Almost Alternating Diagrams and Fibered Links in S3

Let R be a Seifert surface obtained by applying Seifert's algorithmto a connected diagram D for a link L. In this paper, lettingD be almost alternating, we give a practical algorithm to determinewhether L is a fibered link and R is a fiber surface. We furthershow that L is a fibered link and R is a fiber surface for Lif and only if R is a Hopf plumbing, that is, a successive plumbingof a finite number of Hopf bands. It has been known for sometime that this is true if D is alternating, and we show thatit is not always true if D is 2-almost alternating. In the appendix,we partially answer C. Adams's open question concerning almostalternating diagrams. 2000 Mathematical Subject Classification:57M25.     

Enantiomer-selective radical cyclopolymerization of rac-2,4-pentanediyl dimethacrylate using a ruthenium-mediated chiral atom transfer radical polymerization initiating system

The enantiomer-selective radical polymerization of rac-2,4-pentanediyl dimethacrylate, an equimolar mixture of (2S,4S)-2,4-pentanediyl dimethacrylate (SS- 1 ) and (2R,4R)-2,4-pentanediyl dimethacrylate (RR- 1 ), was carried out with a chiral atom transfer radical polymerization initiating system consisting of methyl 2-bromoisobutyrate ( 3 ), dichlorotris(triphenylphosphine)ruthenium [RuCl₂(PPh₃)₃], and a chiral additive in anisole at 60 °C. When (S)-1,1′-bi-2-naphthol ( a-3 ) was used as the chiral additive, the recovered monomer was enriched in SS- 1 , and the enantiomeric excess was 16.9% at a 22.6% monomer conversion. The specific rotation ([α]₄₃₅, c 0.3, CHCl₃) of the resulting polymer was +40.3° at a 22.6% monomer conversion. For the copolymerization of SS- 1 and RR- 1 with 3 /RuCl₂(PPh₃)₃/ a-3 in anisole at 60 °C, the monomer reactivity ratio for RR- 1 (r_R) was determined to be 4.94, and that for SS- 1 (r_S) was 0.27. For the homopolymerizations of SS- 1 and RR- 1 with 3 /RuCl₂(PPh₃)₃/ a-3 in anisole at 60 °C, the polymerization rate of RR- 1 was considerably faster than that of SS- 1 , and the rate constants for the homopolymerizations were determined to be k_SS = 2.0 × 10⁻³ h⁻¹ and k_RR = 8.2 × 10⁻³ h⁻¹, respectively. With the values of k_SS, k_RR, r_R, and r_S, the relative ratio k_SS/k_RR/k_SR/k_RS was determined to be 1.2:4.9:4.5:1, which indicated that both the growing end of SS- 1 and that of RR- 1 preferentially reacted with RR- 1 . © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4563–4569, 2004     

Bench‐Stable Stock Solutions of Silicon Grignard Reagents: Application to Iron‐ and Cobalt‐Catalyzed Radical C(sp3)–Si Cross‐Coupling Reactions

A robust method for the preparation of silicon‐based magnesium reagents is reported. The MgBr₂ used in the lithium‐to‐magnesium transmetalation step is generated in situ from 1,2‐dibromoethane and elemental magnesium in hot THF. No precipitation of MgBr₂ occurs in the heat, and transmetalation at elevated temperature leads to homogeneous stock solutions of the silicon Grignard reagents that are stable and storable in the fridge. This method avoids the preparation of silicon pronucleophiles such as Si?Si and Si?B reagents. The new Grignard reagents were applied to unprecedented iron‐ and cobalt‐catalyzed cross‐coupling reactions of unactivated alkyl bromides. The functional‐group tolerance of these magnesium reagents is excellent.     

Biochemical, molecular genetic, and structural analyses of the staphylococcal nucleoid.

The nucleoid structure of an important human pathogen, Staphylococcus aureus, was dissected by atomic force microscopy (AFM). The nucleoids dispersed on a cover glass consisted of fibrous units with two different widths of 40 and 80 nm, a feature shared with those of Escherichia coli. On the other hand, cells exposed to an oxidative stress exhibited clogged nucleoids. A knock-out of mrgA (metallo regulated genes A) encoding a staphylococcal homolog of the nucleoid compaction factor (E. coli Dps) eliminated the compaction response to the oxidative stress and reduced the susceptibilities to H2O2 and UV irradiation. We also observed that the negative supercoiling of plasmids is increased by the oxidative stress. A possible interrelation between the helical density and the nucleoid compaction is discussed in relation to the oxidative stress response.     

A porphyrin nanochannel: formation of cationic channels by a protonated saddle-distorted porphyrin and its inclusion behavior

A highly saddle-distorted dodecaphenylporphyrin dication (H4DPP2+) was revealed by X-ray crystallography to form positively charged porphyrin nanochannels which were 1 nm in diameter; chloride anion and redox-active hydroquinone could be incorporated in the channels.     

Catalytic asymmetric synthesis of alpha-amino phosphonates using enantioselective carbon-carbon bond-forming reactions

We have developed highly enantioselelctive reactions of silicon enolates with N-acyl-alpha-iminophosphonates leading to optically active alpha-amino phophonates. A copper (II)-diamine complex was shown to be effective in this reaction, and high levels of yield and selectivity were achieved. It is noteworthy that this reaction opens a way to various biologically important, optically active alpha-amino phosphonate derivatives.     

Reversible and stable redox behavior of a Pt(II) bis(dithiobenzoate)-type complex attributed to rotaxane-based stabilization

A three-dimensionally insulated Pt(II) bis(dithiobenzoate) complex with a [1]rotaxane structure was synthesized using permethylated cyclodextrins. We have confirmed macrocyclic insulation is necessary to yield the Pt(II) bis(dithiobenzoate) complex with high selectivity. Furthermore, the formed Pt(II) complex showed highly stable and reversible two-step redox behavior in cyclic voltammetry due to the three-dimensional insulation.     

The effect of neuromuscular electrical stimulation on muscle EMG activity and the initial phase rate of force development during tetanic contractions in the knee extensor muscles of healthy adult males

Objective: Neuromuscular electrical stimulation (NMES) has been noted as an effective pre- contraction for an increase of neural and muscle factors during twitch contractions. However, it is unknown if this intervention is effective for the rate of force development (RFD), which is the ability to increase joint torque strength as quickly as possible, during tetanic contractions. NMES can be safely used by anyone, but, the strength setting of NMES requires attention so as not to cause pain. Therefore, the purpose of this study investigated whether NMES at less painful levels was effective for RFD during tetanic contractions. We also investigated effect activation by analyzing electromyogram (EMG) and RFD for each phase. Methods: Eighteen healthy males were studied. Before and after NMES intervention at 10% or 20% maximal voluntary isometric contraction (MVIC) level (10%NMES, 20%NMES respectively), EMG activity and the initial phase (30-, 50-, 100-, and 200-msec) RFD were measured. Visual analog scale (VAS) was also measured as an indicator of pain during each NMES. Results: 20%NMES increased EMG activity and 30-, 50-, and 100-msec of RFD during MVIC, but could not improve 200 msec of RFD. However, 10%NMES could be failed to increase all phases RFD, but VAS was lower than that of 20% NMES. Conclusion: These results suggest that muscle pre-contraction using 20%NMES could induce moderate pain, but could be an effective intervention to improve RFD via neural factor activity.     

Synthesis of sulfonyloxy furoxans via hydroxyfuroxan ammonium salts

Furoxans are distinctive heteroaromatic compounds in that they are potentially capable of releasing nitric oxide under physiological conditions. In order to utilize the furoxan scaffold for the development of functional molecules, synthetically relevant functional groups are required for access to diverse furoxans. In this report, a facile route to furoxans with sulfonyloxy groups, which are halide surrogates, has been developed. The key features of this strategy include the synthesis and utilization of bench-stable hydroxyfuroxan salts, the use of sulfonyl anhydrides in the sulfonylation step instead of sulfonyl chlorides, and the photochemical isomerization of one regioisomer to another in order to gain access to both.