Synthesis and properties of conjugated polymers containing 3,9‐carbazolylene and silylenevinylene moieties in the main chain

Novel conjugated polymers containing 3,9‐carbazolylene and silylenevinylene moieties were synthesized by the hydrosilylation polymerization of 1,4‐bis(3‐ethynyl‐9‐carbazolyl)benzene ( 1 ) with various bis(hydrosilane)s or dihydrosilanes using a rhodium catalyst. Polymers with weight‐average molecular weights ranging from 5400 to 20,000 were obtained in 55–97% yields by the polyaddition with a rhodium catalyst in toluene at 25 °C for 24 h. All the polymers were soluble in CHCl₃ and THF, and had predominantly trans‐structures. The polymers exhibited λ_max at a longer wavelength region than 1 , and emitted fluorescence in 14–50% quantumn yields. The polymers were oxidized and reduced in the region of 0.4–1.6 V, and thermally stable up to 200 °C under air. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 1815–1821, 2010     

Charge transport in boron-doped nano MOSFETs: Towards single-dopant electronics

We investigate the hole transport in p-channel field-effect transistors doped with boron, at low temperatures (6-28 K). In transistors with a relatively large dimension, we observe the acceptor-mediated hopping and carrier freezeout, both of which are strongly influenced by the gate bias. In nanoscale transistors, these features turn into single-charge tunneling, i.e., the trapping/detrapping of single holes by/from individual acceptors. The statistics of the appearance of the modulation in a few ten samples indicates that the number of acceptors is small, or even just one, indicating that what we have observed is single-charge-transistor operation by a single-acceptor quantum dot.     

Behavior of the effective fields for a regular ising model on the Cayley tree

A regular Ising model with nearest-neighbor interactions ofJ and–J(J>0) on a Cayley tree of coordination number 3 is investigated for the behavior of effective fields in a uniform external field. The effective fields show periodic and also aperiodic structures in the temperature-field plane. At absolute zero temperature, the equations determining effective fields are reduced to a nonlinear, one-dimensional, iterative equation. Arithmetic furcations of period and a screening of the furcations are observed.     

Synthesis of 6-substituted 9-benzyl-8-hydroxypurines with potential interferon-inducing activity

Various 6-substituted 9-benzyl-8-hydroxypurines were synthesized in order to investigate the structure-activity relationship at the 6-position of 9-benzyl-8-hydroxyadenine (1), which is a lead compound for the screening of interferon (IFN)-inducing activity. 6-Unsubstituted, mercapto-, methylthio- and hydroxy-9-benzyl-8-hydroxypurines (2-5) were prepared from 5-amino-1-benzyl-4-cyano-2-hydroxyimidazole (9). Synthesis of a 6-methoxy analog (6) was conducted from 5-amino-4-benzylamino-6-chloropyrimidine (13). 6-Alkylamino and acylaminopurines (7 and 8) were also prepared by alkylation and acylation of 1, respectively. Since these compounds (2-8) indicated no activity, it was found that a free amino group of 1 is required for the expression of IFN-inducing activity.     

Ring transformation of pyrimidines to pyridines. Synthesis of 4-alkylaminopyridin-2-ones by alkaline hydrolysis of 6-(2-dimethylaminovinyl)uracils

Alkaline hydrolysis of 1,3-disubstituted 6-(2-dimethylaminovinyl)uracils 2 induced a novel ring transformation giving 4-alkylaminopyridin-2-ones 3 via ring-opening and ring-closure processes. The 4-methylamino-3-nitropyridin-2-one ( 3a ) thus obtained was employed for the synthesis of 3-deazahypoxanthine derivative 8. 4-Alkylamino-3-cyanopyridin-2-ones 11 , ricinine analogs, were also prepared by the reaction of 4-chloro-3-cyano-1-methylpyridin-2-one ( 10 ) with amines.     

Synthesis of amphiphilic particles in the presence of inert solvents and their application to lipase immobilization

To develop monodisperse amphiphilic polymer particles on which a large amount of lipase could be immobilized, we performed seed polymerizations of glycidyl methacrylate and allyl methacrylate in the presence of nonpolar inert and polar inert solvents. The amphiphilic porous polymer particles, which had both hydrophilic guanidino groups and hydrophobic stearoyl groups, were synthesized in the presence of n‐decane and had a large amount of macropores with diameters of 50–1000 nm. The amount of lipase immobilized on the amphiphilic particles synthesized in the presence of n‐decane was 3.85 times that of the lipase immobilized on the amphiphilic particles synthesized in the absence of a solvent. The immobilized lipase prepared with the amphiphilic particles synthesized in the presence of n‐decane exhibited a high transesterification activity in n‐hexane and could be used repeatedly without a considerable activity loss. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 874–884, 2002; DOI 10.1002/pola.10178     

A correlation between spin state and electrochemical electron-transfer rate for tris(N,N-disubtituted dithiocarbamato) iron(III) complexes

The electrochemical electron-transfer rate constants for the redox systems Fe(IV)L₃⁺/Fe(III)L₃ (L=N,N-disubstituted dithicarbamate ion) and Fe(III)L₃/Fe(II)L₃^? with a variety of substituents were measured at a platinum electrode in acetonitrile with the galvanostatic double-pulse method. It is known that each of the Fe(III) complexes exists both in a highspin state ⁶A₁ and a low-spin state ²T₂ in equilibirium of which position is widely changed by a subtle change in substituent. The standard rate constants for Fe(IV)L₃⁺/Fe(III)L₃ were larger or smaller than those for Fe(III)L₃/Fe(II)L₃^? according as the Fe(III)L₃ complexes are predominantly low- or high-spin complexes. Since the Fe(IV) and Fe(II) complexes are low-and high-spin complexes respectively, these findings suggest that electrochemical electron-transfer reactions accompanied by a spin-state change are slower than those without it. Such spin-state effect on electrode reactions has rarely been discussed so far.     

Pruned optical banyan networks on vertical stacking scheme for faster connection establishment

In this paper, we address the issue of faster connection establishment in a large vertically stacked optical Banyan (VSOB) network. The best known global routing algorithm, which turns an N × N crosstalk-free VSOB network into a rearrangeably non-blocking one, has time complexity O (NlogN). This is quite large compared to O (NlogN) time complexity of a single plane banyan network, which is a self-routing network with very high blocking probability. For a large size of switching network this O (NlogN) time complexity may result unacceptably long delay. Therefore, an optical network with very low blocking probability and O (NlogN) time complexity will be useful. Previously proposed Plane Fixed Routing (PFR) algorithm has O (logN) time complexity but results in higher than 2% blocking probability with zero-crosstalk constraint for a network as large as 4096 × 4096 at full load. In this paper, first we propose the pruning of VSOB networks that reduces the hardware cost by almost 30%. The networks can still use the PFR algorithm and results in the same blocking probability. However, we show that the blocking probability can be reduced dramatically while keeping the optimum time complexity O (logN) by allowing only a small amount of crosstalk. Then, we propose a new kind of switching networks in which extra regular banyan planes have been added with the pruned VBOS (P-VSOB) networks. Necessary routing algorithms, namely, PFR_RS and PFR_LS show that this new switching network can reduce the blocking probability to very low value even with zero-crosstalk constraint while keeping the hardware cost 3almost the same as for P-VSOB networks. Both these algorithms also have time complexity O (NlogN).