Coupling of the relaxation and resonant elements in the autonomous chaotic relaxation oscillator (ACRO)

If a harmonic oscillator is embedded in a relaxation oscillator, the resulting system may behave like an autonomous chaotic relaxation oscillator (ACRO). The discharge transient of the relaxation oscillator excites sinusoidal oscillations in the harmonic oscillator and these sinusoids affect when the next discharge occurs. This can lead to chaotic intervals in the oscillator periods. A simple electronic model of the ACRO is studied over a wide range of parameters using numerical, analytic, and experimental techniques. The dynamics of the ACRO is found to be determined by three parameters: (1) tuning, (2) coupling, and (3) damping. Complex, intermittent outputs can always be inhibited by increasing the damping of the harmonic oscillator. For weak damping, strong coupling yields chaotic periods. With weak damping and weak coupling, complex behavior only occurs if the relaxation oscillator is tuned near a resonance of the harmonic oscillator. A new path to chaos, called a disruption bifurcation, is the source for intermittency in the ACRO. This bifurcation occurs when the amplitude of internal resonances is excited to the degree that existing limit cycles are disrupted.     

Rearrangement reactions of the transient lewis acids (CF(3))(3)B and (CF(3))(3)BCF(2): an experimental and theoretical study

Short-lived (CF(3))(3)B and (CF(3))(3)BCF(2) are generated as intermediates by thermal dissociation of (CF(3))(3)BCO and F(-) abstraction from the weak coordinating anion [B(CF(3))(4)](-), respectively. Both Lewis acids cannot be detected because of their instability with respect to rearrangement reactions at the B-C-F moiety. A cascade of 1,2-fluorine shifts to boron followed by perfluoroalkyl group migrations and also difluorocarbene transfer reactions occur. In the gas phase, (CF(3))(3)B rearranges to a mixture of linear perfluoroalkyldifluoroboranes C(n)()F(2)(n)()(+1)BF(2) (n = 2-7), while the respective reactions of (CF(3))(3)BCF(2) result in a mixture of linear (n = 2-4) and branched monoperfluoroalkyldifluoroboranes, e.g., (C(2)F(5))(CF(3))FCBF(2). For comparison, the reactions of [CF(3)BF(3)](-) and [C(2)F(5)BF(3)](-) with AsF(5) are studied, and the products in the case of [CF(3)BF(3)](-) are BF(3) and C(2)F(5)BF(2) whereas in the case of [C(2)F(5)BF(3)](-), C(2)F(5)BF(2) is the sole product. In contrast to reports in the literature, it is found that CF(3)BF(2) is too unstable at room temperature to be detected. The decomposition of (CF(3))(3)BCO in anhydrous HF leads to a mixture of the new conjugate Br?nsted-Lewis acids [H(2)F][(CF(3))(3)BF] and [H(2)F][C(2)F(5)BF(3)]. All reactions are modeled by density functional calculations. The energy barriers of the transition states are low in agreement with the experimental results that (CF(3))(3)B and (CF(3))(3)BCF(2) are short-lived intermediates. Since CF(2) complexes are key intermediates in the rearrangement reactions of (CF(3))(3)B and (CF(3))(3)BCF(2), CF(2) affinities of some perfluoroalkylfluoroboranes are presented. CF(2) affinities are compared to CO and F(-) affinities of selected boranes showing a trend in Lewis acidity, and its influence on the stability of the complexes is discussed. Fluoride ion affinities are calculated for a variety of different fluoroboranes, including perfluorocarboranes, and compared to those of the title compounds.     

Synthesen und NMR‐Untersuchungen von Salzen mit den neuen Anionen [PtXn(CF3)6‐n]2— (n = 0 ‐ 5, X = F,OH, Cl,CN) und die Kristallstrukturanalyse von K2[(CF3)2F2Pt(μ‐OH)2PtF2(CF3)2]·2H2O

Syntheses and NMR Spectroscopic Ivestigations of Salts containing the Novel Anions [PtX_n(CF₃)_6‐n]^2— (n = 0 ‐ 5, X = F, OH, Cl, CN) and Crystal Structure of K₂[(CF₃)₂F₂Pt(μ‐OH)₂PtF₂(CF₃)₂]·2H₂O The first syntheses of trifluoromethyl‐complexes of platinum through fluorination of cyanoplatinates are reported. The fluorination of tetracyanoplatinates(II), K₂[Pt(CN)₄], and hexacyanoplatinates(IV), K₂[Pt(CN)₆], with ClF in anhydrous HF leads after working up of the products to K₂[(CF₃)₂F₂Pt(μ‐OH)₂PtF₂(CF₃)₂]·2H₂O. The structure of the salt is determined by a X‐ray structure analysis, P2₁/c (Nr. 14), a = 11.391(2), b = 11.565(2), c = 13.391(3)Å, β = 90.32(3)°, Z = 4, R₁ = 0.0326 (I > 2σ(I)). The reaction of [Bu₄N]₂[Pt(CN)₄] with ClF in CH₂Cl₂ generates mainly cis‐[Bu₄N]₂[PtCl₂(CF₃)₄] and fac‐[Bu₄N]₂[PtCl₃(CF₃)₃], but in contrast that of [Bu₄N]₂[Pt(CN)₆] with ClF in CH₂Cl₂ results cis‐[Bu₄N]₂[PtX₂(CF₃)₄], [Bu₄N]₂[PtX(CF₃)₅] (X = F, Cl) and [Bu₄N]₂[Pt(CF₃)₆]. In the products [Bu₄N]₂[PtX_n(CF₃)_6‐n] (X = F, Cl, n = 0—3) it is possibel to exchange the fluoro‐ligands into chloro‐ and cyano‐ligands by treatment with (CH₃)₃SiCl und (CH₃)₃SiCN at 50 °C. With continuing warming the trifluoromethyl‐ligands are exchanged by chloro‐ and cyano‐ligands, while as intermediates CF₂Cl and CF₂CN ligands are formed. The identity of the new trifluoromethyl‐platinates is proved by ¹⁹⁵Pt‐ and ¹⁹F‐NMR‐spectroscopy.     

Enhancing 2-iodoxybenzoic acid reactivity by exploiting a hypervalent twist

A rearrangement of hypervalent bonds, or twisting, proves to be the rate-determining step in the 2-iodoxybenzoic acid (IBX) oxidation of alcohols. From this insight, derived from density functional theory calculations, we explain why IBX oxidizes large alcohols faster than small ones and propose a modification to the reagent predicted to make it more active.     

Recognition and catalysis in allylic alkylations

[structure: see text] A cavitand outfitted with a chelated palladium atom catalyzes allylic alkylation reactions. Molecular recognition by the cavitand distinguishes between closely related structures and results in subtle substrate specificities.     

Synthesis and characterization of novel elastomeric poly(D,L-lactide urethane) maleate composites for bone tissue engineering

Here, we report the synthesis and characterization of a novel 4-arm poly(lactic acid urethane)-maleate (4PLAUMA) elastomer and its composites with nano-hydroxyapatite (nHA) as potential weight-bearing composite. The 4PLAUMA/nHA ratios of the composites were 1:3, 2:5, 1:2 and 1:1. FTIR and NMR characterization showed urethane and maleate units integrated into the PLA matrix. Energy dispersion and Auger electron spectroscopy confirmed homogeneous distribution of nHA in the polymer matrix. Maximum moduli and strength of the composites of 4PLAUMA/nHA, respectively, are 1973.31 ± 298.53 MPa and 78.10 ± 3.82 MPa for compression, 3630.46 ± 528.32 MPa and 6.23 ± 1.44 MPa for tension, 1810.42 ± 86.10 MPa and 13.00 ± 0.72 for bending, and 282.46 ± 24.91 MPa and 5.20 ± 0.85 MPa for torsion. The maximum tensile strains of the polymer and composites are in the range of 5–93%, and their maximum torsional strains vary from 0.26 to 0.90. The composites exhibited very slow degradation rates in aqueous solution, from approximately 50% mass remaining for the pure polymer to 75% mass remaining for composites with high nHA contents, after a period of 8 weeks. Increase in ceramic content increased mechanical properties, but decreased maximum strain, degradation rate, and swelling of the composites. Human bone marrow stem cells and human endothelial cells adhered and proliferated on 4PLAUMA films and degradation products of the composites showed little-to-no toxicity. These results demonstrate that novel 4-arm poly(lactic acid urethane)-maleate (4PLAUMA) elastomer and its nHA composites may have potential applications in regenerative medicine.     

Vinylimidazole‐based asymmetric ion pair comonomers: Synthesis,polymerization studies and formation of ionically crosslinked PMMA

Vinylimidazole‐based asymmetric ion pair comonomers ( IPC s) which are free from nonpolymerizable counter ions have been synthesized, characterized and polymerized by free radical polymerization (FRP), atom transfer radical polymerization (ATRP), and reversible addition‐fragmentation chain transfer (RAFT) mediated polymerizations in solution and by dispersion polymerization in water. The asymmetric nature of IPC s is due to the fact that cationic component of these IPCs is derived from vinylimidazole (VIm) and anionic component is derived from either styrenesulfonate (SS) or 2‐acrylamido‐2‐methyl‐1‐propanesulfonate. Although under ATRP, conversions are either very low or negligible, FRP and RAFT produces polymers with high to moderate monomer conversions but with different solubility characteristics. This investigation provides insight to the polymerization behavior of each component of the asymmetric IPCs and also its effects on composition and solubility characteristics of the resulting polymers. The IPCs studied here are high temperature ionic liquid and thus the polymers synthesized from these IPCs are highly ionic in nature and possess very strong intermolecular interactions which makes some of these IPC based polymers completely insoluble in organic and aqueous solvents. This highly ionic interaction is exploited to synthesize ionically crosslinked PMMA. MMA on copolymerization with 5–6 mol % of IPC yielded copolymer which is insoluble in common organic solvents like THF, DMF, etc., unlike homo PMMA. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 3260–3273