Davydov Soliton Dynamics in Proteins: III. Applications and Calculation of Vibrational Spectra

The mechanism for energy and signal transport in proteins as suggested by Davydov is discussed. The idea is based on a coupling of amide-I oscillators to acoustic phonons in a hydrogen bonded chain. Results as obtained with the usually used ansätze are discussed. The quality of these states for an approximate solution of the time-dependent Schrödinger equation is investigated. It is found that the semiclassical ansatz is a poor approximation, while the more sophisticated |D₁> state seems to represent the exact dynamics quite well. This was shown by extensive calculations, both analytically and numerically in the two preceding papers. Calculations at a temperature of 300K for one chain, as well as for three coupled ones (as they are present in an α-helix) are presented and discussed. From the calculations it is evident, that Davydov solitons are stable for reasonable parameter values at 300K for special initial excitations close to the terminal sites of the chain. Further vibrational spectra are presented and discussed. Our results suggest, that due to their strong dependence on the initial state, the Davydov |D₁> model system might be a (quantum) chaotic one.     

Davydov Soliton Dynamics in Proteins: II. The General Case

We performed long time simulations using the |D₁> approximation for the solution of the Davydov Hamiltonian. In addition we computed expectation values of the relevant operators with the state (_D/J)|D₁> and the deviation |> from the exact solution over long times, namely 10 ns. We found that in the very long time scale the |D₁> ansatz is very close to an exact solution, showing expectation values of the relevant physical observables in the state (_D/J)|D₁> being about 5-6 orders of magnitudes larger than in the deviation state |>. In the intermediate time scale of the ps range such errors, as known from our previous work, are somewhat larger, but still more or less negligibly. Thus we also report results from an investigation of the very short time (in the range 0-0.4 ps) behaviour of the |D₁> state compared with that of an expansion of the exact solution in powers of time t. This expansion is reliable for about 0.12 ps for special cases as shown in the previous paper. However, the accuracy of the exactly known value of the norm and the expectation value of the Hamiltonian finally indicates up to what time a given expansion is valid, as also shown in the preceding paper. The comparison of the expectation values of the operators representing the relevant physical observables, formed with the third order wave function and with the corresponding results of |D₁> simulations has shown, that our expansion is valid up to a time of roughly 0.10-0.15 ps. Within this time the second and third order corrections turned out to be not very important. This is due to the fact that our first order state contains already some terms of the expansion, summed up to inifinite order. Further we found good agreement of the results obtained with our expansion and those from the corresponding |D₁> simulations within the time of about 0.10 ps. At later times, the factors with explicit powers of t in second and third order become dominant, making the expansion meaningless. Possibilities for the use of such expansions for larger times are described. Alltogether we have shown (together with previous work on medium times), that the |D₁> state, although of approximative nature, is very close to an exact solution of the Davydov model on time scales from some femtoseconds up to nanoseconds. Especially the very small time region is of importance, because in this time a possible soliton formation from the initial excitation would start.     

Davydov Soliton Dynamics in Proteins: I. Initial States and Exactly Solvable Special Cases

For the Davydov Hamiltonian several special cases are known which can be solved analytically. Starting from these cases we show that the initial state for a simulation using Davydovs |D₁> approximation has to be constructed from a given set of initial lattice displacements and momenta in form of a coherent state with its amplitudes independent of the lattices site, corresponding to Davydovs |D₂> approximation. In the |D₁> ansatz the coherent state amplitudes are site dependent. The site dependences evolve from this initial state exclusively via the equations of motion. Starting the |D₁> simulation from an ansatz with site dependent coherent state amplitudes leads to an evolution which is different from the analytical solutions for the special cases. Further we show that simple construction of such initial states from the expressions for displacements and momenta as functions of the amplitudes leads to results which are inconsistent with the expressions for the lattice energy. The site-dependence of coherent state amplitudes can only evolve through the exciton-phonon interactions and cannot be introduced already in the initial state. Thus also in applications of the |D₁> ansatz to polyacetylene always |D₂> type initial states have to be used in contrast to our previous suggestion [W. Förner, J. Phys.: Condens. Matter 1994, 6, 9089-9151, on p. 9105]. Further we expand the known exact solutions in Taylor serieses in time and compare expectation values in different orders with the exact results. We find that for an approximation up to third order in time (for the wave function) norm and total energy, as well as displacements and momenta are reasonably correct for a time up to 0.12-0.14 ps, depending somewhat on the coupling strengh for the transportless case. For the oscillator system in the decoupled case the norm is correct up to 0.6-0.8 ps, while the expectation values of the number operators for different sites are reasonably correct up to roughly 0.6 ps, when calculated from the third order wave function. The most important result for the purpose to use such expansions for controlling the validity of ansatz states is, however, that the accuracy of S(t) and H(t) (constant in time, exact values known in all cases) is obviously a general indicator for the time region in which a given expansion yields reliable values also for the other, physically more interesting expectation values.     

Physical Parameters of a Reactor-Stellarator with Small Ripples of the Helical Magnetic Field

The paper describes the calculation data on the physical parameters of a reactor-stellarator, where the nonuniformities of the helical field are smaller than the toroidal magnetic field nonuniformities: ε_h < ε_t. Unlike the previous studies, where the ion-component transport coefficients had the collision frequency dependence proportional to ν^1/2, this being equivalent to the ε_h > ε_t case, in the present calculations, these coefficients were assumed to be in proportion to the first power of the collision frequency, D_i ∝ ν for ν_eff < 2ω_E, and to D_i ∝ ν^?1 for the inverse inequality. Here, ω_E is the rotation frequency of plasma in the radial electric field. As before, the plasma electrons corresponded to the mode of D_e ∝ ν^?1. As initial parameters for numerical calculations, a reactor with R = 8 m, r_p = 2 m, and B₀ = 5 Т was taken. A numerical code was used to solve the set of equations that describes the plasma space?time behavior in the reactor-stellarator under the conditions of equal diffusion fluxes. The start of reactor operation in the mode of thermonuclear burning was provided by heating sources with a power of several tens of megawatts. Steady-state operating conditions of a self-sustained thermonuclear reaction were attained by maintaining the plasma density through DT fuel pellet injection into the plasma.     

A theoretical model of hydraulic conductivity recovery from embolism with comparison to experimental data on Acer saccharum

A theoretical model of bubble dissolution in xylem conduits of stems was designed using the finite differential method and iterative calculations via computer. The model was based on Fick's, Henry's and Charles' laws and the capillary equation. The model predicted the tempo of recovery from embolism in small diameter branches of woody plants with various xylem structures under different xylem water pressures. The model predicted the time required to recover conductivity in any position in the stem. Repeated iterative solution of the model for different situations yielded an empirical formula to calculate the time for complete recovery of conductivity in stems from a fully embolised initial state. The time, t_p, is given by: where α is a temperature coefficient; D is the coefficient of diffusion of air in wood at 25°C; r_cs is the ratio of the area of total conduit cross section to the stem cross section; Ψ_xp is the stem xylem pressure potential (Pa, where 0 Pa equals atmospheric pressure); τ is solution surface tension (0.072 N m^?1); and D_c and D_s are diameters of the conduits and the stem, respectively (m). The equation is valid only when Ψ_xp > –4τ/D_c. The model predicts no recovery of conductivity when Ψ_xp≤–4τ/D_c. The model agreed with experiments.     

Hardness maximization or equalization? New insights and quantitative relations between hardness increase and bond dissociation energy

It has been overlooked that the change of hardness, η, upon bonding is intimately connected to thermochemical cycles, which determine whether hardness is increased according to Pearson’s “maximum hardness principle” (MHP) or equalized, as expected by Datta’s “hardness equalization principle” (HEP). So far the performances of these likely incompatible “structural principles” have not been compared. Computational validations have been inconclusive because the hardness values and even their qualitative trends change drastically and unsystematically at different levels of theory. Here I elucidate the physical basis of both rules, and shed new light on them from an elementary experimental source. The difference, Δη = η _mol – <η _at>, of the molecular hardness, η _mol, and the averaged atomic hardness, <η _at>, is determined by thermochemical cycles involving the bond dissociation energies D of the molecule, D ⁺ of its cation, and D ^? of its anion. Whether the hardness is increased, equalized or even reduced is strongly influenced by ΔD = 2D – D ⁺  ? D ^?. Quantitative expressions for Δη are obtained, and the principles are tested on 90 molecules and the association reactions forming them. The Wigner-Witmer symmetry constraints on bonding require the valence state (VS) hardness, η _VS, instead of the conventional ground state (GS) hardness, η _GS. Many intriguingly “unpredictable” failures and systematic shortcomings of said “principles” are understood and overcome for the first time, including failures involving exotic and/or challenging molecules, such as Be_2, B₂, O₃, and transition metal compounds. New linear relationships are discovered between the MHP hardness increase Δη _VS and the intrinsic bond dissociation energy D _i . For bond formations, MHP and HEP are not compatible, and HEP does not qualify as an ordering rule.     

Synthesis and characterization of a stable paramagnetic hexacoordinated oxochromium(IV) complex with dianionic tetradentate Schiff base ligand salen

A paramagnetic octahedral oxochromium(IV) complex with dianionic tetradentate ligand salen (where H₂salen is N,N′-bis(salicylidene)-1,2-ethylenediamine) has been synthesized. This compound [CrO(OH₂)(salen)] (1) is characterized by elemental analysis, magnetic moment measurement, IR, UV-Vis and EPR spectroscopic studies. Measured room temperature (RT) magnetic moment value is 2.96 BM for 1 indicates a d² system with a triplet ground state. The magnetic moment value rules out a large spin-orbit coupling. The RT and LNT powder EPR spectra of 1 in X-band clearly shows two lines, one around g = 1.965 and the other with larger intensity at g = 4.26 ± 0.10. The first line at g = 1.965 corresponds to the |0> ↔ |±1> transition from the Kramers doublet |±1>, while the broad and intense line at low field with the g-value of 4.26 ± 0.10 is due to the forbidden transition |−1> ↔ |+1>. Compound 1 displays two successive reductions at −0.76 and −1.63 V (versus Ag/AgCl), respectively, while it undergoes only one irreversible oxidation as evident from the well-defined anodic wave at +1.48 V in its cyclic voltammogram.     

Molecular origin of the pH dependence of tyrosine D oxidation kinetics and radical stability in photosystem II

A role for redox-active tyrosines has been demonstrated in many important biological processes, including water oxidation carried out by photosystem II (PSII) of oxygenic photosynthesis. The rates of tyrosine oxidation and reduction and the Tyr/Tyr reduction potential are undoubtedly controlled by the immediate environment of the tyrosine, with the coupling of electron and proton transfer, a critical component of the kinetic and redox behavior. It has been demonstrated by Faller et al. that the rate of oxidation of tyrosine D (Tyr_D) at room temperature and the extent of Tyr_D oxidation at cryogenic temperatures, following flash excitation, dramatically increase as a function of pH with a pK_a of ≈ 7.6 [Faller et al. 2001 Proc. Natl. Acad. Sci. USA 98, 14368-14373; Faller et al. 2001 Biochemistry 41, 12914-12920]. In this work, we investigated, using FTIR difference spectroscopy, the mechanistic reasons behind this large pH dependence. These studies were carried out on Mn-depleted PSII core complexes isolated from Synechocystis sp. PCC 6803, WT unlabeled and labeled with ¹³C₆-, or ¹³C₁(4)-labeled tyrosine, as well as on the D2-Gln164Glu mutant. The main conclusions of this work are that the pH-induced changes involve the reduced Tyr_D state and not the oxidized Tyr_D state and that Tyr_D does not exist in the tyrosinate form between pH 6 and 10. We can also exclude a change in the protonation state of D2-His189 as being responsible for the large pH dependence of Tyr_D oxidation. Indeed, our data are consistent with D2-His189 being neutral both in the Tyr_D and Tyr_D states in the whole pH6-10 range. We show that the interactions between reduced Tyr_D and D2-His189 are modulated by the pH. At pH greater than 7.5, the ν(CO) mode frequency of Tyr_D indicates that Tyr_D is involved in a strong hydrogen bond, as a hydrogen bond donor only, in a fraction of the PSII centers. At pH below 7.5, the hydrogen-bonding interaction formed by Tyr_D is weaker and Tyr_D could be also involved as a hydrogen bond acceptor, according to calculations performed by Takahashi and Noguchi [J. Phys. Chem. B 2007 111, 13833-13844]. The involvement of Tyr_D in this strong hydrogen-bonding interaction correlates with the ability to oxidize Tyr_D at cryogenic temperatures and rapidly at room temperature. A strong hydrogen-bonding interaction is also observed at pH 6 in the D2-Gln164Glu mutant, showing that the residue at position D2-164 regulates the properties of Tyr_D. The IR data point to the role of a protonatable group(s) (with a pK_a of ≈ 7) other than D2-His189 and Tyr_D, in modifying the characteristics of the Tyr_D hydrogen-bonding interactions, and hence its oxidation properties. It remains to be determined whether the strong hydrogen-bonding interaction involves D2-His189 and if Tyr_D oxidation involves the same proton transfer route at low and at high pH.     

Spectroscopic properties of reaction center pigments in photosystem II core complexes: revision of the multimer model

Absorbance difference spectra associated with the light-induced formation of functional states in photosystem II core complexes from Thermosynechococcus elongatus and Synechocystis sp. PCC 6803 (e.g., ) are described quantitatively in the framework of exciton theory. In addition, effects are analyzed of site-directed mutations of D1-His¹⁹⁸, the axial ligand of the special-pair chlorophyll P_D1, and D1-Thr¹⁷⁹, an amino-acid residue nearest to the accessory chlorophyll Chl_D1, on the spectral properties of the reaction center pigments. Using pigment transition energies (site energies) determined previously from independent experiments on D1-D2-cytb559 complexes, good agreement between calculated and experimental spectra is obtained. The only difference in site energies of the reaction center pigments in D1-D2-cytb559 and photosystem II core complexes concerns Chl_D1. Compared to isolated reaction centers, the site energy of Chl_D1 is red-shifted by 4 nm and less inhomogeneously distributed in core complexes. The site energies cause primary electron transfer at cryogenic temperatures to be initiated by an excited state that is strongly localized on Chl_D1 rather than from a delocalized state as assumed in the previously described multimer model. This result is consistent with earlier experimental data on special-pair mutants and with our previous calculations on D1-D2-cytb559 complexes. The calculations show that at 5 K the lowest excited state of the reaction center is lower by ∼10 nm than the low-energy exciton state of the two special-pair chlorophylls P_D1 and P_D2 which form an excitonic dimer. The experimental temperature dependence of the wild-type difference spectra can only be understood in this model if temperature-dependent site energies are assumed for Chl_D1 and P_D1, reducing the above energy gap from 10 to 6 nm upon increasing the temperature from 5 to 300 K. At physiological temperature, there are considerable contributions from all pigments to the equilibrated excited state P*. The contribution of Chl_D1 is twice that of P_D1 at ambient temperature, making it likely that the primary charge separation will be initiated by Chl_D1 under these conditions. The calculations of absorbance difference spectra provide independent evidence that after primary electron transfer the hole stabilizes at P_D1, and that the physiologically dangerous charge recombination triplets, which may form under light stress, equilibrate between Chl_D1 and P_D1.     

Theoretical investigation of the dissociative interchange (Id) mechanism for water exchange on magnesium(II) in aqueous solution

A dissociative (D) and a solvent-assisted dissociative interchange (I_d) water-exchange pathways for magnesium(II) in aqueous solution were simulated with density functional theory calculations. The D mechanism of includes a five-coordinated intermediate, while the I_d water-exchange pathway of proceeds with the assistance of a solvent water molecule, which supports the experimental assignment of the reaction mechanism. The intrinsic activation volume was used to differentiate between I_d and I_a mechanisms despite of the exclusion of the contribution of transmission coefficient. The calculated intrinsic activation volume for the I_d mechanism is consistent with the experimental data, and is closer to the experimental data than that for D mechanism. The I_d mechanism is suggested as the dominate water-exchange pathway of depending on the intrinsic activation volume with the assistance of the activation entropy. The calculations also showed that the influences of the explicit and bulk waters on energy barriers for D and I_d mechanisms are obviously different.     

Analysis of the dependence of surfatron acceleration of electrons by an electromagnetic wave in space plasma on the particle momentum along the wave front

Based on the numerical solution of the nonlinear nonstationary second-order equation for the wave phase on the particle trajectory, the dynamics of surfatron acceleration of electrons by an electromagnetic wave propagating across the external magnetic field in space plasma is analyzed as a function of the electron momentum along the wave front. Numerical calculations show that, for strongly relativistic initial values of the electron momentum component along the wave front g _y (0) (the other parameters of the problem being the same), electrons are trapped into the regime of ultrarelativistic surfatron acceleration within a certain interval of the initial wave phase Ψ(0) on the particle trajectory. It is assumed in the calculations that |Ψ(0)| ≤ π. For strongly relativistic values of g _y (0), electrons are immediately trapped by the wave for 19% of the initial values of the phase Ψ(0) (favorable phases). For the rest of the values of Ψ(0), trapping does not occur even at long times. This circumstance substantially simplifies estimations of the wave damping due to particle acceleration in subsequent calculations. The dynamics of the relativistic factor and the components of the electron velocity and momentum under surfatron acceleration is also analyzed. The obtained results are of interest for the development of modern concepts of possible mechanisms of generation of ultrarelativistic particle fluxes in relatively calm space plasma, as well as for correct interpretation of observational data on the fluxes of such particles and explanation of possible reasons for the deviation of ultrarelativistic particle spectra detected in the heliosphere from the standard power-law scalings and the relation of these variations to space weather and large-scale atmospheric processes similar to tropical cyclones.     

Al4(C5Me4H)4: Structure, reactivity and bonding

The synthesis of Al₄R₄ (R = C₅(CH₃)₄H) (3) and the tetrahedral structure in the solid state are described. These results as well as the ²⁷Al NMR spectra of 3 in solution are in line with the data obtained from DFT calculations. These calculations also support the failed observation of a monomeric AlR species in solution. Monomeric and tetrameric molecules of 3 are discussed with respect to those of (AlCp^∗)₄ (1) and (AlCp)₄ (2). The increasing Al-Al bond strength from 1 to 3 and 2 from X-ray data is also supported by structural and energetic results from DFT calculations.     

Syntheses, structures and magnetic properties of two copper(II) tricyanomethanide complexes with 2,2′-bipyrimidine as bridging ligands

Two copper(II) tricyanomethanide (tcm) complexes with 2,2′-bipyrimidine (bpym) as co-ligands Cu₄(bpym)₅(tcm)₈ · 2H₂O (1) and [Cu₂(bpym)₂(tcm)₄ · H₂O]_n (2) have been synthesized, and structurally and magnetically characterized. Compound 1 displays a tetranuclear structure, in which each middle copper(II) atom is coordinated by two bridging bpym molecules and two terminal tcm ligands to form a tetragonal bipyramidal geometry, while each side copper(II) atom is surrounded by one bridging bpym, one terminal bpym, one terminal bonded tcm and one terminal weakly coordinated tcm ligands to give a square bipyramidal geometry. In 1 the four neighbouring copper(II) atoms are joined to each other by the bpym molecules, which leads to the formation of a tetranuclear structure. Compound 2 features an infinite chain structure, in which two slightly different chains exist. In each chain the copper(II) atom is bonded to two bridging bpym molecules and two terminal tcm ligands to form a tetragonal bipyramidal geometry, the adjacent copper(II) atoms are linked each other by the bpym ligands to define an infinite chain structure. In 2 the distances between two neighbouring copper(II) atoms in one chain are different. Moreover these distances in one chain are also different from those of the other chain. Magnetic susceptibility measurements for the two complexes in the temperature range 2-300 K reveal the occurrence of significant antiferromagnetic interactions for 1 (J₁ = −20.42 cm⁻¹, J₂ = −5.29 cm⁻¹ and g = 2.22) and 2 (T > 50 K, θ = −20.00 K, C = 0.86 cm³ mol⁻¹ K), respectively.     

The effect of treatment with 5,5'-dithiobis-(2-nitrobenzoic acid) on the initial rapid proton liberation during hydrolysis of adenosine triphosphate by myosin

The initial rate of proton liberation during MgATP hydrolysis by myosin was followed in a stopped flow spectrophotometer: before and after treatment with 5,5′-dithiobis-(2-nitrobenzoic acid) (DTNB) with and without removal of the corresponding light chain. At pH 8, 20°, and in the presence of MgCl₂, the biphasic pattern of the initial rate of proton liberation for native myosin became monophasic following treatment with DTNB, removal of the corresponding light chain, and regeneration of the steady state ATPase activity. The rate constant characterizing the single exponential term increased with MgATP concentration attaining a maximum value of 100 s^?1 at 300 μM MgATP with an apparent 2° rate constant of 7 × 10⁵ M^?1s^?1. Both the biphasic and monophasic pattern of initial proton liberation observed for myosin and subfragment 1 respectively (Pemrick, S.M. and F.G. Walz, 1972. J. Biol. Chem. $\text{247}$: 2959) can be explained by differences in the relative amounts of the DTNB light chain.     

Magnetic and optical properties of trans-RSSR-[CrCl2(cyclam)]2ZnCl4 (cyclam = 1,4,8,11-tetraazacyclotetradecane) attributed to counterion via hydrogen bonding

This is the first reported example of a photochromic property presented by the change of a counterion in a coordination compound: the colour of the trans-[CrCl₂(cyclam)]₂ZnCl₄ (1) is dark green while the trans-[CrCl₂(cyclam)]Cl (2) is a reddish purple. The dark green colour of 1 under a fluorescent lamp changes to a deep purple when it is irradiated with an incandescent lamp; when the latter light is turned off, the dark green colour reappears instantaneously, this being a reversible process. Besides, the electron paramagnetic resonance (EPR) spectra of these polycrystalline samples show a very broad isotropic peak centred at g = 1.995 for 1 and for 2 a rhombic one at g = 4.309, 3.107 and 1.223. Their molar magnetic susceptibilities, χ_Mdc, against temperature (2-300 K) follow Curie Weiss behaviour. For 1, a low antiferromagnetic coupling (θ = −2.78 K) in the solid state was found as it approaches 2 K, while for 2, there was found a smaller antiferromagnetic coupling (θ = −0.40 K). From the luminescence studies at 17 K, the lifetime for 1 was found to be twice that for 2. The crystal and molecular structure of 2 were determined and discussed. Compounds 1 and 2 show the same trans-RSSR configuration with different hydrogen bonding networks. In 1 the supramolecular array includes intermolecular interactions in which the chromium atoms interact through the zinc atom of the tetrachlorozincate counterion via hydrogen bonding with the extraordinary consequence of showing the previously described physical properties. This has been supported by theoretical calculations, in which it is clearly observed that the HOMO orbital of 1 is a highly delocalised molecular orbital among Cr(III)?Zn(II)?Cr(III), thus giving even more evidence for the strong Cr(III)-Cr(III) interaction through the ZnCl₄ moiety via hydrogen bonding.     

Ferromagnetic interactions in copper(II) and nickel(II) coordination polymers containing nitronyl nitroxide radical and terephthalate

Two new complexes [Cu(NITmPy)₂(tp)] 1 and [Ni(NITmPy)₂(tp)(H₂O)₂] 2 (NITmPy=2-(3^′-pyridyl)-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide and tp=terephthalato dianion) were synthesized and structurally and magnetically characterized. The structure of 1 is a neutral infinite chain where Cu(NITmPy)₂ units are linked by terephthalate ligands. In complex 2, the 1-D chains of Ni(NITmPy)₂ (H₂O)₂ units connected by tp develop into 2-D network via hydrogen bond interactions. The magnetic properties of 1 and 2 have been investigated in the temperature range 2-300 K. Both complexes exhibit ferromagnetic coupling and antiferromagnetic interactions dominate at low temperature. The magnetic behavior is discussed based on their structures.     

Phloretin and phloretin analogs: Mode of action in planar lipid bilayers and monolayers

Summary Phloretin and other neutral phloretin-like molecules are able to decrease the electrostatic potential within neutral lipid bilayers and monolayers. The relationship between the change in the dipole potential and the aqueous concentration of the molecule is well described by a Langmuir isotherm. From the Langmuir isotherm, the apparent dissociation constants (K _D ^A ) and the maximum dipole potential change ( _max) are obtained for the different phloretin-like molecules tested. Considering the phloretin analogs as derivatives of acetophenone containing two kinds of substituents, one on the benzene ring and another on the carbon chain, it is found that (a)K _D ^A is related to the hydrophobicity of the compound and is also a function of the position of the hydroxyl substituent in the ring; (b) from the dependence ofK _D ^A on the length of the acyl chain, it is estimated that the free-energy change is 650 cal/mole CH₂; (c) _max is not a simple function of the dipole moment of the molecule but depends on the substituent on the carbon chain and on the position and number of hydroxyl groups on the benzene ring; (d) phloretin adsorption parameters are a function of membrane lipid composition. The results are discussed in terms of the effect of these compounds on chloride transport in red blood cells.     

Model study of muscle spindle primary endings subjected to dynamic fusimotor activation

An earlier proposed model of the de-efferented muscle spindle mechano-receptors has been developed further to simulate the effects of the dynamic fusimotor ( _D) activation of the group Ia afferents (primary endings).The rate sensitivity of the original second order receptor model might be increased simply by increasing the overall viscous damping of the simulated polar regions of the nuclear bag fibre. However, adequate simulation of the typical time course of the stretch response of the primary endings during _D-activation required a subdivision of the polar regions into an active and a passive part. A reasonable behaviour of the model was obtained by simulating a local contraction covering about 50–90% of the polar regions of the nuclear bag fibres.The ramp response of the model showed a quick rate response component that increased by increasing the rate of the simulated stretch. This component was not significantly influenced by the simulated _D-activation.A slow rate component appeared to increase approximately in the same proportion as the intensity of the simulated _D-activation.The behaviour of the model closely corresponds to that of the biological prototype. The study demonstrates that the electrophysiological effects of activating the dynamic fusimotor fibres are indeed compatible with peripheral mechanical events associated with contraction phenomena within the polar regions of the nuclear bag intrafusal muscle fibres.     

Determination of the Primary and Fine Structures of a Galactomannan from the Seed of Gleditsia triacanthos f. inermis L.

Galactomannan, a polysaccharide with a molecular weight of 660 kDa, was isolated for the first time from the seed of Gleditsia triacanthos f. inermis (yield, 15.4%). Its aqueous solutions were optically active ([] _D = +31.0°) and highly viscous ([] = 578 ml/g). Analysis of this heteropolysaccharide using chemical, enzymatic, and chromatographic procedures, as well as IR and ¹³C NMR spectroscopy, showed that it consists of D-mannopyranose and D-galactopyranose residues (molar ratio, 2.42 : 1). The main chain of this galactomannan comprises 1,4--D-mannopyranose residues, 41% of which are substituted at C6 with single residues of -D-galactopyranose. The probability of occurrence in the chain of mannobiose units substituted otherwise, determined experimentally, was 0.16 for the Man–Man unit, 0.50 for the Gal(Man–Man) and (Man–Man)Gal units, and 0.34 for the disubstituted Gal(Man–Man)Gal unit.