Maximum H+/h{nu}PSI Stoichiometry of Proton Transport during Cyclic Electron Flow in Intact Chloroplasts Is at Least Two, but Probably Higher than Two

Effects of antimycin A on 9-aminoacridine (9AA) fluorescencequenching by intact chloroplasts during light-dependent electronflow to different electron acceptors indicated that considerablecyclic electron flow occurs concurrently with linear electrontransport already at low PFDs, when oxygen supported electronflow, but not, when nitrite or methylviologen (MV) were present.Quantum efficiencies of the use of 696 and 675 nm light werecalculated for oxygen-, nitrite- and MV-dependent linear electronflows. Since H⁺/e=3 during linear electron transport [Ivanov(1993) Photosynthesis, p. 111; Kobayashi et al. (1995) PlantCell Physiol. 36: 1613] and comparable 9AA fluorescence quenchingindicates comparable transthylakoid proton gradients, totalproton transport could be calculated and part of it could beassigned to linear and the remainder to cyclic electron transportwhen oxygen was electron acceptor. Quanta of 696 nm light notused to support linear electron flow to oxygen at h/e=2 wereassumed to be available for coupled proton transport duringcyclic electron flow. H⁺/h ratios for cyclic electron transportobtained on this basis were consistently higher than 1 and occasionallyapproached 3. No allowance was made in these calculations foroxidized P700 in the reaction center of PSI, which could notdonate electrons to the cyclic pathway, and for reduced Q_A inthe reaction center of PSII. It therefore appears likely thatmaximum H⁺/h ratios in cyclic electron transport are higherthan values calculated in this work. Our observations with intactchloroplasts agree in principle with those of [Heath (1972)Biochim. Biophys. Acta 256: 645] with thylakoids, who also reportedhigh H⁺/ e ratios in cyclic electron transport. These ratiosare briefly discussed in relation to the H⁺/ATP stoichiometryof ATP production during carbon assimilation of leaves and toprotection of chloroplasts against photoinactivation. ²Present address: Timiriasev Institute of Plant Physiology,Russian Academy of Sciences, Botanicheskaya, 35, Moscow, Russia ³Present address: Department of Forestry, Faculty of Agriculture,Kyushu University, Hakozaki, Higashi-ku, Fukuoka, 812 Japan     

Coupling Ratios H+/e=3 versus H+/e=2 in Chloroplasts and Quantum Requirements of Net Oxygen Exchange during the Reduction of Nitrite, Ferricyanide or Methylviologen

Using intact and osmotically ruptured chloroplasts, ratios ofcoupling between deposition of protons in the intrathylakoidspace and light-dependent transport of electrons from waterto an external acceptor were determined. The data indicate couplingbetween proton and electron transport at a ratio of H⁺/e=3 withmethylviologen as electron acceptor in thylakoids and with nitriteas electron acceptor in intact chloroplasts. With ferricyanideas electron acceptor in thylakoids, values close to H⁺/e=2 wereobserved. Evidence is discussed that H⁺/e=3 is a fixed valuein intact chloroplasts at levels of thylakoid energization sufficientfor supporting effective carbon assimilation. In the presence of methylviologen and ascorbate, the minimumquantum requirement of oxygen uptake by thylakoids was about2.7 quanta of 675 nm light per O₂ indicating an e/O₂ ratio of1.33. In the absence of ascorbate, and with KCN present in additionto methylviologen, e/O₂ ratios up to 4 were observed. The minimumquantum requirement of oxygen evolution by thylakoids in thepresence of ferricyanide and by intact chloroplasts in the presenceof nitrite was about 8 quanta/O₂. (Received May 1, 1995; Accepted October 2, 1995)     

Regulation of Photosynthetic Electron Transport in Intact Spinach Chloroplasts: II. MECHANISM OF SALT-INDUCED INCREASE IN OXALOACETATE PHOTOREDUCTION

The main focus of this study was to determine the mechanism by which certain exogenous monovalent salts stimulate rates of net O₂ evolution linked to oxaloacetate reduction in intact spinach chloroplasts. The influence of salts on the dicarboxylate translocator involved in the transport of oxaloacetate and on the activity and activation of the chloroplast enzyme NADP-malate dehydrogenase, which mediates electron transport to oxaloacetate, was examined. High concentrations of KCl (155 millimolar) increased the apparent K_m for oxaloacetate but did not significantly alter the maximal velocity of uptake. Likewise, external salts (KCl, MgCl₂, or KH₂PO₄) had minimal effects on the magnitude of light activation of NADP-malate dehydrogenase. In contrast, measurements of chloroplast NADP-malate dehydrogenase activity (after release by osmotic shock) showed a marked dependence on salt concentration. Rates were stimulated approximately 2-fold by both monovalent (optimally 75 millimolar) and divalent (optimally 20 millimolar) salts. It was inferred that the salt-induced increase in net rates of O₂ evolution linked to oxaloacetate reduction is due, at least in part, to stimulation of NADP-malate dehydrogenase caused by monovalent cation permeability of the chloroplast inner envelope membrane.     

Regulation of Photosynthetic Electron Transport in Intact Spinach Chloroplasts: I. INFLUENCE OF EXOGENOUS SALTS ON OXALOACETATE REDUCTION

Relatively high concentrations of monovalent salts (150 millimolar) stimulated light-saturated uncoupled rates of O₂ evolution linked to oxaloacetic acid (OAA) reduction by intact chloroplasts 2-to 3-fold. In contrast, monovalent salts partially inhibited light-saturated rates of O₂ evolution coupled to CO₂ fixation and uncoupled rates of nitrite reduction. In the presence of high salt concentration, light-saturated rates of electron transport were about equivalent for all three terminal electron acceptors. It is inferred that exogenous monovalent salts have at least two effects on photosynthetic electron transport, independent of photophosphorylation and CO₂ metabolism: a partial inhibitory effect common to OAA, NO₂⁻ and CO₂ reduction and a marked stimulatory effect unique to the photoreduction of OAA.     

Characterization of an Electron Transport Pathway Associated with Glucose and Fructose Respiration in the Intact Chloroplasts of Chlamydomonas reinhardtii and Spinach

The role of an electron transport pathway associated with aerobic carbohydrate degradation in isolated, intact chloroplasts was evaluated. This was accomplished by monitoring the evolution of ¹⁴CO₂ from darkened spinach (Spinacia oleracea) and Chlamydomonas reinhardtii chloroplasts externally supplied with [¹⁴C]fructose and [¹⁴C]glucose, respectively, in the presence of nitrite, oxaloacetate, and conventional electron transport inhibitors. Addition of nitrite or oxaloacetate increased the release of ¹⁴CO₂, but it was shown that O₂ continued to function as a terminal electron acceptor. ¹⁴CO₂ evolution was inhibited up to 30 and 15% in Chlamydomonas and spinach, respectively, by 50 μm rotenone and by amytal, but at 500- to 1000-fold higher concentrations, indicating the involvement of a reduced nicotinamide adenine dinucleotide phosphate-plastoquinone oxidoreductase. ¹⁴CO₂ release from the spinach chloroplast was inhibited 80% by 25 μm 2,5-dibromo-3-methyl-6-isopropyl-p-benzoquinone. ¹⁴CO₂ release was sensitive to propylgallate, exhibiting approximately 50% inhibition in Chlamydomonas and in spinach chloroplasts of 100 and 250 μm concentrations, respectively. These concentrations were 20- to 50-fold lower than the concentrations of salicylhydroxamic acid (SHAM) required to produce an equivalent sensitivity. Antimycin A (100 μm) inhibited approximately 80 to 90% of ¹⁴CO₂ release from both types of chloroplast. At 75 μm, sodium azide inhibited ¹⁴CO₂ evolution about 50% in Chlamydomonas and 30% in spinach. Sodium azide (100 mm) combined with antimycin A (100 μm) inhibited ¹⁴CO₂ evolution more than 90%. ¹⁴CO₂ release was unaffected by uncouplers. These results are interpreted as evidence for a respiratory electron transport pathway functioning in the darkened, isolated chloroplast. Chloroplast respiration defined as ¹⁴CO₂ release from externally supplied [1-¹⁴C]glucose can account for at least 10% of the total respiratory capacity (endogenous release of CO₂) of the Chlamydomonas reinhardtii cell.     

The Coupling of Electron Flow to ATP Synthesis in Pea and Maize Mesophyll Chloroplasts : I. INTERACTION OF ADENINE NUCLEOTIDES AND ENERGY TRANSFER INHIBITORS WITH THE COUPLING FACTOR COMPLEX

The rate of nonphosphorylating electron transport (in the absence of ADP and inorganic phosphate) in well-coupled (ATP/2e⁻ = 0.9-1.1) maize mesophyll chloroplasts is not modulated by external pH (6.5-8.5), low levels of ADP or ATP, or energy transfer inhibitors, e.g. triphenyltin and Hg²⁺ ions. In contrast nonphosphorylating electron flow in pea chloroplasts is sensitive to alterations in medium pH, and to the presence of adenine nucleotides and energy transfer inhibitors in the assay medium. Although ATP is without effect on the rate of basal electron transport in maize chloroplasts, steady-state proton uptake is stimulated 3- to 5-fold by low levels of ATP. These results suggest that differences may exist in the manner in which the coupling factor complex controls proton efflux from the intrathylakoid space in C₃ and C₄ mesophyll chloroplasts.     

Adaptations of Photosynthetic Electron Transport,Carbon Assimilation,and Carbon Partitioning in Transgenic Nicotiana plumbaginifolia Plants to Changes in Nitrate Reductase Activity

Transgenic Nicotiana plumbaginifolia plants that express either a 5-fold increase or a 20-fold decrease in nitrate reductase (NR) activity were used to study the relationships between carbon and nitrogen metabolism in leaves. Under saturating irradiance the maximum rate of photosynthesis, per unit surface area, was decreased in the low NR expressors but was relatively unchanged in the high NR expressors compared with the wild-type controls. However, when photosynthesis was expressed on a chlorophyll (Chl) basis the low NR plants had comparable or even higher values than the wild-type plants. Surprisingly, the high NR expressors showed very similar rates of photosynthesis and respiration to the wild-type plants and contained identical amounts of leaf Chl, carbohydrate, and protein. These plants were provided with a saturating supply of nitrate plus a basal level of ammonium during all phases of growth. Under these conditions overexpression of NR had little impact on leaf metabolism and did not stimulate growth or biomass production. Large differences in photochemical quenching and nonphotochemical quenching components of Chl a fluorescence, as well as the ratio of variable to maximum fluorescence, (FV/FM), were apparent in the low NR expressors in comparison with the wild-type controls. Light intensity-dependent increases in nonphotochemical quenching and decreases in FV/FM were greatest in the low NR expressors, whereas photochemical quenching decreased uniformly with increasing irradiance in all plant types. Nonphotochemical quenching was increased at all except the lowest irradiances in the low NR expressors, allowing photosystem II to remain oxidized on its acceptor side. The relative contributions of photochemical and nonphotochemical quenching of Chl a fluorescence with changing irradiance were virtually identical in the high NR expressors and the wild-type controls. Zeaxanthin was present in all leaves at high irradiances; however, at high irradiance leaves from the low NR expressors contained considerably more zeaxanthin and less violaxanthin than wild-type controls or high NR expressors. The leaves of the low NR expressors contained less Chl, protein, and amino acids than controls but retained more carbohydrate (starch and sucrose) than the wild type or high NR expressors. Sucrose phosphate synthase activities were remarkably similar in all plant types regardless of the NR activity. In contrast phosphoenolpyruvate carboxylase activities were increased on a Chl or protein basis in the low NR expressors compared with the wild-type controls or high NR expressors. We conclude that large decreases in NR have profound repercussions for photosynthesis and carbon partitioning within the leaf but that increases in NR have negligible effects.     

Influence of pH upon the Warburg Effect in Isolated Intact Spinach Chloroplasts: I. Carbon Dioxide Photoassimilation and Glycolate Synthesis

The influence of pH upon the O₂ inhibition of ¹⁴CO₂ photoassimilation (Warburg effect) was examined in intact spinach (Spinacia oleracea) chloroplasts. With conditions which favored the Warburg effect, i.e. rate-limiting CO₂ and 100% O₂, O₂ inhibition was greater at pH 8.4 to 8.5 than at pH 7.5 to 7.8. At pH 8.5, as compared with 7.8, there was an enhanced ¹⁴C-labeling of glycolate, and a decrease of isotope in some phosphorylated Calvin cycle intermediates, particularly triose-phosphate. The ¹⁴C-labeling of starch was also more inhibited by O₂ at higher pH. The enhanced synthesis of glycolate during ¹⁴CO₂ assimilation at higher pH resulted in a diminution in the level of phosphorylated intermediates of the Calvin cycle, and this was apparently a causal factor of the increased severity of the Warburg effect.     

Regulation of Steady-State Photosynthesis in Isolated Intact Chloroplasts under Constant Light: Responses of Carbon Fluxes, Metabolite Pools and Enzyme-Activation States to Changes of Electron Pressure

The reactions of isolated intact spinach chloroplasts at saturatinglight and CO₂ to changes in steady-state electron flow werefollowed at the various stages of photosynthesis. Alterationsin the rate of electron flow were induced by the addition ofoxaloacetate (OAA), nitrite or methyl viologen (MV). Two typesof effect can be distinguished: (1) When a small fraction ofthe electrons produced are accepted by OAA or nitrite (up to20% of the electrons produced in the light), the activationstate of the NADP⁺-dependent malate dehydrogenase (NADP-MDH)was strongly decreased, whereas qP and the rate of O₂-productionwere increased. qN, the stromal metabolite pools and the [¹⁴C]-CO₂-fixationrate were only marginally influenced. (2) Higher amounts ofnitrite or MV decreased O₂ production and strongly inhibited[¹⁴C]CO₂ fixation. This treatment further increased the ATP/ADPratio, but had little effect on the NADPH + H⁺/NADP⁺ ratio.The stromal concentrations of 3PGA, DHAP and FBP, and the ratesof 3PGA and DHAP export were drastically changed. In particular,the DHAP/3PGA ratio increased, and the rate of 3PGA export wasdecreased by minor changes in the rate of electron flow. Additionof high amounts of nitrite or MV, but not of OAA decreased theactivation states of NADP-MDH and fructose 1,6-bisphosphatase(FBPase), while the activation states of NADP⁺-dependent glyceraldehyde3-phosphate dehydrogenase (GAPDH) and phosphoribulokinase (PRK)remained unchanged under all conditions. (Received February 10, 1997; Accepted September 2, 1997)     

Adaptation of the Photosynthetic Apparatus in Maize Leaves as a Result of Nitrogen Limitation : Relationships between Electron Transport and Carbon Assimilation

In maize (Zea mays L., cv Contessa), nitrogen (NO₃⁻) limitation resulted in a reduction in shoot growth and photosynthetic capacity and in an increase in the leaf zeaxanthin contents. Nitrogen deficiency had only a small effect on the quantum yield of CO₂ assimilation but a large effect on the light-saturated rate of photosynthesis. Linear relationships persisted between the quantum yield of CO₂ assimilation and that of photosystem II photochemistry in all circumstances. At high irradiances, large differences in photochemical quenching and nonphotochemical quenching of Chl a fluorescence as well as the ratio of variable to maximal fluorescence (Fv/Fm) were apparent between nitrogen-deficient plants and nitrogen-replete controls, whereas at low irradiances these parameters were comparable in all plants. Light intensity-dependent increases in nonphotochemical quenching were greatest in nitrogen-deficient plants as were the decreases in Fv/Fm ratio. In nitrogen-deficient plants, photochemical quenching decreased with increasing irradiance but remained higher than in controls at high irradiances. Thermal dissipative processes were enhanced as a result of nitrogen deficiency (nonphotochemical quenching was elevated and Fv/Fm was lowered) allowing PSII to remain relatively oxidised even when carbon metabolism was limited via nitrogen limitation.     

Fixation of O(2) during Photorespiration: Kinetic and Steady-State Studies of the Photorespiratory Carbon Oxidation Cycle with Intact Leaves and Isolated Chloroplasts of C(3) Plants

Mass spectrometric techniques were used to trace the incorporation of [¹⁸O]oxygen into metabolites of the photorespiratory pathway. Glycolate, glycine, and serine extracted from leaves of the C₃ plants, Spinacia oleracea L., Atriplex hastata, and Helianthus annuus which had been exposed to [¹⁸O]oxygen at the CO₂ compensation point were heavily labeled with ¹⁸O. In each case one, and only one of the carboxyl oxygens was labeled. The abundance of ¹⁸O in this oxygen of glycolate reached 50 to 70% of that of the oxygen provided after only 5 to 10 seconds exposure to [¹⁸O]oxygen. Glycine and serine attained the same final enrichment after 40 and 180 seconds, respectively. This confirms that glycine and serine are synthesized from glycolate.

The labeling of photorespiratory intermediates in intact leaves reached a mean of 59% of that of the oxygen provided in the feedings. This indicates that at least 59% of the glycolate photorespired is synthesized with the fixation of molecular oxygen. This estimate is certainly conservative owing to the dilution of labeled oxygen at the site of glycolate synthesis by photosynthetic oxygen. We examined the yield of ¹⁸O in glycolate synthesized in vitro by isolated intact spinach chloroplasts in a system which permitted direct sampling of the isotopic composition of the oxygen at the site of synthesis. The isotopic enrichment of glycolate from such experiments was 90 to 95% of that of the oxygen present during the incubation.

The carboxyl oxygens of 3-phosphoglycerate also became labeled with ¹⁸O in 20- and 40-minute feedings with [¹⁸O]oxygen to intact leaves at the CO₂ compensation point. Control experiments indicated that this label was probably due to direct synthesis of 3-phosphoglycerate from glycolate during photorespiration. The mean enrichment of 3-phosphoglycerate was 14 ± 4% of that of glycine or serine, its precursors of the photorespiratory pathway, in 10 separate feeding experiments. It is argued that this constant dilution of label indicates a constant stoichiometric balance between photorespiratory and photosynthetic sources of 3-phosphoglycerate at the CO₂ compensation point.

Oxygen uptake sufficient to account for about half of the rate of ¹⁸O fixation into glycine in the intact leaves was observed with intact spinach chloroplasts. Oxygen uptake and production by intact leaves at the CO₂ compensation point indicate about 1.9 oxygen exchanged per glycolate photorespired. The fixation of molecular oxygen into glycolate plus the peroxisomal oxidation of glycolate to glyoxylate and the mitochondrial conversion of glycine to serine can account for up to 1.75 oxygen taken up per glycolate.

These studies provide new evidence which supports the current formulation of the pathway of photorespiration and its relation to photosynthetic metabolism. The experiments described also suggest new approaches using stable isotope techniques to study the rate of photorespiration and the balance between photorespiration and photosynthesis in vivo.

     

Influence of pH upon the Warburg Effect in Isolated Intact Spinach Chloroplasts: II. Interdependency of Glycolate Synthesis upon pH and Calvin Cycle Intermediate Concentration in the Absence of Carbon Dioxide Photoassimilation

The light-dependent synthesis of glycolate derived from fructose 1,6-diphosphate, ribose 5-phosphate, or glycerate 3-phosphate was studied in the intact spinach (Spinacia oleracea) chloroplasts in the absence of CO(2). Glycolate yield increased with an elevation of O(2), pH, and the concentration of the phosphorylated compound supplied. No pH optimum was observed as the pH was increased from 7.4 to 8.5. The average maximal rate of glycolate synthesis was 50 mumoles per milligram chlorophyll per hour while the highest rate observed was 92 with 2.5 mm fructose 1,6-diphosphate in 100% O(2). The highest yields of glycolate synthesized from fructose 1,6-diphosphate, ribose 5-phosphate, or glycerate 3-phosphate were 0.14, 0.24, and 0.30, respectively, on a molar basis.     

Photoreduction of 18O2 and H218O2 with Concomitant Evolution of 16O2 in Intact Spinach Chloroplasts: Evidence for Scavenging of Hydrogen Peroxide by Peroxidase

Illuminated intact spinach chloroplasts decomposed one moleculeof H₂¹⁸O₂ which resulted in the evolution of a half moleculeof ¹⁶O₂, but little ¹⁸O₂. The chloroplasts showed the same rateof photoreduction of ¹⁸C₂ as that of the evolution of ¹⁶O₂ withoutaccumulation of H₂¹⁸O₂. These reactions were suppressed by DCMU,and also by several inhibitors of ascorbate peroxidase and dehydroascorbateand monodehydroascorbate reductases in chloroplasts. These observationsindicate that the hydrogen peroxide produced in chloroplastsis reduced to water by a peroxidase using a photoreductant asthe electron donor. The hydrogen peroxide scavenging systemof chloroplasts was inactivated if hydrogen peroxide was addedin the dark, but not if added during the light. (Received May 4, 1984; Accepted July 10, 1984)     

Electron Microscope Studies of Deoxyribonucleic Acid Synthesis in Escherichia coli: Localization of [3H]Thymidine in Deoxyribonucleic Acid-Membrane Complexes

The attachment of deoxyribonucleic acid to the membrane in Escherichia coli 15 T(-) cells incubated with [(3)H]thymidine was studied by electron microscopy. Isolated deoxyribonucleic acid-membrane complexes were prepared from synchronized and unsynchronized cells during the exponential or stationary phase of growth and were examined by autoradiography. After short pulses with [(3)H]thymidine, a specific enrichment in radioactivity was observed in areas of membranous structures in exponentially growing cells. In contrast, the grain tracks produced in autoradiographs of chromosomes from cells in stationary phase were randomly distributed. The autoradiographic patterns are, therefore, evidence that deoxyribonucleic acid replication is closely related to the bacterial membrane.     

Reduction of Mitochondrial Electron Transport Complex Activity Is Restricted to the Ischemic Focus After Transient Focal Cerebral Ischemia in Rats: A Histochemical Volumetric Analysis

Using histochemical methods offering high topographical resolution for evaluation of changes in the ischemic focus and the penumbra, the mitochondrial electron transport chain (ETC) complexes I, II, and IV were examined in rats subjected to 2 h of proximal occlusion of the middle cerebral artery (MCAO) followed by no reperfusion, 1 h reperfusion, 4 h reperfusion, or 4 h reperfusion plus treatment with the free radical scavenger -PBN. Serial brain cryosections were histochemically stained to visualize activity of complexes I, II, and IV, and the volumes of tissue with reduced activity in the ipsilateral cortex and caudate putamen were measured by densitometric image analysis. Reductions in complex I, II, and IV activity were restricted to areas in the ischemic foci in cortex and caudate putamen, which microscopically displayed signs of early morphological damage. In cortex, the tissue volume with reduced activity did not change significantly during reperfusion but progressively increased in the caudate putamen, possibly reflecting a faster maturation of morphological damage in this region. Treatment with -PBN did not affect the observed reductions in activities. We deduce that inhibition of mitochondrial ETC complex activity does not play a critical role for recruitment of the penumbra in the infarction process.     

Photosynthetic Electron Transport Involved in PxcA-Dependent Proton Extrusion in Synechocystis sp. Strain PCC6803: Effect of pxcA Inactivation on CO2, HCO3−, and NO3− Uptake

The product of pxcA (formerly known as cotA) is involved in light-induced Na⁺-dependent proton extrusion. In the presence of 2,5-dimethyl-p-benzoquinone, net proton extrusion by Synechocystis sp. strain PCC6803 ceased after 1 min of illumination and a postillumination influx of protons was observed, suggesting that the PxcA-dependent, light-dependent proton extrusion equilibrates with a light-independent influx of protons. A photosystem I (PS I) deletion mutant extruded a large number of protons in the light. Thus, PS II-dependent electron transfer and proton translocation are major factors in light-driven proton extrusion, presumably mediated by ATP synthesis. Inhibition of CO₂ fixation by glyceraldehyde in a cytochrome c oxidase (COX) deletion mutant strongly inhibited the proton extrusion. Leakage of PS II-generated electrons to oxygen via COX appears to be required for proton extrusion when CO₂ fixation is inhibited. At pH 8.0, NO₃⁻ uptake activity was very low in the pxcA mutant at low [Na⁺] (~100 μM). At pH 6.5, the pxcA strain did not take up CO₂ or NO₃⁻ at low [Na⁺] and showed very low CO₂ uptake activity even at 15 mM Na⁺. A possible role of PxcA-dependent proton exchange in charge and pH homeostasis during uptake of CO₂, HCO₃⁻, and NO₃⁻ is discussed.     

Mechanochemical Synthesis: A Tool to Tune Cation Site Disorder and Ionic Transport Properties of Li3MCl6 (M = Y,Er) Superionic Conductors

The lithium‐conducting, rare‐earth halides, Li₃MX₆ (M = Y, Er; X = Cl, Br), have garnered significantly rising interest recently, as they have been reported to have oxidative stability and high ionic conductivities. However, while a multitude of materials exhibit a superionic conductivity close to 1 mS cm^?1, the exact design strategies to further improve the ionic transport properties have not been established yet. Here, the influence of the employed synthesis method of mechanochemical milling, compared to subsequent crystallization routines as well as classic solid‐state syntheses on the structure and resulting transport behavior of Li₃ErCl₆ and Li₃YCl₆ are explored. Using a combination of X‐ray diffraction, pair distribution function analysis, density functional theory, and impedance spectroscopy, insights into the average and local structural features that influence the underlying transport are provided. The existence of a cation defect within the structure in which Er/Y are disordered to a new position strongly benefits the transport properties. A synthetically tuned, increasing degree of this disordering leads to a decreasing activation energy and increasing ionic conductivity. This work sheds light on the possible synthesis strategies and helps to systematically understand and further improve the properties of this class of materials.     

Glutamine Synthesis and Its Relation to Photophosphorylation in Pisum Chloroplasts: Effects of 3-(3,4-Dichlorophenyl)-1,1-dimethylurea and Antimycin A

Illuminated pea (Pisum sativum) chloroplasts can convert glutamate to glutamine using ATP generated by photophosphorylation to drive the glutamine-synthetase reaction. Light-dependent glutamine synthesis is sensitive to 3-(3,4-dichlorophenyl)-1,1-dimethyl urea (DCMU), but only at concentrations higher than are necessary to suppress photoreduction of ferricyanide or phosphoglycerate. Conversely, glutamine synthesis is far more sensitive to antimycin A than is photoconversion of phosphoglycerate to triosephosphate. When 3.8 mm phosphoglycerate is supplied, glutamine synthesis is stimulated in both the presence and absence of antimycin A.These data seem to be consistent with the operation of an endogenous, DCMU-sensitive, phosphorylation process-possibly cyclic-which can support glutamine synthesis in white light under aerobic conditions. The stimulatory effect of phosphoglycerate suggests that noncyclic phosphorylation is initiated or accelerated when this substrate is supplied. This noncyclic process evidently provides ATP over and above the amount required for phosphoglycerate photoreduction, i.e. the ATP/e(2) ratio exceeds 1.0. The additional ATP produced under these conditions is available for glutamine synthesis and lessens its dependence on cyclically (or pseudocyclically) generated ATP.