Low-frequency vibrations of bacteriochlorophyll

Frequencies and normal vibrational modes of bacteriochlorophyll are calculated using the semiempirical quantum-mechanical MNDO-PM3 method. To analyze the structure of normal modes, the indices of delocalization of the vibrations and the distribution functions of normal modes over atoms in the molecule are introduced. It is shown that normal vibrational modes of bacteriochlorophyll in the region from 3 to 20 cm^?1 represent “intermolecular” vibrational modes of phytol and tetrapyrrole macrocycle. As the vibrational frequency increases, the normal modes delocalized both on phytol and tetrapyrrole atoms alternate with the modes that are delocalized only on phytol atoms or only on tetrapyrrole atoms. The structural properties of some modes are considered in the aspect of their possible involvement in the formation of absorption spectra of the pigments of reaction centers in photosynthesis and in the formation in them of the coordinate of a primary reaction of the intermolecular electron transfer.     

Substantiation of the mechanism of biphoton nonresonance excitation of molecules of bacteriochlorophyll of purple bacteria by femtosecond pulses

In a series of published experimental works, there has been observed nonresonance biphoton excitation, by femtosecond IR pulses (1250–1500 nm) of molecules of bacteriochlorophyll-a and the pigment in the composition of light-absorbing natural “antenna” complexes of photosynthesizing purple bacteria. The authors of these works believe that IR quanta excite hypothetical forbidden levels of pigments of these bacteria in the dual frequency range of 625–750 nm. In this study, an alternative mechanism of intramolecular electron transport apparently responsible for this phenomenon is suggested and substantiated. The mechanism should manifest itself in powerful electric fields, which are achieved in the pulses of picofemtosecond lasers.     

On the biphoton excitation of the fluorescence of the bacteriochlorophyll molecules of purple photosynthetic bacteria by powerful near IR femto-picosecond pulses

The authors of a number of experimental works detected nonresonance biphoton excitation of bacteriochlorophyll molecules, which represent the main pigment in the light-absorbing natural “antenna” complexes of photosynthesizing purple bacteria, by femtosecond IR pulses (1250–1500 nm). They believe that IR quanta excite hypothetic forbidden levels of the pigments of these bacteria in the double frequency range 625–750 nm. We propose and ground an alternative triplet mechanism to describe this phenomenon. According to our hypothesis, the mechanism of biphoton excitation of molecules by IR quanta can manifest itself specifically, through high triplet levels of molecules in the high fields induced by femtosecond-picosecond laser pulses.     

Energetics of carbon nanotubes

We have investigated the energetics of carbon nanotubes. Calculations have been performed by using the empirical many-body potential energy function developed by Tersoff for carbon. Received: 30 March 1998 / Accepted: 28 July 1998     

Energetics of stochastic resonance

In this paper, we discuss the motion of a Brownian particle in a double-well potential driven by a periodic force in terms of energies delivered by the periodic and the noise forces and energy dissipated into the viscous environment. It is shown that, while the power delivered by the periodic force to the Brownian particle is controlled by the strength of the noise, the power delivered by the noise itself is independent of the amplitude and frequency of the periodic force. The implications of this result for the mechanism of stochastic resonance in an equilibrium system is that it is not energy from the noise force which enhances a small periodic force, but rather an increase of energy delivered by the periodic force, regulated by the strength of the noise. We further re-evaluate the frequency dependence of stochastic resonance in terms of energetic terms including efficiency.     

Energetics and dynamics of decaying cluster ions

The recent addition of (i) a third sector field to our two sector field mass spectrometer (resulting in a BE1E2 field configuration) and of (ii) a high performance electron gun enables us now to study in detail the time dependence of the kinetic energy release distribution (KERD) over a relatively wide range of cluster ion lifetimes. Using this newly constructed device we have studied here for the first time KERDs and deduced binding energies BEs (using finite heat bath theory) of large rare gas cluster ions (an upper size limit in earlier studies arose from the fact that different naturally occurring isotopes will contribute to a chosen metastable peak when the size exceeds a certain value) and in addition of fullerene ions smaller and larger than (here again contaminating coincidences did not allow such studies earlier). Moreover, high precision KERD measurements for the decay of rare gas dimer ions in conjunction with model calculations (using recently calculated potential energy curves for the rare gas dimer ions) also enable us to obtain information on the dynamics and the mechanisms of the underlying spontaneous decay reactions . In addition, we are also reporting here a novel method (unified breakdown graph method) to determine cluster ion binding energies using a recently constructed tandem mass spectrometer BESTOF allowing us to measure fragmentation patterns arising from the unimolecular decay of molecular cluster ions induced by surface collisions. The fragmentation and reaction patterns of protonated ethanol cluster ions investigated here clearly demonstrate in contrast to some of the earlier cluster ion studies that unimolecular dissociation kinetics determines the formation of product ions in the surface-induced decomposition.     

Site-selection optical spectra of bacteriochlorophyll and bacteriopheophytin in frozen solutions

Site-selection spectra of title compounds in different frozen solvents at 5K have been obtained: fluorescence spectra on selective excitation in vibronic as well as in the O-O absorption region and excitation spectra with narrow-band fluorescence recording. Frequencies of vibrational modes active in fluorescence and excitation spectra of bacteriochlorophyll a (BChl) and its metal-free derivative have been determined from these fine-line spectra. Most favourable vibronic line-to-background intensity ratios have been found in non-polar aprotic glassy environments (triethylamine, di-iso-amylether). The intensity of zero-phonon lines in microcrystallic protic matrices was low, indicating strong electron-phonon coupling. The vibrational frequencies of the excited electronic state characteristic of axially (at Mg atom) mono- and disolvated BChl species have been identified. Narrow spectral holes of about 20% of the initial absorption could be burned with ≈10^-4 quantum yield within the O-O band of BChl and bacteriopheophytin.     

生物细胞中的能量学和力学

世界上的生物总是在不停地运动着。动物在奔跑、飞翔、游泳。植物日复一日追逐着太阳。即使是微生物,也在不停地运动。我们体内的细胞的各个部分也在不停地运动,这些运动使我们的细胞可以生长、分裂、改变形状、甚至运动。 除了运动之外,我们的身体还必须能够感知到周围的世界。活体细胞可以对周围很多种机械刺激产生反馈,比如伸展,液体的流动,渗透压的改变,周围环境的硬度。我们的触觉和听觉要求细胞能够感知非常细微的机械力。我们对血压的调节能力依赖于分布在体内动脉和静脉的机械敏感性。