Probing the effect of the binding site on the electrostatic behavior of a series of carotenoids reconstituted into the light-harvesting 1 complex from purple photosynthetic bacterium Rhodospirillum rubrum detected by stark spectroscopy

Reconstitutions of the LH1 complexes from the purple photosynthetic bacterium Rhodospirillum rubrum S1 were performed with a range of carotenoid molecules having different numbers of C=C conjugated double bonds. Since, as we showed previously, some of the added carotenoids tended to aggregate and then to remain with the reconstituted LH1 complexes (Nakagawa, K.; Suzuki, S.; Fujii, R.; Gardiner, A.T.; Cogdell, R.J.; Nango, M.; Hashimoto, H. Photosynth. Res. 2008, 95, 339-344), a further purification step using a sucrose density gradient centrifugation was introduced to improve purity of the final reconstituted sample. The measured absorption, fluorescence-excitation, and Stark spectra of the LH1 complex reconstituted with spirilloxanthin were identical with those obtained with the native, spirilloxanthin-containing, LH1 complex of Rs. rubrum S1. This shows that the electrostatic environments surrounding the carotenoid and bacteriochlorophyll a (BChl a) molecules in both of these LH1 complexes were essentially the same. In the LH1 complexes reconstituted with either rhodopin or spheroidene, however, the wavelength maximum at the BChl a Qy absorption band was slightly different to that of the native LH1 complexes. These differences in the transition energy of the BChl a Qy absorption band can be explained using the values of the nonlinear optical parameters of this absorption band, i.e., the polarizability change Tr(Deltaalpha) and the static dipole-moment change |Deltamu| upon photoexcitation, as determined using Stark spectroscopy. The local electric field around the BChl a in the native LH1 complex (ES) was determined to be approximately 3.0x10(6) V/cm. Furthermore, on the basis of the values of the nonlinear optical parameters of the carotenoids in the reconstituted LH1 complexes, it is possible to suggest that the conformations of carotenoids, anhydrorhodovibrin and spheroidene, in the LH1 complex were similar to that of rhodopin glucoside in crystal structure of the LH2 complex from Rhodopseudomonas acidophila 10050.     

Syntheses and Synthetic Applications of Functionalized Propargylic and Allylic Fluorides

This account presents the synthesis and application of propargylic and allylic fluorides containing hydroxy or carbonyl functional groups. In particular, the Barbier-type reaction of difluoropropargyl bromides with aldehydes or chloroformates provides versatile propargylic fluorides, and the organocatalytic fluorination of dienamine intermediates has been demonstrated as an effective method to obtain allylic fluorides stereoselectively. Additionally, mechanistic insights into such reactions are discussed with the aid of density functional theory calculations. The report also describes the preparation of fluorinated 1,7-diyne or 1,7-enyne derivatives of these compounds. These propargylic and allylic fluorides can be used as building blocks for fluorinated heterocycles, such as fluorinated furans, tetrahydrofurans, and lactams. Additionally, fluorinated bi- or tri-heterocyclic compounds can be synthesized via transition-metal-catalyzed reactions with fluorinated 1,7-diyne or 1,7-enyne derivatives.     

High-performance liquid chromatographic determination of a new beta-lactamase inhibitor and its metabolite in combination therapy with piperacillin in biological materials

[2S-(2 alpha,3 beta,5 alpha)]-3-Methyl-7-oxo-3-(1H-1,2,3-triazol-1-yl- methyl)-4-thia-1-azabicyclo [3.2.0]-heptane-2-carboxylic acid 4,4-dioxide (YTR-830H) is a new beta-lactamase inhibitor and the combination therapy of this compound with piperacillin is now under study. For the determination of the beta-lactamase inhibitor and piperacillin in biological materials, plasma and visceral tissue homogenates were deproteinized, whereas diluted urine and filtered faeces homogenates were treated with a Sep-Pak C18 cartridge. In order to assay the inactive metabolite of beta-lactamase inhibitor, each sample was treated with a Sep-Pak C18 cartridge. Aliquots of each preparation were chromatographed using ion-pair and reversed-phase chromatographic techniques on a high-performance liquid chromatograph equipped with a UV detector, set at 220 nm. The detection limits of beta-lactamase inhibitor and piperacillin were 0.2 microgram/ml in plasma, 2.5-5.0 micrograms/ml in urine and 0.2-0.5 microgram/g in visceral tissue and faeces. Those of the metabolite were 1.0 microgram/ml in plasma, 2.5-5.0 micrograms/ml in urine and 1.0 microgram/g in visceral tissue and faeces. A precise and sensitive assay for the determination of the beta-lactamase inhibitor, its metabolite and piperacillin is described, and their stabilities in several media are reported.     

Convenient preparation and effective separation of the C-2 and C-3 tosylates of α-cyclodextrin

Secondary tosylates of α-cyclodextrin were conveniently prepared by the reaction of the cyclodextrin with tosyl chloride in alkaline water where pH of the mixture should be allowed to decrease as the proceeding of reaction, and were effectively separated by reversed-phase column chromatography.     

A capacity-rounding algorithm for the minimum-cost circulation problem: A dual framework of the Tardos algorithm

Recently, É. Tardos gave a strongly polynomial algorithm for the minimum-cost circulation problem and solved the open problem posed in 1972 by J. Edmonds and R.M. Karp. Her algorithm runs in O(m ² T(m, n) logm) time, wherem is the number of arcs,n is the number of vertices, andT(m, n) is the time required for solving a maximum flow problem in a network withm arcs andn vertices. In the present paper, taking an approach that is a dual of Tardos's, we also give a strongly polynomial algorithm for the minimum-cost circulation problem. Our algorithm runs in O(m ² S(m, n) logm) time and reduces the computational complexity, whereS(m, n) is the time required for solving a shortest path problem with a fixed origin in a network withm arcs,n vertices, and a nonnegative arc length function. The complexity is the same as that of Orlin's algorithm, recently developed by efficiently implementing the Edmonds-Karp scaling algorithm.     

Selective aggregation of single-walled carbon nanotubes using the large optical field gradient of a focused laser beam

We demonstrate the selective aggregation of single-walled carbon nanotubes by photon forces, using the large optical field gradient of a laser focused through a high numerical aperture objective lens. The nanotubes, dispersed in an aqueous solution with a surfactant, are detected via Raman scattering from the confocal volume of the optical trap. By using a visible-light laser for both trapping and detection, the dynamics of the radial breathing mode signal taken at short intervals shows an increase of a single breathing mode over time, indicating the increase in the density of only one species of tube in the focal volume. This result represents a significant step toward the development of techniques for the arbitrary manipulation and sorting of nanotubes by optical fields.     

Full-valence density matrix renormalisation group calculations on meta-benzyne based on unrestricted natural orbitals. Revisit of seamless continuation from broken-symmetry to symmetry-adapted models for diradicals

ABSTRACT

In this work, we show that the natural orbitals of unrestricted hybrid density functional theory (UHDFT) can be used as the active space orbitals to perform multireference (MR) calculations, for example, the density matrix renormalisation group (DMRG) and Mukherjee-type (Mk) MR coupled-cluster (CC) method. By including a sufficiently large number of these natural orbitals, full-valence (FV) active space can be identified without recourse of the expensive self-consistent procedures for DMRG-SCF. Several useful chemical indices are derived based on the occupation numbers of the natural orbitals for seamless continuation from broken-symmetry (BS) to symmetry-adapted (SA) methods. These procedures are used on 1,3-didehydrobenzene (meta-benzyne) to calculate its singlet (S)-triplet (T) gap. We compare our results to available experiments and computational results obtained by several other groups. We see our procedures as a seamless bridge between single-reference BS methods, such as UHDFT, and the SA MR methods, such as FV DMRG and MkMRCC.     

Head-to-tail regioregularity of poly(3-hexylthiophene) in oxidative coupling polymerization with FeCl3

We investigated a head-to-tail regioregularity of poly(3-alkylthiophenes) from 3-alkylthiophene by an oxidative coupling polymerization, which is the simplest and easiest way for the synthesis of polythiophenes. The polymerizations were conducted using ferric chloride (III) as an oxidant in chloroform. Investigating the polymerization conditions, a lower temperature and a lower concentration were effective for increasing the head-to-tail (HT) content. The best HT content of 88% was obtained when the temperature was −45°C and the initial monomer concentration was 0.02 mol L⁻¹. Washing the resulting polymer by n-hexane further increased the content to 91%. Thus, it was found that the high regioselectivity can be achieved by the simple polymerization and the simple operation such as washing. The polymerization mechanism causing the regularity is also discussed. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 1943–1948, 1999