The distribution of acid deposition in Germany

Summary The distribution of acid deposition by atmospheric precipitation in the Federal Republic of Germany is discussed, based on investigations of the wet H⁺-deposition during the five years 1980–1984, using a network of 16 automated samplers of our own construction located in various categories of ecosystems. Analytical problems of sampling and the electrometric determination of pH in rainwater are briefly discussed. Results for the average amounts of precipitation, the average H⁺-concentrations and average H⁺-depositions in the 16 typical regions of the Federal Republic of Germany are compared and the influences of meteorological parameters are discussed. An increase of the H⁺-concentration and H⁺-deposition values has been observed from 1980 onwards with a maximum in 1981 and a slow decrease in the next two years. The comparison of the values found for rural regions with those for more significantly polluted regions shows that in the latter regions the removal of H⁺-ions by wash-out is more effective. Whereas in the Ruhr region the pH is shifted to more acid values, due to the wash-out of acid particles and aerosols, in regions with metallurgical industry the pH is shifted to more alkaline values due to the wash-out of alkaline particles. In general the free acid in rain and snow is rather uniformly distributed over the whole area as a result of mesoscalic transport of the acid precursors SO₂ and NO_x and the concomitant formation of acid in the cloud droplets leading to acid deposition by rain-out. The composition of rainwater and the possibility of determining the proportion of the acid anions in rain which are of anthropogenic origin is briefly discussed.Deseased (May 12th, 1985).     

Vorgänge bei pH-Änderung und bei Belichtung eines Anthocyanidins

Summary The anthocyanidin investigated here exists below pH 4 as a cationAH ₂ ⁺ (wave length of absorption maximum _max=459 mµ), between pH 5 and 7 in the neutral formAH ( _max=492 mµ) and above pH 8 as an anionA ^– ( _max=537 mµ). At pH 5 the freshly dissolved substance is partially converted into a colourless formBH ( _max=372 mµ) and a chemical equilibrium betweenAH andBH is reached within 1 h. A kinetic study of the process of formation ofBH shows that an intermediate productZ is formed. This process can be reversed by light exposure. It can be concluded from a kinetic investigation by using flash light thatBH is transformed by the absorbing light into a new substanceL ( _max 275 mµ and 225 mµ), andL changes partially intoBH, partially intoZ, which itself is transformed partially intoAH ₂ ⁺ ,AH,A ^–, partially intoBH. The reactionZ AH,AH ₂ ⁺ ,A ^– is proportional to the concentration of protons [H ⁺], the reactionZ BH independent of [H ⁺]. Thus a photochemical production ofAH ₂ ⁺ ,AH,A ^– fromBH is readily obtained in the presence ofH ⁺ and not obtained in the absence ofH ⁺.     

Réversibilité de la réponse du potentiel de membrane chezNitella flexilis L. à des variations de pH

Summary The better the recovering of the membrane potential ofNitella on restoring the initial value of the external pH after a change, the more acid is the pH of the medium (Table I). On the other hand, a better repeatability was observed in alkaline solutions (Table II) for a change in the external K⁺ concentration. These results are interpreted as a manifestation of the binding of K⁺ ions to ionizable fixed charges (pK about 5–6) at the membrane surface and of the control of molecular structure of the membrane by the pH.     

Amiloride impairs the cholinergic regulation of potassium permeability in the human sweat gland but not in the rat submandibular gland

Potassium permeability was monitored in human sweat glands and rat submandibular glands. Acetylcholine increased permeability in both tissues and the responses consisted of transient, calcium-independent and sustained, calcium-dependent components. Amiloride, a drug which inhibits Na⁺?H⁺ countertransport, impaired the regulation of potassium permeability in sweat glands but not in the submandibular gland. It is suggested that the stimulus-permeability coupling process in the sweat gland may be sensitive to the lowering of internal pH.     

Kationengleichgewichte in biologischen Systemen

Summary The affinity of H⁺ and various metal-ions towards complexing agents of biological importance is characterised by the formation constantk*. The binding state of Cu²⁺ in human plasma is discussed and the amount of free Cu²⁺ is estimated to about 10^–6 moles per liter.     

The effect of temperature on the ouabain-sensitivity of Na+−K+-activated ATPase and fluid secretion by the Malpighian tubules ofLocusta

Summary Temperature markedly affected the ouabain-sensitivity of both the Na⁺–K⁺-activated ATPase activity and the secretion of fluid by the Malpighian tubules ofLocusta. Varying the K⁺ concentration in the bathing medium did not affect the ouabain-sensitivity of the fluid secretory process.     

Dual modes of 5-(N-ethyl-N-isopropyl)amiloride modulation of apical dipeptide uptake in the human small intestinal epithelial cell line Caco-2

Selective pharmacological Na⁺/H⁺ exchange (NHE) inhibitors were used to identify functional NHE isoforms in human small intestinal enterocytes (Caco-2) and to distinguish between direct and indirect effects on transport via the intestinal di/tripeptide transporter hPepT1. The relative potencies of these inhibitors to inhibit ²²Na⁺ influx identifies NHE3 and NHE1 as the apical and basolateral NHE isoforms. The Na⁺-dependent (NHE3-sensitive) component of apical dipeptide ([¹⁴C] Gly-Sar) uptake was inhibited by the selective NHE inhibitors with the same order of potency observed for inhibition of apical ²²Na⁺ uptake. However, 5-(N-ethyl-N-isopropyl) amiloride (EIPA) also reduced [¹⁴C]Gly-Sar uptake in the absence of Na⁺ and this inhibition was concentration and pH (maximal at pH 5.5) dependent. NHE3 inhibition by S1611 and S3226 modulates dipeptide uptake indirectly by reducing the transapical driving force (H⁺ electrochemical gradient). EIPA (at 100 μM) has similar effects, but at higher concentrations (>200 μM) also has direct inhibitory effects on hPepT1.Received 28 February 2005; received after revision 20 April 2005; accepted 20 May 2005     

Untersuchungen an Ionenaustauschmodellen zum Verständnis der Physiologie biogener Amine. Austauschversuche an einem schwefelsäuregruppentragenden Harz zum Verständnis von sogenannten Histaminliberationsvorgängen

Summary Mixtures of histamine and other basic substances as hydrochlorides were added in equivalent amounts to an acid ion exchange system containing SO₄-groups in the H⁺-form (Dowex 50 W × 2). After completion of the equilibrium, the amounts of both the free histamine and the competing substance were determined by potentiometric titration.Values are presented for the relative amounts of each substance which are retained by the resin.The results obtained show that histamine and a given competing substance are selectively distributed on the resin. The method may be useful as a test for the possible histamine-liberating capacity of biologically important substances.     

The ATP synthase (F0−F1) complex in oxidative phosphorylation

The transmembrane electrochemical proton gradient generated by the redox systems of the respiratory chain in mitochondria and aerobic bacteria is utilized by proton translocating ATP synthases to catalyze the synthesis of ATP from ADP and P_i. The bacterial and mitochondrial H⁺-ATP synthases both consist of a membranous sector, F₀, which forms a H⁺-channel, and an extramembranous sector, F₁, which is responsible for catalysis. When detached from the membrane, the purified F₁ sector functions mainly as an ATPase. In chloroplasts, the synthesis of ATP is also driven by a proton motive force, and the enzyme complex responsible for this synthesis is similar to the mitochondrial and bacterial ATP synthases. The synthesis of ATP by H⁺-ATP synthases proceeds without the formation of a phosphorylated enzyme intermediate, and involves co-operative interactions between the catalytic subunits.     

An isoform of the vacuolar (H+)-ATPase accessory subunit Ac45

The vacuolar (H⁺)-ATPase (V-ATPase) is the main regulator of intraorganellar pH and in neuroendocrine cells is controlled by its accessory subunit, Ac45. Here, we report the discovery of the first isoform of a V-ATPase accessory subunit, namely an Ac45-like protein, denoted Ac45LP. Phylogenetic analysis revealed a lineage-dependent evolutionary history: Ac45 is absent in birds, and Ac45LP is absent in placental mammals, whereas all other tetrapod species contain both genes. In contrast to Ac45, Ac45LP is not proteolytically cleaved, a prerequisite for proper Ac45 routing. Intriguingly, Xenopus Ac45LP mRNA was expressed in developing neural tissue and in neural crest cells. In adult Xenopus, Ac45 mRNA is widely expressed mostly in neuroendocrine tissues, while Ac45LP mRNA expression was found to be restricted to the kidney and the lung. This novel Ac45LP may provide additional possibilities for V-ATPase regulation during neurodevelopment as well as in kidney and lung cells.     

Untersuchungen an Ionenaustauschmodellen zum Verständnis der Physiologie biogener Amine

Summary A synthetic ion exchanger containingR-PO(OH)₂ as active groups was shown to retain histamine and other basic substances selectively and, in most cases, with marked preference over the other cations (Na⁺, H⁺) present in the system. The results are taken to indicate that similar exchange reactions may occur on biogenic polyelectrolytes bearing similar active groups.     

Monovalent cation conductance in liposomes induced by ionophore A23187

Summary In the absence of divalent cations, ionophore A23187 supports low rates of monovalent cations loss (Na⁺>K⁺) from unilamellar liposomes containing the sulfate salts. Monovalent cation efflux is optimal when a pH gradient (interior alkaline) is applied. The maximum observed rate of 0.56 ngion K⁺·min^–1·nmole^–1 A23187 is insufficient to account for the rates of K⁺ efflux induced by the ionophore in mitochondria (150 ngion K⁺·min^–1·nmole^–1 A23187). These studies therefore support the concept that A23187 induces loss of K⁺ from mitochondria by removal of regulating divalent cations from an endogenous K⁺/H⁺ exchanger.These studies were supported in part by United States Public Health Services Grant HL09364.     

Increased Na+-H+ exchanger activity in the ileal brush-border membrane of spontaneously hypertensive rats

In the present study, we have examined the intestinal Na⁺ transport, through the Na⁺-H⁺ exchanger, in ileal brush-border membrane vesicles (BBMV) isolated from spontaneously hypertensive rats (SHR), and normotensive Wistar Kyoto (WKY) rats as a control group. Na⁺ uptake into ileal BBMV was stimulated in the presence of a proton gradient (pH 5.5 inside/pH 7.5 outside) in SHR and WKY rats, resulting in a transient accumulation (overshoot) in both groups of rats. No overshoot was observed in the absence of a pH gradient. The magnitude of the accumulation was significantly higher in SHR than in WKY rats. Uptake of Na⁺ at equilibrium was identical in the presence and the absence of a proton gradient and was not changed in SHR. The use of amiloride inhibited pH gradient-driven Na⁺ uptake in a dose-dependent manner with a Ki of 90 μM and 100 μM for SHR and WKY rats, respectively. The relationship between proton gradient-driven Na⁺ uptake and external Na⁺ concentration was saturable and conformed to Michaelis-Menten kinetics in both SHR and WKY rats. Lineweaver-Burk analysis of the pH gradient-driven Na⁺ uptake indicated values of V_max that were significantly increased in SHR compared to WKY rats (11.4±0.55 nmol/mg/8 s vs. 4.96±0.78 nmol/mg/8 s for SHR and WKY rats, respectively). In contrast, similar K_m values for Na⁺ were found between SHR and WKY rats (4.0±0.2 mM vs. 4.9±0.6 mM for SHR and WKY rats, respectively). These studies show derangement in ileal BBMV Na⁺ transport of SHR, which is characterized by increased Na⁺-H⁺ exchanger activity. Received 18 December 1996; received after revision 3 February 1997; accepted 7 February 1997     

Potentiation by taurine of the inotropic effect of ouabain and the content of intracellular Ca++ and taurine in the heart

Summary Under certain conditions, taurine (3.0 mM) potentiated cardiac contractile response to ouabain in the normal medium. The potentiation by taurine was also observed in the low K⁺ medium, in which the positive inotropic effect of ouabain increased. The potentiation as seen in both media was, at least in part, due to the increase by taurine of Ca⁺⁺ content in the heart. Taurine in the heart was not directly related to this potentiation.     

Bicarbonate and chloride transport across rat ileal basolateral membrane

The mechanisms of HCO ₃ ^– and Cl^– transport across basolateral membranes from rat ileum were investigated in isolated vesicles by means of uptake experiments. Neither Cl^–/HCO ₃ ^– exchanger nor Na⁺–(HCO ₃ ^– )_n cotransport seem to be present in ileal basolateral membranes. Moreover Cl^– uptake is unaffected bycis Na⁺ and/or K⁺ gradients, indicating the absence of Na⁺–Cl^–, K⁺–Cl^– and Na⁺–K⁺–2Cl^– symport activity. An electrically conductive pathway seems to be responsible for both HCO ₃ ^– and Cl^– fluxes. Evidence is also given for the presence of a Na⁺/H⁺ exchanger at the basolateral pole of ileal enterocytes.     

Selective blockade of components of potassium activation inMyxicola axons

Summary The K⁺ conductance inMyxicola giant axons activates in two phases which are pharmacologically separable. The fast phase of K⁺ activation is specifically inhibited by 4-aminopyridine and by the substitution of D₂O for H₂O. We suggestMyxicola giant axons, like the amphibian node of Ranvier, may possess more than one variety of K⁺ channel.     

Biochemistry,evolution and physiological function of the Rnf complex,a novel ion-motive electron transport complex in prokaryotes

Microbes have a fascinating repertoire of bioenergetic enzymes and a huge variety of electron transport chains to cope with very different environmental conditions, such as different oxygen concentrations, different electron acceptors, pH and salinity. However, all these electron transport chains cover the redox span from NADH + H⁺ as the most negative donor to oxygen/H₂O as the most positive acceptor or increments thereof. The redox range more negative than −320 mV has been largely ignored. Here, we have summarized the recent data that unraveled a novel ion-motive electron transport chain, the Rnf complex, that energetically couples the cellular ferredoxin to the pyridine nucleotide pool. The energetics of the complex and its biochemistry, as well as its evolution and cellular function in different microbes, is discussed.     

Blockade by zinc ions of K+-induced contraction and calcium in guinea pigTaenia coli

Preincubation with 0.3 mM Zn²⁺ markedly inhibited both the tonic response and Ca²⁺ binding at low affinity sites induced by K⁺ (60 mM), with smaller effects on the phasic response and the high affinity Ca²⁺ sites, inTaenia coli. However, when the muscle was kept in Zn²⁺-containing medium following the first stimulation with the K⁺, the phasic response and the high affinity Ca²⁺ sites were more severely inhibited during the second stimulation with K⁺. This probably indicates that Zn²⁺ reduced the tonic tension response to K⁺ mainly by inhibiting Ca²⁺ influx at the cell membranes ofTaenia coli. However, when Zn²⁺ is continuously present, Ca²⁺ is not supplied at the storage sites and is not available for the phasic response to a second stimulation with K⁺.     

Effects of corpora cardiaca extract,furosemide and ion substitution on sodium and chloride flux in perfused Malpighian tubules ofLocusta

Treatment with the co-transport inhibitor, furosemide decreased³⁶Cl^– flux across perfused Malpighian tubules ofLocusta. However, exclusion of³⁶Cl^– from the bathing medium had not effect on²²Na⁺ flux whereas substitution of bathing medium Na⁺ by K⁺ increased³⁶Cl^– flux. Diuretic extract of corpora cardiaca increased²²Na⁺ (by 106%) and³⁶Cl^– (by 335%) fluxes differentially.     

Effects of pCai and pHi on cell-to-cell coupling

Summary Internal longitudinal resistance (r_i), a determinant of cardiac conduction, is affected by changes in intracellular calcium and protons. However, the role and mechanism by which H⁺ and Ca²⁺ may modulate r_i is uncertain. Cable analysis was performed in cardiac Purkinje fibers to measure r_i during various interventions. In some experiments, intracellular pH (pH_i) was recorded simultaneously to study the pH_i-r_i relation. Both intracellular Ca²⁺ and H⁺ independently modified r_i. However, internal resistance of cardiac fibers was insensitive to pH_i changes compared to other tissues. A latent period preceded the pH_i-related changes in r_i and the amount of change depended upon methodology. The results suggest that direct action of protons on r_i may be subordinate to other regulatory processes. Ionic regulation of internal longitudinal resistance may occur by more than one mechanism: i) direct cationic binding to sites on junctional membrane proteins; and ii) H⁺- or Ca²⁺-dependent phosphorylation of junctional proteins.