Sensitivity and the available free space per molecule in the unit cell

Invoking the known link between impact sensitivity and compressibility, we have expanded upon an earlier preliminary study of the significance of the available free space per molecule in the unit cell, ΔV. We express ΔV as V_eff – V_int, where V_eff corresponds to zero free space, V_eff = molecular mass/density. V_int is the intrinsic gas phase molecular volume. We demonstrate that V_int can be appropriately defined as the volume enclosed by the 0.003 au contour of the molecule’s electronic density; this produces packing coefficients that have the range and average value found crystallographically. Measured impact sensitivities show an overall tendency to increase as ΔV becomes larger. For nitramines, the dependence upon ΔV is rather weak; we interpret this as indicating that a single overriding factor dominates their initiation mechanism, e.g., N-NO₂ rupture. (An analogous situation appears to hold for many organic azides.) In addition to the conceptual significance of identifying ΔV as a factor in impact sensitivity, the present results allow rough estimates of relative sensitivities that are not known.     

Theoretical description of hydrogen bonding in oxalic acid dimer and trimer based on the combined extended-transition-state energy decomposition analysis and natural orbitals for chemical valence (ETS-NOCV)

In the present study we have analyzed hydrogen bonding in dimer and trimer of oxalic acid, based on a recently proposed charge and energy decomposition scheme (ETS-NOCV). In the case of a dimer, two conformations, α and β, were considered. The deformation density contributions originating from NOCV’s revealed that the formation of hydrogen bonding is associated with the electronic charge deformation in both the σ—(Δρ_σ) and π-networks (Δρ_π). It was demonstrated that σ-donation is realized by electron transfer from the lone pair of oxygen on one monomer into the empty r_{H - O}^* \rho_{H - O}^* orbital of the second oxalic acid fragment. In addition, a covalent contribution is observed by the density transfer from hydrogen of H-O group in one oxalic acid monomer to the oxygen atom of the second fragment. The resonance assisted component (Δρ_π), is based on the transfer of electron density from the π—orbital localized on the oxygen of OH on one oxalic acid monomer to the oxygen atom of the other fragment. ETS-NOCV allowed to conclude that the σ(O---HO) component is roughly eight times as important as π (RAHB) contribution in terms of energetic estimation. The electrostatic factor (ΔE_elstat) is equally as important as orbital interaction term (ΔE_orb). Finally, comparing β-dimer of oxalic acid with trimer we found practically no difference concerning each of the O---HO bonds, neither qualitative nor quantitative.     

Theoretical studies on nitrogen rich energetic azoles

Different nitro azole isomers based on five membered heterocyclics were designed and investigated using computational techniques in order to find out the comprehensive relationships between structure and performances of these high nitrogen compounds. Electronic structure of the molecules have been calculated using density functional theory (DFT) and the heat of formation has been calculated using the isodesmic reaction approach at B3LYP/6-31G* level. All designed compounds show high positive heat of formation due to the high nitrogen content and energetic nitro groups. The crystal densities of these energetic azoles have been predicted with different force fields. All the energetic azoles show densities higher than 1.87 g/cm³. Detonation properties of energetic azoles are evaluated by using Kamlet-Jacobs equation based on the calculated densities and heat of formations. It is found that energetic azoles show detonation velocity about 9.0 km/s, and detonation pressure of 40GPa. Stability of the designed compounds has been predicted by evaluating the bond dissociation energy of the weakest C-NO₂ bond. The aromaticity using nucleus independent chemical shift (NICS) is also explored to predict the stability via delocalization of the π-electrons. Charge on the nitro group is used to assess the impact sensitivity in the present study. Overall, the study implies that all energetic azoles are found to be stable and expected to be the novel candidates of high energy density materials (HEDMs).     

Energetic and regulatory role of proton potential in chloroplasts

The review focuses on the energetic and regulatory role of proton potential in the activity of chloroplasts, the light energy-converting organelles of plant cells. Mechanisms of generation of the transmembrane difference of electrochemical potentials of hydrogen ions in the chloroplast thylakoid membranes are considered. Methods for measuring the intrathylakoid pH in chloroplasts are described. It is shown that under conditions of phosphorylation in chloroplasts, the pH of the intrathylakoid space decreases moderately (pH_in ⩾ 6.0–6.2, at the stroma pH_out ∼ 7.8–8.0), with a corresponding concentration component of equal to ΔpH ⩽ 1.6–2.0. On analyzing the energy and structural features of ATP synthase of chloroplasts, we conclude that the energy stored as the concentration component of the proton potential ΔpH is sufficient to sustain ATP synthesis. The mechanisms of pH-dependent regulation of electron transport in chloroplasts (photosynthetic control of electron transport, enhancement of non-photochemical quenching of chlorophyll excitation in the light-harvesting antenna, light-induced activation of the Calvin-Benson cycle reactions, activation of ATP synthase) are considered briefly.     

Theoretical studies on 2-diazo-4,6-dinitrophenol derivatives aimed at finding superior propellants

In an attempt to find superior propellants, 2-diazo-4,6-dinitrophenol (DDNP) and its –NO₂, –NH₂, –CN, –NC, –ONO₂, and –NF₂ derivatives were studied at the B3LYP/6-311++G^** level of density functional theory (DFT). Sensitivity was evaluated using bond dissociation enthalpies (BDEs) and molecular surface electrostatic potentials. The C–NO₂ bond appears to be the trigger bond during the thermolysis process for these compounds, except for the –ONO₂ and –NF₂ derivatives. Electrostatic potential results show that electron-withdrawing substituents make the charge imbalance more anomalous, which may change the strength of the bond, especially the weakest trigger bond. Most of the DDNP derivatives have the impact sensitivities that are higher than that of DDNP, making them favorable for use as solid propellants in micro-rockets. The theoretical densities (ρ), heats of formation (HOFs), detonation energies (Q), detonation pressures (P), and detonation velocities (D) of the compounds were estimated. The effects of various substituent groups on ρ, HOF, Q, D, and P were investigated. Some derivatives exhibit perfect detonation properties. The calculated relative specific impulses (I _r,sp) of all compounds except for –NH₂ derivatives were higher than that of DDNP, and also meet the requirements of propellants.     

Using light as a lure is an efficient predatory strategy in <Emphasis Type="Italic">Arachnocampa flava,</Emphasis> an Australian glowworm

Trap-building, sit-and-wait predators such as spiders, flies and antlions tend to have low standard metabolic rates (SMRs) but potentially high metabolic costs of trap construction. Members of the genus Arachnocampa (glowworms) use an unusual predatory strategy: larvae bioluminesce to lure positively phototropic insects into their adhesive webs. We investigated the metabolic costs associated with bioluminescence and web maintenance in larval Arachnocampa flava. The mean rate of CO₂ production ([(V)\dot] \dot{V}CO₂) during continuous bioluminescence was 4.38 μl h⁻¹ ± 0.78 (SEM). The mean [(V)\dot] \dot{V}CO₂ of inactive, non-bioluminescing larvae was 3.49 ± 0.35 μl h⁻¹. The mean [(V)\dot] \dot{V}CO₂ during web maintenance when not bioluminescencing was 8.95 ± 1.78 μl h⁻¹, a value significantly lower than that measured during trap construction by other predatory arthropods. These results indicate that bioluminescence itself is not energetically expensive, in accordance with our prediction that a high cost of bioluminescence would render the Arachnocampa sit-and-lure predatory strategy inefficient. In laboratory experiments, both elevated feeding rates and daily web removal caused an increase in bioluminescent output. Thus, larvae increase their investment in light output when food is plentiful or when stressed through having to rebuild their webs. As light production is efficient and the cost of web maintenance is relatively low, the energetic returns associated with continuing to glow may outweigh the costs of continuing to attract prey.     

Hydrogen bonding interactions in PN···HX complexes: DFT and ab initio studies of structure, properties and topology

Spin-restricted DFT (X3LYP and B3LYP) and ab initio (MP2(fc) and CCSD(fc)) calculations in conjunction with the Aug-CC-pVDZ and Aug-CC-pVTZ basis sets were performed on a series of hydrogen bonded complexes PN···HX (X = F, Cl, Br) to examine the variations of their equilibrium gas phase structures, energetic stabilities, electronic properties, and vibrational characteristics in their electronic ground states. In all cases the complexes were predicted to be stable with respect to the constituent monomers. The interaction energy (ΔE) calculated using a super-molecular model is found to be in this order: PN···HF > PN···HCl > PN···HBr in the series examined. Analysis of various physically meaningful contributions arising from the Kitaura-Morokuma (KM) and reduced variational space self-consistent-field (RVS-SCF) energy decomposition procedures shows that the electrostatic energy has significant contribution to the over-all interaction energy. Dipole moment enhancement (Δμ) was observed in these complexes expected of predominant dipole-dipole electrostatic interaction and was found to follow the trend PN···HF > PN···HCl > PN···HBr at the CCSD level. However, the DFT (X3LYP and B3LYP) and MP2 levels less accurately determined these values (in this order HF < HCl < HBr). Examination of the harmonic vibrational modes reveals that the PN and HX bands exhibit characteristic blue- and red shifts with concomitant bond contraction and elongation, respectively, on hydrogen bond formation. The topological or critical point (CP) analysis using the static quantum theory of atoms in molecules (QTAIM) of Bader was considered to classify and to gain further insight into the nature of interaction existing in the monomers PN and HX, and between them on H-bond formation. It is found from the analysis of the electron density ρ _c , the Laplacian of electron charge density ∇²ρ_c, and the total energy density (H _c ) at the critical points between the interatomic regions that the interaction N···H is indeed electrostatic in origin (ρ_c > 0, ∇²ρ_c > 0 and H_c > 0 at the BCP) whilst the bonds in PN (ρ_c > 0, ∇²ρ_c > 0 and H_c < 0) and HX ((ρ_c > 0, ∇²ρ_c < 0 and H_c < 0)) are predominantly covalent. A natural bond orbital (NBO) analysis of the second order perturbation energy lowering, E⁽²⁾, caused by charge transfer mechanism shows that the interaction N···H is n(N) → BD*(HX) delocalization.     

Flow-Dependent Activation of Maxi K+ Channels in Apical Membrane of Rabbit Connecting Tubule

The Ca²⁺-activated maxi K⁺ channel was found in the apical membrane of everted rabbit connecting tubule (CNT) with a patch-clamp technique. The mean number of open channels (NP _o ) was markedly increased from 0.007 ± 0.004 to 0.189 ± 0.039 (n= 7) by stretching the patch membrane in a cell-attached configuration. This activation was suggested to be coupled with the stretch-activation of Ca²⁺-permeable cation channels, because the maxi K⁺ channel was not stretch-activated in both the cell-attached configuration using Ca²⁺-free pipette and in the inside-out one in the presence of 10 mm EGTA in the cytoplasmic side. The maxi K⁺ channel was completely blocked by extracellular 1 μm charybdotoxin (CTX), but was not by cytoplasmic 33 μm arachidonic acid (AA). On the other hand, the low-conductance K⁺ channel, which was also found in the same membrane, was completely inhibited by 11 μm AA, but not by 1 μm CTX. The apical K⁺ conductance in the CNT was estimated by the deflection of transepithelial voltage (ΔV _t ) when luminal K⁺ concentration was increased from 5 to 15 mEq. When the tubule was perfused with hydraulic pressure of 0.5 KPa, the ΔV _t was only −0.7 ± 0.4 mV. However, an increase in luminal fluid flow by increasing perfusion pressure to 1.5 KPa markedly enhanced ΔV _t to −9.4 ± 0.9 mV. Luminal application of 1 μm CTX reduced the ΔV _t to −1.3 ± 0.6 mV significantly in 6 tubules, whereas no significant change of ΔV _t was recorded by applying 33 μm AA into the lumen of 5 tubules (ΔV _t =−7.2 ± 0.5 mV in control vs.ΔV _t =−6.7 ± 0.6 mV in AA). These results suggest that the Ca²⁺-activated maxi K⁺ channel is responsible for flow-dependent K⁺ secretion by coupling with the stretch-activated Ca²⁺-permeable cation channel in the rabbit CNT. Received: 21 August 1997/Revised: 20 March 1998     

Ferredoxin-quinone reductase benefits cyclic electron flow around photosystem 1 in tobacco leaves upon exposure to chilling stress under low irradiance

The function of chloroplast ferredoxin quinone reductase (FQR)-dependent flow was examined by comparing a wild type tobacco and a tobacco transformant (ΔndhB) in which the ndhB gene had been disrupted with their antimycin A (AA)-fed leaves upon exposure to chilling temperature (4 °C) under low irradiance (100 μmol m⁻² s⁻¹ photon flux density). During the chilling stress, the maximum photochemical efficiency of photosystem (PS) 2 (F_v/F_m) decreased markedly in both the controls and AA-fed leaves, and P700⁺ was also lower in AA-fed leaves than in the controls, implying that FQR-dependent cyclic electron flow around PS1 functioned to protect the photosynthetic apparatus from chilling stress under low irradiance. Under such stress, non-photochemical quenching (NPQ), particularly the fast relaxing NPQ component (q_f) and the de-epoxidized ratio of the xanthophyll cycle pigments, (A+Z)/(V+A+Z), formed the difference between AA-fed leaves and controls. The lower NPQ in AA-fed leaves might be related to an inefficient proton gradient across thylakoid membranes (ΔpH) because of inhibiting an FQR-dependent cyclic electron flow around PS1 at chilling temperature under low irradiance.     

Applications of the ETS-NOCV method in descriptions of chemical reactions

The present study characterizes changes in the electronic structure of reactants during chemical reactions based on the combined charge and energy decomposition scheme, ETS-NOCV (extended transition state–natural orbitals for chemical valence). Decomposition of the activation barrier, ΔE ^#, into stabilizing (orbital interaction, ΔE _orb, and electrostatic, ΔE _elstat) and destabilizing (Pauli repulsion, ΔE _Pauli, and geometry distortion energy, ΔE _dist) factors is discussed in detail for the following reactions: (I) hydrogen cyanide to hydrogen isocyanide, HCN → CNH isomerization; (II) Diels-Alder cycloaddition of ethene to 1,3-butadiene; and two catalytic processes, i.e., (III) insertion of ethylene into the metal-alkyl bond using half-titanocene with phenyl-phenoxy ligand catalyst; and (IV) B–H bond activation catalyzed by an Ir-containing catalyst. Various reference states for fragments were applied in ETS-NOCV analysis. We found that NOCV-based deformation densities (Δρ _i) and the corresponding energies ΔE _orb(i) obtained from the ETS-NOCV scheme provide a very useful picture, both qualitatively and quantitatively, of electronic density reorganization along the considered reaction pathways. Decomposition of the barrier ΔE^# into stabilizing and destabilizing contributions allowed us to conclude that the main factor responsible for the existence of positive values of ΔE ^# for all processes (I, II, III and IV) is Pauli interaction, which is the origin of steric repulsion. In addition, in the case of reactions II, III and IV, a significant degree of structural deformation of the reactants, as measured by the geometry distortion energy, plays an important role. Depending on the reaction type, stabilization of the transition state (relatively to the reactants) originating either from the orbital interaction term or from electrostatic attraction can be of vital importance. Finally, use of the ETS-NOCV method to describe catalytic reactions allows extraction of information on the role of catalysts in determination of ΔE ^#.     

Stereoelectronic Properties of N-acetyl-α,β-dehydroamino acid N′-methylamides

Summary α,β-Dehydroamino acids are useful peptide modifiers. However, their stereoelectronic properties still remain insufficiently recognized. Based on FTIR experiments in the range ofv _s(N-H), AI, AII andv _s(C^α=C^β) and ab initio calculations with B3LYP/6–31G*, we studied the solution conformational preferences and the amide electron density perturbation of Ac-ΔXaa-NHMe, where ΔXaa=ΔAla, (E)-ΔAbu, (Z)-ΔAbu, (Z)-ΔLeu, (Z)-ΔPhe and ΔVal. Each of these dehydroamides adopts a C₅ structure, which in Ac-ΔAla-NHMe is fully extended and accompanied by the strong C₅ hydrogen bond. Interaction with bond C^α=C^β lessens the amidic resonance within the flanking amide groups. TheN-terminal C=O bond is noticeably shorter, both amide bonds are longer than the corresponding bonds in the saturated entities and the N-terminal amide system is distorted. Ac-ΔAla-NHMe constitutes an exception. ItsC-terminal amide bond is shorter than the standard one and both amide systems are ideally planar. Ac-(E)-ΔAbu-NHMe shares stereoelectronic features with both Ac-ΔAla-NHMe and (Z)-dehydroamides.     

A monte carlo approach to population dynamics of cells in a HIV immune response model

Summary Using a direct Monte Carlo simulation, population growth of helper T-cells (N _H) and viral cells (N _v) is studied for an immune response model with an enhanced spatial inter-cellular interaction relevant to HIV as a function of viral mutation. In the absence of cellular mobility (P _mob=0), the helper T-cells grow nonmonotonically before reaching saturation and the viral population grows monotonically before reaching a constant equilibrium. Cellular mobility (P _mob=1) enhances the viral growth and reduces the stimulative T-cell growth. Below a mutation threshold (P _c), the steady-state density of helper T-cell (p _H) is larger than that of the Virus (p _v); the density difference Δp _o(=pV−pH) remains a constant at P _mob=1 while −Δp _o→0 as P _mut→P _c at P _mob=0. Above the mutation threshold, the difference Δp _o in cell density, grows with ΔP=P _mut−P _c monotonically: ΔP _o ∞ (ΔP)^β ≃ with β≈0.574±0.016 in absence of mobility, while Δp _o≈6(ΔP) with P _mob=1.     

Theoretical study of the effect of N-oxides on the performances of energetic compounds

In order to study the effects of N-oxide on structure and performance, six categories of energetic compounds were systemically investigated. The results indicated that the C–C bonds in the rings were shortened, and the C–N bonds close to the N?→?O bond were elongated when N atoms was oxidized to form N?→?O bonds. N?→?O bonds can increase the densities of most categories of compounds, and the increment will increase with the number of N?→?O bonds. As to their detonation performances, almost all categories of compounds had an increased trend, except for some NO₂-, NHNO₂- and ONO₂-substituted compounds. The contribution of 1,2,3,4-tetrazine and 1,2,4,5-tetrazine to performances was better than that of pyrazine and [1,2,5] oxadiazolo [3,4-b] pyrazine on the whole, and the groups, especially energetic groups, made a huge contribution to performance. When R was a NH₂ or ONO₂ group, all compounds had lower impact sensitivities, and thus represent candidates for novel energetic compounds. However, other than the sixth category of compounds, all compounds had higher impact sensitivities when R was a NO₂ or NHNO₂ group, and have little significance in application.

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Graphical abstract To study the effects of N-oxide on the structure and performance of energetic compounds, and to propose theoretical guidance for the design of novel compounds, the six categories (94 species) listed in the figure were investigated systemically by density functional theory methods and some empirical formulae

     

Computational design and structure–property relationship studies on heptazines

This study aimed to design novel nitrogen-rich heptazine derivatives as high energy density materials (HEDM) by exploiting systematic structure–property relationships. Molecular structures with diverse energetic substituents at varying positions in the basic heptazine ring were designed. Density functional techniques were used for prediction of gas phase heat of formation by employing an isodesmic approach, while crystal density was assessed by packing calculations. The results reveal that nitro derivatives of heptazine possess a high heat of formation and further enhancement was achieved by the substitution of nitro heterocycles. The crystal packing density of the designed compounds varied from 1.8 to 2 g cm⁻³, and hence, of all the designed molecules, nitro derivatives of heptazine exhibit better energetic performance characteristics in terms of detonation velocity and pressure. The calculated band gap of the designed molecules was analyzed to establish sensitivity correlations, and the results reveal that, in general, amino derivatives possess better insensitivity characteristics. The overall performance of the designed compounds was moderate, and such compounds may find potential applications in gas generators and smoke-free pyrotechnic fuels as they are rich in nitrogen content.     

Molecular characterization of <Emphasis Type="Italic">Vibrio cholerae</Emphasis> Δ<Emphasis Type="Italic">relA</Emphasis> Δ<Emphasis Type="Italic">spoT</Emphasis> double mutants

In Escherichia coli cellular levels of pppGpp and ppGpp, collectively called (p)ppGpp, are maintained by the products of two genes, relA and spoT. Like E. coli, Vibrio cholerae also possesses relA and spoT genes. Here we show that similar to E. coli, V. cholerae ΔrelA cells can accumulate (p)ppGpp upon carbon starvation but not under amino acid starved condition. Although like in E. coli, the spoT gene function was found to be essential in V. cholerae relA ⁺ background, but unlike E. coli, several V. cholerae ΔrelA ΔspoT mutants constructed in this study accumulated (p)ppGpp under glucose starvation. The results suggest a cryptic source of (p)ppGpp synthesis in V. cholerae, which is induced upon glucose starvation. Again, unlike E. coli ΔrelA ΔspoT mutant (ppGpp⁰ strain), the V. cholerae ΔrelA ΔspoT mutants showed certain unusual phenotypes, which are (a) resistance towards 3-amino-1,2,4-triazole (AT); (b) growth in nutrient poor M9 minimal medium; (c) ability to stringently regulate cellular rRNA accumulation under glucose starvation and (d) initial growth defect in nutrient rich medium. Since these phenotypes of ΔrelA ΔspoT mutants could be reverted back to ΔrelA phenotypes by providing SpoT in trans, it appears that the spoT gene function is crucial in V. cholerae. Part of this work was presented at the International Symposium on Chemical Biology, Kolkata, India, 7–9 March 2007.     

Multilocus epistasis,linkage, and genetic variance in breeding populations with few parents

In a previous study of maize (Zea mays L.) populations formed from few parents, we found that estimates of genetic variances were inconsistent with a simple additive genetic model. Our objective in the current study was to determine how multilocus epistasis and linkage affect the loss of genetic variance in populations created from a small number of parents (N). In simulation experiments, F₂ individuals from the same single cross were intermated to form progeny populations from N = 1, 2, 4, and 8 parents. Additive gene effects and metabolic flux epistasis due to L = 10, 50, and 100 loci were modeled. For additive, additive-with-linkage, epistatic, and epistasis-with-linkage models, we estimated the ratio between total genetic variance in the progeny population (V _N ) and base population (V _B ) as well as the 95th (Δ_95%) and 75th (Δ_75%) percentile differences between the estimated V _N /V _B and the V _N /V _B expected for the additive model. The mean V _N /V _B ratio was lower under epistasis than under additivity, indicating that metabolic flux epistasis hastens the decline in genetic variance due to small N. In contrast, Δ_95% was higher with epistasis than with additivity across the different levels of N and L. Linkage had little effect on the mean V _N /V _B , whereas it increased Δ_95% and Δ_75% under both additivity and epistasis. Smaller N and L led to higher V _N /V _B particularly when epistasis was present. Overall, the results indicated that while metabolic flux epistasis led to a faster average decline in genetic variance, it also led to greater variability in this decline to the point that V _N /V _B was larger than expected in many populations.     

Synthesis of secasterol and 24-episecasterol and their toxicity for MCF-7 cells

The convergent synthesis of biosynthetic precursors of brassinosteroids with a Δ₂-bond in cycle A—secasterol and 24-episecasterol—was performed. The key stages in the construction of the side chain in these compounds were the Julia olefination of the steroid 22-aldehyde followed by the Sharpless asymmetric dihydroxylation of the intermediate Δ₂₂-olefin. The cytotoxicity of the synthesized compounds for breast carcinoma MCF-7 cells was assessed.     

Photosynthetic and stomatal responses of two tropical and two temperate trees to atmospheric humidity

The effects of leaf to air vapour pressure differences (ΔW) on net photosynthetic rate (P_N) and stomatal conductance (g_s) were examined in the leaves of two tropical rain forest trees, Eugenia grandis and Pongamia pinnata, and two temperate evergreen trees, Viburnum awabuki and Daphniphyllum macropodum. A single leaf was set inside a small chamber and ΔW was varied from 7 to 24 mmol mol^-1 at 25 and 500 μmol m^-2 s^-1 of photon flux density. P_N and g_s of the two tropical rain forest trees decreased with increasing ΔW, while the two temperate evergreen trees were not highly responsive to ΔW. P. pinnata was more sensitive to ΔW in its stomatal response, and had a higher stomatal density and higher stomatal index than did the two temperate trees and another tropical tree. Significant reductions i n g_s and intercellular CO₂ concentrations in the two tropical trees at high ΔW suggest that the decline of P_N was due to the decrease in g_s. The responses of P_N and g_s indicated that the tropical trees were more sensitive to ΔW than were the temperate ones. This revised version was published online in September 2006 with corrections to the Cover Date.     

Induction changes in photosystems I and II in plant leaves upon modulation of membrane ion transport

The steady-state regime of linear photosynthetic electron transport implies concerted operation of photosystems I and II (PSI and PSII) in plant leaves. Acidification of the thylakoid lumen is known to cause down-regulation of PSII photochemical activity but it is not yet clear how the proton accumulation in the lumen affects the PSI activity and coordinated operation of the two photosystems in intact leaves. Chlorophyll fluorescence and absorbance of oxidized chlorophyll P700 in the near-infrared region ΔA _810–870 (ΔA ₈₁₀) are convenient noninvasive indicators of the redox state of PSII and PSI components, respectively. Simultaneous measurements of chlorophyll fluorescence and ΔA ₈₁₀ in pea leaves revealed that some kinetic stages in the induction curves occur synchronously both in dark-adapted and preilluminated leaves. After the treatment of leaves with ionophores promoting or inhibiting the light-induced thylakoid pH gradient (valinomycin, nigericin, monensin), the induction curves of ΔA ₈₁₀ and chlorophyll fluorescence were consistently modified. The results suggest that characteristic stages of ΔA ₈₁₀ induction curve, representing the second and the third waves of P700 photooxidation, are closely related to ΔpH generation, although the bases of ΔpH dependence differ for these two stages. The second wave of ΔA ₈₁₀ depends presumably on stroma alkalinization as a precondition for photoactivation of electron flow from PSI to terminal acceptors. The third wave of ΔA ₈₁₀ is apparently due to retardation of electron flow between PSII and PSI upon acidification of the lumen.