Voltage‐Switchable HCl Transport Enabled by Lipid Headgroup–Transporter Interactions

Synthetic anion transporters that facilitate transmembrane H⁺/Cl^? symport (cotransport) have anti‐cancer potential due to their ability to neutralize pH gradients and inhibit autophagy in cells. However, compared to the natural product prodigiosin, synthetic anion transporters have low‐to‐modest H⁺/Cl^? symport activity and their mechanism of action remains less well understood. We report a chloride‐selective tetraurea macrocycle that has a record‐high H⁺/Cl^? symport activity similar to that of prodigiosin and most importantly demonstrates unprecedented voltage‐switchable transport properties that are linked to the lack of uniport activity. By studying the anion binding affinity and transport mechanisms of four other anion transporters, we show that the lack of uniport and voltage‐dependent H⁺/Cl^? symport originate from strong binding to phospholipid headgroups that hampers the diffusion of the free transporters through the membrane, leading to an unusual H⁺/Cl^? symport mechanism that involves only charged species. Our work provides important mechanistic insights into different classes of anion transporters and a new approach to achieve voltage‐switchability in artificial membrane transport systems.     

Effects of ionizing radiation on bio-active plant extracts useful for preventing oxidative damages

Humans are exposed to ionizing radiations in medical radiodiagnosis and radiotherapy that cause oxidative damages and degenerative diseases. Airplane pilots, and even more astronauts, are exposed to a variety of potentially harmful factors, including cosmic radiations. Among the phytochemicals, phenols are particularly efficient in countering the oxidative stress. In the present study, different extracts obtained from plant food, plant by-products and dietary supplements, have been compared for their antioxidant properties before and after irradiation of 140 cGy, a dose absorbed during a hypothetical stay of three years in the space. All the dry extracts, characterized in terms of vitamin C and phenolic content, remained chemically unaltered and maintained their antioxidant capability after irradiation. Our results suggest the potential use of these extracts as nutraceuticals to protect humans from oxidative damages, even when these extracts must be stored in an environment exposed to cosmic radiations as in a space station.     

Template effect of tetrathiafulvalene in the formation of cyclobis(paraquat-p-phenylene)

[reaction: see text] The template effect exerted by tetrathiafulvalene (TTF) in the ring-closure reaction of the trication 5(3+) yielding cyclobis(paraquat-p-phenylene) has been quantitatively evaluated in acetonitrile at 62 degrees C with UV-vis spectrophotometry. The rate of ring closure of the trication 5(3+) largely increases in the presence of the template (a maximum increase of ca. 80 times at [TTF] approximately 0.14 M). The results are compared with those of other aromatic templates, 2 and 3, that were provided with polyethereal sidearms and indicate that the template ability of tetrathiafulvalene is comparable or better than that of the others.     

Two-point self-coordination of a dizinc(II) bispyridylporphyrin ruthenium complex leading selectively to a discrete molecular assembly: solution and solid-state characterization

The dizinc(II) bispyridylporphyrin ruthenium complex trans,cis,cis[RuCl2(CO)2(Zn.4'-cisDPyP)2] (1Zn, 4'-cisDPyP = 5,10-bis(4'-pyridyl)-15,20-diphenylporphyrin) features two donor (the uncoordinated 4'-N(py) atoms) and two acceptor (the Zn atoms) sites and is thus a building block suited for two-point coordination. 1H NMR spectroscopy indicates that 1Zn self-assembles in solution through Zn-4'-N(py) interactions to yield selectively a highly symmetrical discrete species, in which all donor and all acceptor sites of 1Zn are mutually saturated. Single-crystal X-ray analysis established that this adduct is a dimeric species, (1Zn)2, with a global S4 symmetry, in which the four porphyrins have a propeller-like arrangement. The dimeric species (1Zn)2 is a meso form derived from the combination of two 1Zn units with opposite helical chirality. The geometry of this highly symmetrical tetraporphyrin assembly in solution, as determined by NMR spectroscopy, is essentially the same as that found in the solid state. Thus 1Zn is an unprecedented example of metal-containing self-complementary building block that selectively recognizes itself through four Zn-N(py) interactions, and thus yields a very stable and symmetrical dimeric species, (1Zn)2, that features four porphyrins and six metal atoms (two Ru and four Zn).     

How to derive priorities in AHP: a comparative study

A heated discussion has arisen over the “best” priorities derivation method. Using a Monte Carlo simulation this article compares and evaluates the solutions of four AHP ratio scaling methods: the right eigenvalue method, the left eigenvalue method, the geometric mean and the mean of normalized values. Matrices with different dimensions and degree of impurities are randomly constructed. We observe a high level of agreement between the different scaling techniques. The number of ranking contradictions increases with the dimension of the matrix and the inconsistencies. However, these contradictions affect only close priorities.     

The lateral distribution of energetic shower muons

Summary The customary assumption of a unique structure function of the formf(r)∞r ^−αexp[−r/R ₀] with parameters independent of the shower size and the nature of the primary is tested against evidence on the multiplicity distribution of shower muons. The experimental data were obtained with an array of three spark chamber telescopes installed at the Mt. Cappuccini underground station, Torino, at depths of about 40 to 60 hg/cm². They pertain to events with mean shower sizes between about 10⁵ and a few 10⁷ electrons. It is shown that the results are incompatible with this assumption, whatever values are assigned to the exponent α and to the characteristic radiusR ₀ of the structure function. A modified representation allowing for a variation ofR ₀ with the shower size and with the massA of the primary is suggested. The resulting distribution is in reasonable agreement both with thorough Monte Carlo evaluations for proton and iron primaries and with direct experimental observations of other authors.

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Riassunto L'ipotesi usuale di una funzione di struttura unica della formaf(r)∞r ^−αexp[−r/R ₀] con parametri indipendenti dalle dimensioni dello sciame e dalla natura dei primari è provata rispetto alle prove sperimentali sulla distribuzione di molteplicità dei muoni dello sciame. I dati sperimentali sono stati ottenuti con un sistema di tre telescopi con camere a scintille istallati nella stazione sotterranea del Monte dei Capuccini, Torino, a profondità da 40 a 60 hg/cm². Essi riguardano eventi con grandezze medie di sciami tra circa 10⁵ e pochi 10⁷ elettroni. Si mostra che i risultati non sono compatibili con questa ipotesi, qualsiasi valore sia assegnato all'esponente α e al raggio caratteristicoR ₀ della funzione di struttura. Si suggerisce una rappresentazione modificata che consente una variazione diR ₀ con la grandezza dello sciame e con la massaA dei primari. La distribuzione risultante è in ragionevole accordo sia con tutte le valutazioni di Montecarlo per primari di protoni e di ferro e con osservazioni sperimentali dirette di altri autori.

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Резюме Исследуется обычное предположение о единственной структурной функции видаf(r)∼r ^−αexp[−r/R ₀], с параметрами, не зависяцими от размеров ливня и природы первичной частицы, на основе данных о распределении множественности мюонов в ливне. Зкспериментальные данные получены с помошью системы трех телескпов искровых камеп, установленных на подземной стандии Капучини в Турине, на глубинах от 40 до 60 гг/см². Полученные данные относятся к событиям со средними размерами ливня от 10⁵ до 10⁷ злектронов. Показывается, что полученные результаты являются несовместимыми с зтим предположением, какие бы значения зкспоненте α и характерному радиусуR ₀ структурной функции не были бы приписаны. Предлагается модифицированное представление, учитывающее изменение велиьиныR ₀ с размером ливия и с массойA первичной частицы. Полученное распределение хорошо согласуется и с оценками по Монте-Карло для первичных протонов и ядер железа и с непосредственными экспериментальными результатами других авторов.

     

An intermolecular force field for chlorinated benzene crystals

Intermolecular potential parameters corresponding to atom—atom interactions of the Buckingham form are refined on the basis of static and dynamic properties of some chlorinated benzene crystals. The model reproduces well the observed properties, including k ≠ 0 vibrations.     

Commensurate-incommensurate crossover of charge stripe in La2-xSrxNiO4 (x approximately 1/3)

The temperature (T) dependence of the charge-stripe order in La2-xSrxNiO4 has been investigated in the vicinity of x approximately 1/3 by synchrotron radiation x-ray diffraction measurements. With decreasing T, a prominent commensurate-incommensurate (C-IC) crossover is observed in the x<1/3 region, while for the x>1/3 region the IC order is dominant over the whole T range. Such a C-IC crossover is interpreted as the entropy-driven self-doping of the charge stripes, and its x dependence indicates the clear electron-hole asymmetry with the x=1/3 compound as the Mott insulator.     

Enantio- and stereocontrolled formation of the bisspiroacetal core of spirolide B

The bisspiroacetal core of spirolide B, a marine natural toxin, was synthesized from triketone 10 via one-step bisspiroacetalization, methylation, and silylation accompanied by isomerization of the C-15 spirocenter. The equilibrium of two isomers under acidic conditions was also examined.