Characterisation of Nanohybrids of Porphyrins with Metallic and Semiconducting Carbon Nanotubes by EPR and Optical Spectroscopy

Single‐walled carbon nanotubes (SWCNTs) are noncovalently functionalised with octaethylporphyrins (OEPs) and the resulting nanohybrids are isolated from the free OEPs. Electron paramagnetic resonance (EPR) spectroscopy of cobalt(II)OEP, adsorbed on the nanotube walls by π–π‐stacking, demonstrates that the CNTs act as electron acceptors. EPR is shown to be very effective in resolving the different interactions for metallic and semiconducting tubes. Moreover, molecular oxygen is shown to bind selectively to nanohybrids with semiconducting tubes. Water solubilisation of the porphyrin/CNT nanohybrids using bile salts, after applying a thorough washing procedure, yields solutions in which at least 99 % of the porphyrins are interacting with the CNTs. Due to this purification, we observe, for the first time, the isolated absorption spectrum of the interacting porphyrins, which is strongly red‐shifted compared to the free porphyrin absorption. In addition a quasi‐complete quenching of the porphyrin fluorescence is also observed.     

On arrangements of Jordan arcs with three intersections per pair

Motivated by a number of motion-planning questions, we investigate in this paper some general topological and combinatorial properties of the boundary of the union ofn regions bounded by Jordan curves in the plane. We show that, under some fairly weak conditions, a simply connected surface can be constructed that exactly covers this union and whose boundary has combinatorial complexity that is nearly linear, even though the covered region can have quadratic complexity. In the case where our regions are delimited by Jordan acrs in the upper halfplane starting and ending on thex-axis such that any pair of arcs intersect in at most three points, we prove that the total number of subarcs that appear on the boundary of the union is only (n(n)), where(n) is the extremely slowly growing functional inverse of Ackermann's function.The first author is pleased to acknowledge the support of Amoco Fnd. Fac. Dev. Comput. Sci. 1-6-44862 and National Science Foundation Grant CCR-8714565. Work on this paper by the fourth and seventh authors has been supported by Office of Naval Research Grant N00014-87-K-0129, by National Science Foundation Grant NSF-DCR-83-20085, and by grants from the Digital Equipment Corporation and the IBM Corporation. The seventh author in addition wishes to acknowledge support by a research grant from the NCRD—the Israeli National Council for Research and Development. The fifth author would like to acknowledge support in part by NSF grant DMS-8501947. Finally, the eighth author was supported in part by a National Science Foundation Graduate Fellowship.     

Photoelectrochemical Verification of Proton-Releasing Groups in Bacteriorhodopsin

Light-induced transient currents of bacteriorhodopsin (bR) and its mutants (D96N, D85N, E204Q and E194Q) were measured at the interface of an electrode and the aqueous solution in an electrochemical cell. The transient positive (cathodic) and negative (anodic) photocurrents generated upon the onsets of continuous illumination and of turning off light, respectively, were investigated at different electrolyte pH. The wild type exhibits both positive and negative responses, with the sign of the response inverted at pH lt 5. In D85N the response is entirely suppressed, while D96N lacks the negative response. Laser pulse excitation (532 nm) of bR and the mutants showed the response rise time of the positive transient to be uniformly about 100 μs, indicating that the response is linked to the L to M transition in the photocycle. According to these results the positive and negative signals originate from the proton release and uptake reactions, respectively. Photoexcitation of the mutants E204Q and E194Q that lack protonatable residues at position 204 and 194, respectively, produced a negative response at neutral pH, which indicates that in these proteins proton uptake precedes proton release. This result is consistent with our observations made earlier with pH indicator dyes and demonstrates that Glu-204 and Glu-194 constitute the terminal proton release complex in the extracellular region of bR.     

Adenosine Cyclic 3′, 5′-Phosphoramidate and N,N-Dimethylphosphoramidate: Synthesis Via Symmetrical and Mixed Anhydrides and Hydrolysis

Abstract

The title compounds were synthesized by converting cyclic AMP with a sulfonyl chloride to the symmetrical anhydride or with diphenyl phosphorochloridate to the mixed anhydride, then aminolyzing the anhydrides without isolation. The synthesis preferentially gave Sp-amides. Characteristic differences were observed in the behavior of the unsubstituted amide and the dimethylamide under hydrolysis conditions.     

适用于放大自发辐射平滑光束的脉宽压缩方法

为了增加靶上的功率密度和耦合效率,基于饱和增益开关原理,发展了一种适用于放大自发辐射平滑光束的脉宽压缩方法。利用该方法,在赛格德大学的一台放电泵浦KrF准分子激光器上进行了实验,将该激光器输出的脉宽为14.5 ns的放大自发辐射光束压缩到了7.5 ns,并且保持了光束原有的均匀性。     

Ultrathin molecularly imprinted polymer sensors employing enhanced transmission surface plasmon resonance spectroscopy

An ultrathin novel nanosensor (31.5 +/- 4.1 nm thick in the absence of analytes), employing a molecularly imprinted polymer as a recognition element for cholesterol and gold nanoparticle enhanced transmission surface plasmon resonance spectroscopy for detection, was constructed.     

Bilayer Lipid Membrane-Semiconductor Junctions. Spectroscopic and Electrochemical Characterizations and Photoelectron Transfer

Three different systems of glyceryl monooleate (GMO) bilayer lipid membrane (BLM) supported semiconductor particles have been prepared and characterized. A single composition of particulate semiconductor deposited on only one side of the BLM constituted System A, two different compositions of particulate semiconductors sequentially deposited on the same side of the BLM represented System B, and two different compositions of particulate semiconductors deposited on the opposite sides of the BLM made up System C. Effective refractive indices and optical thicknesses of GMO-BLM-supported In₂S₃ and ZnS particles (System A), determined by Brewster-angle and reflection measurements, allowed the assessment of the maximum sizes and the volume fractions of semiconductor particles to be on the order of 1200 Å and 0.3, respectively. Since semiconductor particles are highly porous structures, only the first layer of particulates penetrated into the BLM and were considered in the proposed equivalent circuit and band models. The presence of semiconductors on the BLM surface has been established by voltage-dependent capacitance measurements, absorption spectroscopy, and optical microscopy. Subsequent to the injection of H₂S, the first observable change was the appearance of fairly uniform white dots on the black film. These dots rapidly moved around and grew in size, forming islands which then merged with themselves and with a second generation of dots, which ultimately led to a continuous film which continued to grow in thickness. Cyclic voltammetry established the current rectifying behavior for the semiconductor-particle-coated BLMs. CdS, ZnS, and In₂S₃ (System A) formed an n-type, while Cu_2-(x+y)S (System A) behaved like a p-type, electrolyte-semiconductor (ES) junction. Semiconductor-semiconductor heterojunction (SS') formation was established for System C. Transfer of conduction-band electrons to dissolved oxygen (for the n-type ES junction) and across the membrane was considered to be responsible for the observed dark currents. Steady-state illumination of a CdS-containing BLM resulted in the prompt development of -150 to -200 mV (cis side negative) potential difference in an open circuit across the GMO BLM. This initial photovoltage, V ₁, quickly decayed to a steady value, V _s (- 100 to -150 mV). When the illumination was turned off, the potential difference across the GMO BLM decreased to its dark value in 3-4 minutes.