride Reductions of Morita-Baylis-Hillman Adducts.

Nonracemically ligated copper hydride can be used to effect tandem SN2'/1,2-reductions of racemic Morita-Baylis-Hillman (MBH) acetates to access enantioenriched chiral allylic alcohols with defined olefin geometry. MBH esters, including those with ß-substitution, can be transformed to stereodefined enoates by taking advantage of a bulky, oligomeric, in situ generated trialkoxysiloxane leaving group. Finally, an atypical conversion of easily arrived at MBH alcohol derivatives to nonracemic allylic alcohols is disclosed.

Synthesis of Functionalized [3], [4], [5] and [6]Dendralenes through Palladium-Catalyzed Cross-Couplings of Substituted Allenoates.

A mild method for the synthesis of highly functionalized [3]-[6]dendralenes is reported, representing a general strategy to diversely substituted higher homologues of the dendralenes. The methodology utilizes allenoates bearing various substitution patterns, along with a wide range of boron and alkenyl nucleophiles that couple under palladium catalysis leading to sp-, sp2 -, and sp3 -substituted arrays. Regioselective transformations of the newly formed unsymmetrical dendralene derivatives are demonstrated. The use of micellar catalysis, where water is the global reaction medium, and room temperature reaction conditions, highlights the green nature of this technology.

Molecularly Smooth Self-Assembled Monolayer for High-Mobility Organic Field-Effect Transistors.

Despite the need for molecularly smooth self-assembled monolayers (SAMs) on silicon dioxide surfaces (the most common dielectric surface), current techniques are limited to nonideal silane grafting. Here, we show unique bioinspired zwitterionic molecules forming a molecularly smooth and uniformly thin SAM in "water" in <1 min on various dielectric surfaces, which enables a dip-coating process that is essential for organic electronics to become reality. This monomolecular layer leads to high mobility of organic field-effect transistors (OFETs) based on various organic semiconductors and source/drain electrodes. A combination of experimental and computational techniques confirms strong adsorption (Wad > 20 mJ m-2), uniform thickness (∼0.5 or ∼1 nm) and orientation (all catechol head groups facing the oxide surface) of the "monomolecular" layers. This robust (strong adsorption), rapid, and green SAM represents a promising advancement toward the next generation of nanofabrication compared to the current nonuniform and inconsistent polysiloxane-based SAM involving toxic chemicals, long processing time (>10 h), or heat (>80 °C).

Nucleophilic Aromatic Substitution Reactions in Water Enabled by Micellar Catalysis.

Given the huge dependence on dipolar, aprotic solvents such as DMF, DMSO, DMAc, and NMP in nucleophilic aromatic substitution reactions (SNAr), a simple and environmentally friendly alternative is reported. Use of a "benign-by-design" nonionic surfactant, TPGS-750-M, in water enables nitrogen, oxygen, and sulfur nucleophiles to participate in SNAr reactions. Aromatic and heteroaromatic substrates readily participate in this micellar catalysis, which takes place at or near ambient temperatures.

Copper-catalyzed hydrophosphinations of styrenes in water at room temperature.

Copper-catalyzed hydrophosphinations of styrenyl systems in water, at room temperature is herein reported, enabled by our 'designer' surfactant TPGS-750-M. This is an attractive alternative to the more common Pd and Pt catalyzed versions.

Stereoselective silylcupration of conjugated alkynes in water at room temperature.

Micellar catalysis enables copper-catalyzed silylcupration of a variety of electron-deficient alkynes, thereby providing access to isomerically pure E- or Z-ß-silyl-substituted carbonyl derivatives. These reactions take place in minutes, afford high yields and stereoselectivity, and are especially tolerant of functional groups present in the substrates. The aqueous reaction medium has been successfully recycled several times, and a substrate/catalyst ratio of 10,000:1 has been documented for this methodology.