Biohybrid photosynthetic antenna complexes for enhanced light-harvesting

Biohybrid antenna systems have been constructed that contain synthetic chromophores attached to 31mer analogues of the bacterial photosynthetic core light-harvesting (LH1) β-polypeptide. The peptides are engineered with a Cys site for bioconjugation with maleimide-terminated chromophores, which include synthetic bacteriochlorins (BC1, BC2) with strong near-infrared absorption and commercial dyes Oregon green (OGR) and rhodamine red (RR) with strong absorption in the blue-green to yellow-orange regions. The peptides place the Cys 14 (or 6) residues before a native His site that binds bacteriochlorophyll a (BChl-a) and, like the native LH proteins, have high helical content as probed by single-reflection IR spectroscopy. The His residue associates with BChl-a as in the native LH1 β-polypeptide to form dimeric ββ-subunit complexes [31mer(-14Cys)X/BChl](2), where X is one of the synthetic chromophores. The native-like BChl-a dimer has Q(y) absorption at 820 nm and serves as the acceptor for energy from light absorbed by the appended synthetic chromophore. The energy-transfer characteristics of biohybrid complexes have been characterized by steady-state and time-resolved fluorescence and absorption measurements. The quantum yields of energy transfer from a synthetic chromophore located 14 residues from the BChl-coordinating His site are as follows: OGR (0.30) < RR (0.60) < BC2 (0.90). Oligomeric assemblies of the subunit complexes [31mer(-14Cys)X/BChl](n) are accompanied by a bathochromic shift of the Q(y) absorption of the BChl-a oligomer as far as the 850-nm position found in cyclic native photosynthetic LH2 complexes. Room-temperature stabilized oligomeric biohybrids have energy-transfer quantum yields comparable to those of the dimeric subunit complexes as follows: OGR (0.20) < RR (0.80) < BC1 (0.90). Thus, the new biohybrid antennas retain the energy-transfer and self-assembly characteristics of the native antenna complexes, offer enhanced coverage of the solar spectrum, and illustrate a versatile paradigm for the construction of artificial LH systems.     

Excited-state energy-transfer dynamics of self-assembled imine-linked porphyrin dyads

Toward the development of new strategies for the synthesis of multiporphyrin arrays, we have prepared and characterized (electrochemistry and static/time-resolved optical spectroscopy) a series of dyads composed of a zinc porphyrin and a free base porphyrin joined via imine-based linkers. One dyad contains two zinc porphyrins. Imine formation occurs under gentle conditions without alteration of the porphyrin metalation state. Five imine linkers were investigated by combination of formyl, benzaldehyde, and salicylaldehyde groups with aniline and benzoic hydrazide groups. The imine-linked dyads are quite stable to routine handling. The excited-state energy-transfer rate from zinc to free base porphyrin ranges from (70 ps)(-)(1) to (13 ps)(-)(1) in toluene at room temperature depending on the linker employed. The energy-transfer yield is generally very high (>97%), with low yields of deleterious hole/electron transfer. Collectively, this work provides the foundation for the design of multiporphyrin arrays that self-assemble via stable imine linkages, have predictable electronic properties, and have comparable or even enhanced energy-transfer characteristics relative to those of other types of covalently linked systems.     

Excited-state energy-transfer dynamics in self-assembled triads composed of two porphyrins and an intervening Bis(dipyrrinato)metal complex

The synthesis and characterization of various triads composed of a linear array of two zinc porphyrins joined via an intervening bis(dipyrrinato)metal(II) complex are reported. The preparation exploits the facile complexation of dipyrrins with divalent metal ions to give bis(dipyrrinato)metal(II) complexes [abbreviated (dp)(2)M]. Copper(II) and palladium(II) chelates of dipyrrins (available by oxidation of dipyrromethanes) were prepared in 50-80% yield. A one-flask synthesis of bis(dipyrrinato)zinc(II) complexes was developed by oxidation of a dipyrromethane with DDQ or p-chloranil in the presence of Zn(OAc)(2).2H(2)O in THF ( approximately 80% yield). Three routes were developed for preparing porphyrin-dipyrrins: (1). Suzuki coupling of a boronate-substituted zinc porphyrin (ZnP) and bis[5-(4-iodophenyl)dipyrrinato]Pd(II) to give the (ZnP-dp)(2)Pd triad (50% yield), followed by selective demetalation of the (dp)(2)Pd unit by treatment with 1,4-dithiothreitol under neutral conditions (71% yield); (2). oxidation of a porphyrin-dipyrromethane with p-chloranil in the presence of Zn(OAc)(2).2H(2)O followed by chromatography on silica gel (71% yield); and (3). condensation of a dipyrrin-dipyrromethane and a dipyrromethane-dicarbinol under InCl(3) catalysis followed by oxidation with DDQ (10-16% yield). Four triads of form (ZnP-dp)(2)Zn were prepared in 83-97% yield by treatment of a porphyrin-dipyrrin with Zn(OAc)(2).2H(2)O at room temperature. Free base dipyrrins typically absorb at 430-440 nm, while the bis(dipyrrinato)metal complexes absorb at 460-490 nm. The fluorescence spectra/yields and excited-state lifetimes of the (ZnP-dp)(2)Zn triad in toluene show (1). efficient energy transfer from the bis(dipyrrinato)zinc(II) chromophore to the zinc porphyrins (98.5% yield), and (2). little or no quenching of the resulting excited zinc porphyrin relative to the isolated chromophore. Taken together, these results indicate that bis(dipyrrinato)zinc(II) complexes can serve as self-assembling linkers that further function as secondary light-collection elements in porphyrin-based light-harvesting arrays.     

Homogeneous nucleation of water between 200 and 240 K: new wave tube data and estimation of the Tolman length

We have measured homogeneous nucleation rates of water at 200-240 K in the carrier gas helium, in the range of 10(13) - 10(17) m(-3) s(-1) using an expansion wave tube. The rates agree well with the results of Wolk and Strey [J. Phys. Chem. B 105, 11683 (2001)] in the range of overlap (220-240 K), and are summarized by the empirical fit J = S exp[4.6 + 0.244T-(906.8 - 2.914T)(ln S)(2)], with J the nucleation rate in m(-3) s(-1), S the supersaturation, and T the temperature in K. We find that the supersaturation dependence of both our rates and those of Wolk and Strey is lower than classical theory predicts, and that the critical cluster is smaller than the classical critical size. These deviations are explained in the framework of the Tolman theory for surface tension, and the "Tolman length" is estimated from our experimental results. We find a positive Tolman length that increases with decreasing temperature, from about 0.1 Angstrom at 260 K to (0.6 +/- 0.4) Angstroms at 200 K. We present a nucleation rate expression that takes the Tolman length into account and show that both the supersaturation and temperature dependence are improved, compared to the classical theory.     

Cone-and-plate apparatus: a compact system for studying well-characterized turbulent flow fields

We have investigated the turbulent flow field inside a cone-and-plate Couette flow apparatus (CPA). The CPA presents a compact, easily varied and easily measured flow system with well-characterized turbulent and laminar flow fields and a good full turbulent spectrum. The CPA can also produce the same time-average stress for both laminar and turbulent regimes. The apparatus consisted of a shallow 2° cone of 0.75 m radius rotating above a flat plate in air. A high-resolution X-wire probe was used to measure the turbulent and time-mean flow properties. A single parameter , which is a measure of the centrifugal forces acting on the moving fluid, governs the degree of secondary flow and turbulence in the device. In the fully turbulent region, R > 4, the mean velocity profile has steep gradients near each surface and is nearly uniform in the central core; and the normalized azimuthal velocity closely follows the ubiquitous law of the wall near the plate. The turbulence intensity exhibits two peaks at the edges of the core flow, and the frequency spectrum of velocity fluctuations near the plate resembles that found in isotropic turbulence. This study also suggests that the rotational symmetry with the stationary bottom plate is a much more convenient experimental geometry than a circular Couette flow.     

An experimental investigation of the sonic criterion for transition from regular to Mach reflection of weak shock waves

The signal speed, namely the local sound speed plus the flow velocity, behind the reflected shocks produced by the interaction of weak shock waves (M _i < 1.4) with rigid inclined surfaces has been measured for several shock strengths close to the point of transition from regular to Mach reflection. The signal speed was measured using piezo-electric transducers, and with a multiple schlieren system to photograph acoustic signals created by a spark discharge behind a small aperture in the reflecting surfaces. Both methods yielded results with equal values within experimental error. The theoretical signal speeds behind regularly reflected shocks were calculated using a non-stationary model, and these agreed with the measured results at large angles of incidence. As the angle of incidence was reduced, for the same incident shock Mach number, so as to approach the point of transition from regular to Mach reflection, the measured values of the signal speed deviated significantly from the theoretical predictions. It was found, within experimental uncertainty, that transition from regular to Mach reflection occurred at the experimentally observed sonic point, namely, when the signal speed was equal to the speed of the reflection point along the reflecting surface. This sonic condition did not coincide with the theoretical value.     

Least energy as a criterion for transition between regular and Mach reflection

A new criterion is suggested to define the point of transition between regular and Mach reflection. The suggested criterion is based on the natural tendency of a physical system to minimize its energy. The increases of the specific energy behind the reflected shock of a regular reflection and behind the Mach stem of a Mach reflection are calculated. It is hypothesized that the type of reflection that will occur is that which produces the smaller change of specific energy. The transition angles predicted using this criterion show better agreement with experimental results than those predicted using the detachment criterion for incident shock waves with Mach numbers between 1.1 and 2.0.This article was processed using Springer-Verlag TEX Shock Waves macro package     

Synthesis and physicochemical properties of metallobacteriochlorins

Access to metallobacteriochlorins is essential for investigation of a wide variety of fundamental photochemical processes, yet relatively few synthetic metallobacteriochlorins have been prepared. Members of a set of synthetic bacteriochlorins bearing 0-4 carbonyl groups (1, 2, or 4 carboethoxy substituents, or an annulated imide moiety) were examined under two conditions: (i) standard conditions for zincation of porphyrins [Zn(OAc)(2)·2H(2)O in N,N-dimethylformamide (DMF) at 60-80 °C], and (ii) treatment in tetrahydrofuran (THF) with a strong base [e.g., NaH or lithium diisopropylamide (LDA)] followed by a metal reagent MX(n). Zincation of bacteriochlorins that bear 2-4 carbonyl groups proceeded under the former method whereas those with 0-2 carbonyl groups proceeded with NaH or LDA/THF followed by Zn(OTf)(2). The scope of metalation (via NaH or LDA in THF) is as follows: (a) for bacteriochlorins that bear two electron-releasing aryl groups, M = Cu, Zn, Pd, and InCl (but not Mg, Al, Ni, Sn, or Au); (b) for bacteriochlorins that bear two carboethoxy groups, M = Ni, Cu, Zn, Pd, Cd, InCl, and Sn (but not Mg, Al, or Au); and (c) a bacteriochlorin with four carboethoxy groups was metalated with Mg (other metals were not examined). Altogether, 15 metallobacteriochlorins were isolated and characterized. Single-crystal X-ray analysis of 8,8,18,18-tetramethylbacteriochlorin reveals the core geometry provided by the four nitrogen atoms is rectangular; the difference in length of the two sides is ～0.08 ?. Electronic characteristics of (metal-free) bacteriochlorins were probed through electrochemical measurements along with density functional theory calculation of the energies of the frontier molecular orbitals. The photophysical properties (fluorescence yields, triplet yields, singlet and triplet excited-state lifetimes) of the zinc bacteriochlorins are generally similar to those of the metal-free analogues, and to those of the native chromophores bacteriochlorophyll a and bacteriopheophytin a. The availability of diverse metallobacteriochlorins should prove useful in a variety of fundamental photochemical studies and applications.