Electrophile‐Induced Nucleophilic Substitution of the nido‐Dicarbaundecaborate Anion nido‐7,8‐C2B9H12− by Conjugated Heterodienes

Substitution of the dicarbaundecaborate anion nido‐7,8‐C₂B₉H₁₂^? ( 1 ) by precise hydride abstraction followed by nucleophilic attack usually leads to symmetric products 10‐R‐nido‐7,8‐C₂B₉H₁₁. However, thioacetamide (MeC(S)NH₂) as nucleophile and acetone/AlCl₃ as hydride abstractor gave asymmetric 9‐[MeC(NHiPr)S]‐nido‐7,8‐C₂B₉H₁₁ ( 2 ), whereas N,N‐dimethylthioacetamide (MeC(S)NMe₂) gave the expected symmetric 10‐[MeC(NMe₂)S]‐nido‐7,8‐C₂B₉H₁₁ ( 4 ). For the formation of 2 , acetone and thioacetamide are assumed to give the intermediate MeC(S)N(CMe₂) ( 3 ), which then attacks 1 with formation of 2 . Similarly, reaction of acetyliminium chloride [MeC(O)NH(CPh₂)]Cl ( 5 ) with 1 in THF gave a mixture of 9‐ and 10‐substituted [MeC(NHCHPh₂)O]‐nido‐7,8‐C₂B₉H₁₁ ( 6 and 7 , respectively). These reactions are the first examples in which compounds (here heterodienes) that unite the functionalities of both hydride acceptor and nucleophilic site react with 1 in a bimolecular fashion. Furthermore, the analogous reaction of 1 and 5 (in an equilibrium mixture with acetyl chloride and benzophenone imine) in MeCN afforded 10‐[MeC(NCPh₂)NH]‐nido‐7,8‐C₂B₉H₁₁ ( 8 ) and MeC(O)NHCHPh₂ ( 9 ).     

Thermal,Mechanical and Morphological Behavior of Poly(propylene)/Wood Flour Composites

The comparative studies on the thermal, mechanical and morphological behavior of compression molded poly(propylene) (PP)/wood flour (WF) composites were performed using wood flours (WFs) of different origins. The comparison has been made on the basis of results obtained from thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), scanning electron microscopy (SEM) and tensile testing. It has been demonstrated that an addition of 5 wt.-% of maleic anhydride grafted polypropylene (PP-g-MA) has a significant effect on the morphological and thermomechanical behavior of the composites. Although, microscopic examinations revealed no significant differences in the morphology of the compatibilized composites, a remarkable improvement of thermal degradation behavior was observed. From the view point of mechanical properties, the composites with high amount of filler (60 wt.-%) showed similar behavior irrespective of the origin of wood flour.     

Photoresponsive Circular Supramolecular Polymers: A Topological Trap and Photoinduced Ring‐Opening Elongation

Topological features of one‐dimensional macromolecular chains govern the properties and functionality of natural and synthetic polymers. To address this issue in supramolecular polymers, we synthesized two topologically distinct supramolecular polymers with intrinsic curvature, circular and helically folded nanofibers, from azobenzene‐functionalized supramolecular rosettes. When a mixture of circular and helically folded nanofibers was exposed to UV light, selective unfolding of the latter open‐ended supramolecular polymers was observed as a result of the curvature‐impairing internal force produced by the trans‐to‐cis photoisomerization of the azobenzene. This distinct sensitivity suggests that the topological features of supramolecular polymers define their mechanical stability. Furthermore, the exposure of circular supramolecular polymers in more polar media to UV irradiation resulted in ring opening followed by chain elongation, thus demonstrating that the circular supramolecular polymer can function as a topological kinetic trap.     

Studies of S-But-3-ynyl and gem-Dimethyl S-But-3-ynyl Thioglycoside Donors in Gold-Catalyzed Glycosylations

Gold-catalyzed glycosylation using S-but-3-ynyl and gem-dimethyl S-but-3-ynyl thioglycoside donors has been investigated for the synthesis of various types of complex oligosaccharides. It was found that 2,2-dimethyl S-but-3-ynyl thioglycoside donors are more reactive than their S-but-3-ynyl thioglycoside counterparts and gave the glycoside products in relatively higher yields.     

Current progresses and trends in carbon nanomaterials-based electrochemical and electrochemiluminescence biosensors

The enormous potential of biosensors in medical diagnostics has motivated scientists to develop newer innovative tools and advance biosensing technologies. The use of cell, organelles, nucleotides, aptamers, antibodies, affibodies, proteins, peptides, molecules, and printed polymers, merged with nanotechnology, offers excellent tools to prepare highly sensitive and advanced biosensors. Therefore, the current decade has witnessed a rapid surge in the fabrication of different nanomaterial-based biosensors. Among them, carbon nanomaterials (CNMs) have emerged highly attractive in the fabrication of both electrochemical and electrochemiluminescence (ECL) biosensors. On one hand, CNMs bear prominent electrical conductivity, large surface area to immobilize adequate amount of biomolecules, an enhanced loading capacity, improved biocompatibility, and active site for electrochemical reaction. Additionally, CNMs could be chemically modified for the covalent coupling with the biomolecules. On the other hand, both electrochemical and ECL biosensors allow for cost-effective, rapid, and real-time detection with excellent sensitivity and selectivity, with the capability of integrating different biomolecules and CNMs on the same chip. However, currently there is not a single review, which includes CNM-based electrochemical and ECL biosensors' current progress and trends. Therefore, this review intends to survey the current progress and future trends in CNM-based electrochemical and ECL biosensors.     

Synthesis,structural and chemosensitivity studies of arene d6 metal complexes having N‐phenyl‐N´‐(pyridyl/pyrimidyl)thiourea derivatives

The d⁶ metal complexes of thiourea derivatives were synthesized to investigate its cytotoxicity. Treatment of various N‐phenyl‐N´ pyridyl/pyrimidyl thiourea ligands with half‐sandwich d⁶ metal precursors yielded a series of cationic complexes. Reactions of ligand (L1‐L3) with [(p‐cymene)RuCl₂]₂ and [Cp*MCl₂]₂ (M = Rh/Ir) led to the formation of a series of cationic complexes bearing general formula [(arene)M(L1)к²_(N,S)Cl]⁺, [(arene)M(L2)к²_(N,S)Cl]⁺ and [(arene)M(L3)к²_(N,S)Cl]⁺ [arene = p‐cymene, M = Ru ( 1 , 4 , 7 ); Cp*, M = Rh ( 2 , 5 , 8 ); Cp*, Ir ( 3 , 6 , 9 )]. These compounds were isolated as their chloride salts. X‐ray crystallographic studies of the complexes revealed the coordination of the ligands to the metal in a bidentate chelating N,S‐ manner. Further the cytotoxicity studies of the thiourea derivatives and its complexes evaluated against HCT‐116 (human colorectal cancer), MIA‐PaCa‐2 (human pancreatic cancer) and ARPE‐19 (non‐cancer retinal epithelium) cancer cell lines showed that the thiourea ligands displayed no activity. Upon complexation however, the metal compounds possesses cytotoxicity and whilst potency is less than cisplatin, several complexes exhibited greater selectivity for HCT‐116 or MIA‐PaCa‐2 cells compared to ARPE‐19 cells than cisplatin in vitro. Rhodium complexes of thiourea derivatives were found to be more potent as compared to ruthenium and iridium complexes.     

Detoxification of Organosolv-Pretreated Pine Prehydrolysates with Anion Resin and Cysteine for Butanol Fermentation

Bioconversion of lignocellulose to biofuels suffers from the degradation compounds formed during pretreatment and acid hydrolysis. In order to achieve an efficient biomass to biofuel conversion, detoxification is often required before enzymatic hydrolysis and microbial fermentation. Prehydrolysates from ethanol organosolv-pretreated pine wood were used as substrates in butanol fermentation in this study. Six detoxification approaches were studied and compared, including overliming, anion exchange resin, nonionic resin, laccase, activated carbon, and cysteine. It was observed that detoxification by anion exchange resin was the most effective method. The final butanol yield after anion exchange resin treatment was comparable to the control group, but the fermentation was delayed for 72 h. The addition of Ca(OH)₂ was found to alleviate this delay and improve the fermentation efficiency. The combination of Ca(OH)₂ and anion exchange resin resulted in completion of fermentation within 72 h and acetone–butanol–ethanol (ABE) production of 11.11 g/L, corresponding to a yield of 0.21 g/g sugar. The cysteine detoxification also resulted in good detoxification performance, but promoted fermentation towards acid production (8.90 g/L). The effect of salt on ABE fermentation was assessed and the possible role of Ca(OH)₂ was to remove the salts in the prehydrolysates by precipitation.     

Cu−NHC Complex for Chan-Evans-Lam Cross-Coupling Reactions of N-Heterocyclic Compounds and Arylboronic Acids

An efficient copper(II) N-heterocyclic carbene (NHC) complex with an NCN coordination mode was optimized to catalyze the Chan–Evans-Lam (CEL) cross-coupling reaction of imidazole and other N-heterocyclic nucleophiles with arylboronic acid. This air-stable copper catalyst shows robust catalytic performance and tolerates a diverse array of functional groups on both the N-nucleophile and arylboronic acid coupling partners in C−N bond forming reactions with up to 95 % yield. Formation of the Cu−NHC complex in situ generated similar catalytic performance for CEL coupling. Alternative metal ions (Mn²⁺, Fe²⁺, Co²⁺, Ni²⁺, Zn²⁺, Ru²⁺, and Pd²⁺) were also screened in the presence of the NHC precursor as CEL catalysts.     

Adducts of Bicyclic (Alkyl)(Amino)Carbene with ECl3 and Three Electron Reduction Thereof: Syntheses of BICAAC Stabilized E−E Bonded Compounds (E=P,Sb)

The stoichiometric reaction of bicyclic (alkyl)(amino)carbene (BICAAC) with group 15 chlorides, ECl₃ (E=P, Sb) to form the Lewis adducts BICAAC:ECl₃ (E=P ( 1 ), Sb ( 2 )) has been investigated in the present work. The BICAAC smoothly reacts with PPhCl₂ to form [BICAAC:PPhCl₂] which on in-situ two electron reduction with 2 equivalents of KC₈ afforded the phosphinidene complex, BICAAC=P-Ph ( 3 ). Complete dechlorination of the BICAAC-ECl₃ adducts 1 and 2 with 3 equivalents of KC₈ leads to three-electron reduction to afford low-valent trans bent bis(BICAAC)E₂ complexes (E=P ( 4 ) and Sb ( 5 )). These complexes are the first examples of BICAAC adducts with pnictogens and all the complexes have been characterized by different spectroscopic techniques and their solid-state structure have been elucidated by single crystal X-ray diffraction.     

Formation of linkage isomers via the substitution of halides by selenocyanate in ruthenium(III) complexes

Summary Substitution of the halide ion of [Ru(NH₃)₅X]²⁺ (X=Cl^– or Br^–) by SeCN^– was monitored spectrophotometrically between 45 and 60° C in aqueous medium. The pseudo-first order rate constants were evaluated by Guggenheim's procedure, which shows linearity for 2–3 half-lives. The rate increases linearly with [SeCN^–] and all the plots have a positive intercept on the rate axis. The SeCN^–-independent path represents aquation and the SeCN^–-dependent path represents anation of the aqua complex with simultaneous formation of two isomeric (the N bonded and the Se bonded) products. The formation of the isomeric products is entropy controlled.