Design of a widely tunable laser with a chirped ladder filter

We theoretically investigated a digitally tunable laser with a chirped ladder filter and a ring resonator to obtain a wide wavelength tuning range covering the whole C- or L- band. The clear relation between the tuning range and laser structure, especially the ladder filter, is described analytically. The introduction of a chirped structure into a ladder filter is effective in achieving both wide tunability and a stable lasing mode. A numerical simulation based on multimode rate equations shows that a tuning range of over 40 nm and a mode suppression ratio over 40 dB can be achieved by introducing a chirped ladder filter.     

Synthesis and properties of furo[4,3,2-de][1]benzopyran

A new heterocycle, furo[4,3,2-de][1]benzopyran ( 2 ), was synthesized. A key step in the sequence was the allylic bromination of 3,4-dihydrofuro[4,3,2-de][1]benzopyran ( 8 ) to give 3-bromo-3,4-dihydrofuro[4,3,2-de][1]-benzopyran ( 10 ) using N-bromosuccinimide under irradiation and high dilution conditions. Bromide 10 was dealt with 1,8-diazabicyclo[5.4.0]undec-7-ene to afford compound 2 . Several reactions of 2 were examined. Protonation of 2 in trifluoroacetic acid occurred at the 2-position to form a pyrylium ion 12 . Catalytic hydrogenation of 2 with palladium on charcoal proceeded smoothly to give 8 . Reduction of 2 by sodium and ethanol afforded 3-ethyl-4-hydroxybenzofuran ( 14 ). Electrophilic substitutions of 2 such as formylation, acetylation, and bromination, occurred easily at the 2-position. The above results show that compound 2 has both properties of benzofuran and 4-methylenepyran.     

Electron g-factor in a gated InAs-inserted-channel In0.53Ga0.47As/In0.52Al0.48As heterostructure

We report on electron g-factor in an InAs-inserted In_0.53Ga_0.47As/In_0.52Al_0.48As heterostructure. The gate voltage dependence of g-factor is obtained from the coincidence method. The obtained g-factor values are surprisingly smaller than the g-factor value of bulk InAs, and it is close to the bare g-factor value of In_0.53Ga_0.47As. The large change in g-factor is observed by applying the gate voltage. The obtained gate voltage dependence is not simply explained by the energy dependence of g-factor.     

Correlation between Site ll-Specific Human Serum Albumin (HSA) Binding Affinity and Murine in vivo Photosensitizing Efficacy of Some Photofrin Components

Human serum albumin (HSA) is one of the key components in human blood that may influence drug distribution. As such, it is important to know the affinity of any drug for albumin. Previously, Photofrina mixture of monomeric, dimeric and oligomeric porphyrins, has been subjected to HSA binding studies. However, due to its complex nature, binding studies on Photofrin or other hematoporphyrin derivatives with HSA are inconclusive. In this report, the binding properties of some components (dimers and trimers) of Photofrin® and the relationship between murine photosensitizing efficacy and those binding properties were investigated. The interaction of these porphyrins with HSA was investigated by direct ultrafiltration and fluorescent titration techniques with fluorescent probes such as dansyl-L-proline (DP), which is known to interact selectively with site II on HSA. Porphyrins also were tested for antitumor activity in a mouse model following intravenous administration and exposure to laser light. Together, the results suggest that the photosensitizers that were preferentially bound to site II of HSA were most effective at controlling murine tumor regrowth     

Furan derivatives. Part 8 On substituent effects in the synthesis of 4,5-dihydro-3H-naphtho[1,8-bc]furans

4,5-Dihydro-3H-naphtho[1,8-bc]furans 4 and 6 which have various substituents (R¹ and R²) have been synthesized from 8-oxo-5,6,7,8-tetrahydro-1-naphthyloxyacetic acids 1 and 3 or their ethyl esters 2 . The reaction of acids 1 and 3 with sodium acetate in acetic anhydride gave a mixture of furans 4 and 6 and lactones 5 and 7 . The ratios of the products were varied according to the types of substituents (R¹ and R²) in acids 1 and 3 . As the substituent R¹ (R² = hydrogen) in acids 1 was changed from hydrogen to a methyl, ethyl or isopropyl group, production of furans 4 became more difficult. However, when a phenyl group was used as the substituent, furan 4 was obtained in good yield. Similarly, as the substituent R² (R¹ = hydrogen) in acids 1 was changed from hydrogen to a methyl, ethyl or isopropyl group, furan formation was more difficult. In contrast, acids 3 which had electron-withdrawing substituents such as chlorine, bromine or a nitro group at the 4-position afforded furans 6 in good yield. 4,5-Dihydro-3H-naphtho[1,8-bc]furans 4 and 4,5-dihydro-3H-naphtho[1,8-bc]furan-2-carbocylic acids 8 were synthesized from the reaction of esters 2 and potassium hydroxide in dioxane. When the substituents R¹ or R² in esters 2 were varied from hydrogen to a methyl, ethyl or isopropyl group the total yields of furans 4 and furancarboxylic acids 8 were reduced.     

Initial mode of radical pair formation in n-hydrocarbons irradiated at 1.5 and 4.2 K

The ESR spectra of X-irradiated (at 1.5 and 4.2 K) single crystals of n-decane-d₂₂, n-decane-h₂₂ and their mixtures have been measured at 1.5 and 4.2 K. It is concluded that almost all alkyl radicals are inherently formed in pairs in a fairly random fashion and that the spacial distribution of the radicals depends on the irradiation temperatures. In the crystal of n-decane-d₂₂, a 1,3-carbon intrachain radical pair is identified together with a number of very close interchain pairs which are formed between almost all kinds of the first neighboring chains. The crystal of n-decane-h₂₂ gives considerably larger spacial distribution of radicals, indicating a remarkable mass effect on the radical pair formation.     

Singlet and triplet photocycloaddition reactions of 2-pyridones with propenoate and 2,4-pentadienotes,and the frontier molecular orbital analysis

Regioselective photocycloadditions of 2-pyridones ( 1 ) with 2,4-pentadienoates ( 3 ) were analysed and compared with the reactions with propenoate ( 2 ), and origins of the different regioselectivities were inferred from frontier molecular orbital properties by the use of PM3-CI method. Direct photoreactions of 1 with 3 being α,β,γ,δ-unsaturated carboxylates gave four types of regio-selective [2+2]cycloadducts, 3-β:4-α-4, 5, 3-δ:4-γ-6,7,5-δ: 6-γ-8, 9 and 5-δ:6-γ-[2+2]cycloadducts 10,11. Sensitized photoreactions of 1 with 3 did not occur, and fluorescence of 1 was weakly quenched by 3. Otherwise, main cycloadducts in the sensitized reactions of 1 with 2 have been obtained as 5-α:6-β-[2+2]cycloadducts, which were different from main 3-β:4-α-[2+2]cycloadducts of the direct reactions, and these site-and regio-selectivities were inferred from the different frontier molecular orbital coefficients at the. 3-and 6-positions of 1 for the triplet and singlet states. Formations of 4–7 were also interpreted by both effects of frontier orbital HSOMO-LUMO interactions and of the electrostatic interaction between 1 and 3. The other site-and regioselective adducts 8–11 were inferred to be formed by the electrostatic interactions similar to 2-pyridone photodimerization.     

Unexpected formation of benzaldehydes by the reactions of dithioacetals derived from cinnamaldehydes with 2,3-dichloro-5,6-dicyano-p-benzoquinone in aqueous solvents

1,3-Dithianes 1 , 1,3-dithiolanes 2 , and diphenyl dithioacetals 3 derived from cinnamaldehydes reacted with 2,3-dichloro-5,6-dicyano-p-benzoquinone in aqueous solvents to give benzaldehydes 4 . Hydride transfer from 1–3 to 2,3-dichloro-5,6-dicyano-p-benzoquinone followed by hydrolysis and oxidative carbon-carbon bond cleavage would produce benzaldehydes 4 .     

On the selection of the optimal plasticizer for calix[n]arene-based ion-selective electrodes: Possible correlation between the ion selectivity and the ‘softness’ of the plasticizer

A criterion for the selection of a suitable plasticizer for calix[n]arene-based ion-selective electrodes is discussed. The cation selectivity of plasticized membranes without the ligand was first measured as a reference. The membranes can be roughly classified into two groups. The first group shows cation selectivity in the order Cs⁺+>K⁺>Na⁺>Li⁺. The membranes in the second group are made of phosphorus plasticizers, which show a selectivity in the reverse order. The plasticizers in the first group featured a linear relationship between the dipole moment of the plasticizer (calculated by a PM3 method) and the ratio of cesium selectivity to lithium selectivity. The linear relationship supports the view that the polar membrane which includes a soft plasticizer with a large dipole moment shows selectivity for Cs⁺, whereas the nonpolar membrane including the soft plasticizer with the small dipole moment shows much lower selectivity for Cs⁺. Next, 2-fluorphenyl-2-nitrophenyl ether (FPNPE) which showed the highest Cs⁺ selectivity and tris(2-ethylhexyl)phosphate (TEHP) which showed the highest Li⁺ selectivity were mixed in an appropriate ratio to make membranes with a different affinity for hard ions. The metal selectivities of several crown-based and calixarene-based ionophores were examined in these membranes. Although a few exceptions exist, the polar soft membrane is favorable when the interfering metal ion is hard, whereas the hard membrane is favorable when the interfering metal ion is soft.