Structure and flow of polyelectrolyte microgels: from suspensions to glasses

Polyelectrolyte microgels are soft particles due to their ability to de-swell osmotically. In dilute suspensions, they behave like soft Brownian particles. Above close-packing, they form pastes which share many features with glasses. The flow properties of suspensions and pastes are universal. They can be tuned at will to get the rheological behaviour which is desired. To cite this article: M. Cloitre et al., C. R. Physique 4 (2003).     

Eco-friendly methods of synthesis and preliminary biological evaluation of sulfonamide derivatives of cyclic arylguanidines

The chemotype of arylsulfonamide derivatives of cyclic arylguanidines is a source of molecules with valuable biological activities, including antimicrobial and antitumor properties. The methods of the synthesis presented in the literature are characterized with low selectivity and high environmental nuisance. In this publication, we present a developed alternative and earlier undescribed pathway C, for the synthesis of arylsulfonamide derivatives of cyclic arylguanidines (N-(1H-arylimidazol-2-yl)arylsulfonamides and N-(1,4-dihydroquinazolin-2-yl)arylsulfonamides), including reaction between 2-(methylsulfanyl)-benzimidazole or 2-(methylsulfanyl)-3,4-dihydroquinazoline with arylsulfonamides. We also optimized previously reported methods; A (reaction of 2-aminobenzimidazole or 2-amino-3,4-dihydroquinazoline with arylsulfonyl chlorides) and B (reaction of dimethyl-(arylsulfonyl)carbonodithioimidate with aryldiamines). The conducted research allowed achieving two independent ecological and quick methods of obtaining the desired products. We used ecological methods of ultrasound-assisted or microwave synthesis, solvent-free reactions and a “green” reaction environment. In both pathways, it has proven advantageous to use H₂O as the solvent and K₂CO₃ (1 or 3 equivalent) as the basic agent. In the sonochemical variant, the efficiency reached B: 37–89 %, C: 90 % in 60 min (P = 80 W and f = 40 kHz), while in the microwave synthesis it was B: 38–74 %, C: 63–85 % in 0.5–4 min (P = 50 W). Path A led to a complementary substitution product (i.e. 1-(arylsulfonyl)-1H-benzimidazol-2-amine or 1-(arylsulfonyl)-1,4-dihydroquinazolin-2-amine). We obtained a small group of compounds that were tested for cytotoxicity. The 10f (N-(1,4-dihydroquinazolin-2-yl)naphthalene-1-sulfonamide) showed cytotoxic activity towards human astrocytoma cell line 1321 N1. The calculated IC₅₀ value was 8.22 µM at 24 h timepoint (doxorubicin suppressed 1321 N1 cell viability with IC₅₀ of 1.1 µM). The viability of the cells exposed to 10f for 24 h dropped to 48.0 % compared to vehicle control, while the cells treated with doxorubicin experienced decline to 47.5 %. We assessed its potential usefulness in pharmacotherapy in the ADMET study, confirming its ability to cross the blood–brain barrier (Pe = 5.0 ± 1.5 × 10^-6 cm/s) and the safety of its potential use in terms of DDI and hepatotoxicity.     

2,7-Carbazole and thieno[3,4-c]pyrrole-4,6-dione based copolymers with deep highest occupied molecular orbital for photovoltaic cells

Three kinds of donor–acceptor (D–A) type photovoltaic polymers were synthesized based on 2,7-carbazole and thieno[3,4-c]pyrrole-4,6-dione (TPD). The conjugation of weakly electron (e)-donating 2,7-carbazole and strongly e-accepting TPD moieties yielded a deep highest occupied molecular orbital (HOMO) and its energy level was fine-controlled to be −5.72, −5.67 and −5.57 eV through the incorporation of thiophene (T), thieno[3,2-b]thiophene (TT) and bithiophene (BT) as a π-bridge. Polymer:[6,6]-phenyl-C₇₁ butyric acid methyl ester (PC₇₁BM) based bulk heterojunction solar cells exhibited a high open-circuit voltage (V_OC) in the range, 0.86–0.94 V, suggesting good agreement with the measured HOMO levels. Despite the high V_OC, the thiophene (or thienothiophene)-containing PCTTPD (or PCTTTPD) showed poor power conversion efficiency (PCE, 1.14 and 1.25%) because of the very low short-circuit current density (J_SC). The voltage-dependent photocurrent and photoluminescence quenching measurements suggested that hole transfer from PC₇₁BM to polymer depends strongly on the HOMO level of the polymer. The PCTTPD and PCTTTPD devices suffered from electron–hole recombination at the polymer/PC₇₁BM interfaces because of the insufficient energy offset between the HOMOs of the polymer and PC₇₁BM. The PCBTTPD:PC₇₁BM device showed the best PCE of 3.42% with a V_OC and J_SC of 0.86 V and 7.79 mA cm⁻², respectively. These results show that photovoltaic polymers should be designed carefully to have a deep HOMO level for a high V_OC and sufficient energy offset for ensuring efficient hole transfer from PC₇₁BM to the polymer.     

Synthesis,characterization and luminescence study of dimethyl[N-arylmethylenethiobenzahydrazonato]indium

Five dimethylindium complexes of type Me₂InL [L = N-(4-methoxy)benzylidenethiobenzahydrazonato (1), N-(3,4-dimethoxy)benzylidenethiobenzahydrazonato (2), N-(4-N,N-dimethylamino)benzylidenethiobenzahydrazonato (3), N-(2-naphthyl)methylene thiobenzahydrazonato (4) and N-(9-anthryl)methylenethiobenzahydrazonato (5)] have been synthesized by reaction of trimethylindium with appropriate N-arylmethylenethiobenzahydrozones. The complexes obtained have been characterized by elemental analysis, ¹H NMR, IR and mass spectroscopy. Compounds 1–5 emit blue colors at λ_max = 432–479 nm when irradiated by UV light. The electroluminescent (EL) properties of 1–5 were examined by fabricating EL devices using 1–5 as emitter, respectively. The EL bands are located in the green region (513–578 nm).     

Andreev reflection between a normal metal and the FFLO superconductor II: A self-consistent approach

We consider Andreev reflection in a two dimensional junction between a normal metal and a heavy fermion superconductor in the Fulde–Ferrell (FF) type of the Fulde–Ferrell–Larkin–Ovchinnikov (FFLO) state. We assume s-wave symmetry of the superconducting gap. The parameters of the superconductor: the gap magnitude, the chemical potential, and the Cooper pair center-of-mass-momentum Q, are all determined self-consistently within a mean-field (BCS) scheme. The Cooper pair momentum Q is chosen as perpendicular to the junction interface. We calculate the junction conductance for a series of barrier strengths. In the case of incoming electron with spin σ = ↑ only for magnetic fields close to the upper critical field H_c2, we obtain the so-called Andreev window, i.e. the energy interval in which the reflection probability is maximal, which in turn is indicated by a peak in the conductance. The last result differs with other non-self-consistent calculations existing in the literature.     

UV–Vis and NMR spectroscopic investigations on effective and selective non-covalent interactions between fullerenes and calix[6]arene

Ground state non-covalent interactions between a macro cyclic calixarene receptor, namely, 4-tert-butylcalix[6]arene (1), and fullerenes (C₆₀ and C₇₀) were studied in toluene medium by absorption spectrophotometric method. Absorption band due to the charge transfer (CT) transition have been observed in the visible region between fullerenes and 1. Utilizing the CT absorption bands, various important physicochemical parameters like oscillator strength, resonance energy, transition dipole strength of the fullerene-1 complexes and ionization potential of 1 is determined in present investigations. From Jobs method of continuous variation, it is observed that both C₆₀ and C₇₀ form stable 1:1 complexes with 1. The most fascinating feature of the present study is that 1 binds selectively C₇₀ compared to C₆₀ as obtained from binding constant (K) data of C₆₀–1 (K_C60–1) and C₇₀–1 (K_C70–1) complexes, i.e., K_C60–1 = 32,400 dm³·mol^? 1 and K_C70–1 = 110,000 dm³.mol^? 1 and selectivity (K_C70–1/K_C60–1) = 3.4. ¹H NMR analysis provides very good support in favor of strong binding between C₇₀ and 1.     

Synthesis and fluorescence study of water-soluble conjugated polymers for efficient FRET-based DNA detection

Two cationic conjugated polyelectrolytes (CPs, P1i and P2i) were synthesized and examined as a fluorescence resonance energy transfer (FRET) donor to fluorescein (Fl)-labeled single-stranded DNA (ssDNA–Fl) using steady-state and time-resolved photoluminescence (PL) spectroscopy. The two polymers have the same π-conjugation with the main structural difference being the presence of the spiro-anthracenyl substituents orthogonal to the polymer backbone of P2i. These spiro-substituents can function as a molecular spacer that increases the intermolecular separation in the electrostatic complex with ssDNA–Fl. We measured almost complete PL quenching of the excited Fl1 after electrostatic complexation with P1i (PL lifetime 4 ns → 78 ps) and relatively moderate quenching with P2i (PL lifetime 4 ns → 552 ps). A quenching efficiency (Φ_eT) of 98% and 86% was obtained for P1i/ssDNA–Fl and for P2i/ssDNA–Fl, respectively. Both systems have same thermodynamic driving force for quenching as a result of them having the same electronic structures. This discrepancy can be explained in terms of the reduced quenching (via electron transfer, eT) by the increased D–A distance due to the existence of spiro-attached molecular spacers in P2i. It shows that thermodynamically favorable eT quenching can be controlled kinetically by modulating the D–A intermolecular distance using molecular spacers, which suggests an important molecular design guideline for efficient CPs-based DNA detection.     

The origin of the Ca–Ti–Cr–Fe–Ni isotopic anomalies in the inclusion EK-1-4-1 of the Allende meteorite

The origin of the correlated Ca–Ti–Cr–Fe–Ni isotopic anomalies in the Ca–Al-rich inclusion of the EK-1-4-1 of the Allende is a longstanding puzzle. The search for a stellar environment which could explain the enrichment of neutron-rich stable Ca–⋯–Ni isotopes in a self-consistent way requires nuclear physics data far from stability. Recent experimental data have been obtained in the region of the shell closures N=28 and N=40, where the possible progenitors of these nuclei are found. Astrophysical network calculations have been updated by including the new β-decay properties and microscopic predictions of neutron-capture cross sections. Interplay between nuclear structure far from stability and the observed isotopic anomalies is especially evident for the high entropy (S≃150) scenario which would characterize the neutrino-driven wind in a type II supernova. To cite this article: O. Sorlin et al., C. R. Physique 4 (2003).     

Ultrasound-assisted synthesis of water-soluble monosubstituted diruthenium compounds

The elusive monosubstituted diruthenium complexes [Ru₂Cl(DAniF)(O₂CMe)₃] (1), [Ru₂Cl(DPhF)(O₂CMe)₃] (2), [Ru₂Cl(D-p-CNPhF)(O₂CMe)₃] (3), [Ru₂Cl(D-o-TolF)(O₂CMe)₃] (4), [Ru₂Cl(D-m-TolF)(O₂CMe)₃] (5), [Ru₂Cl(D-p-TolF)(O₂CMe)₃] (6) and [Ru₂Cl(p-TolA)(O₂CMe)₃] (7) have been synthesized using for the first time ultrasound-assisted synthesis to carry out a substitution reaction in metal–metal bonded dinuclear compounds (DAniF⁻ = N,N′-bis(4-anisyl)formamidinate; DPhF⁻ = N,N′-diphenylformamidinate; D-p-CNPhF⁻ = N,N′-bis(4-cyanophenyl)formamidinate; D-o/m/p-TolF⁻ = N,N′-bis(2/3/4-tolyl)formamidinate; p-TolA⁻ = N-4-tolylamidate). This is a simpler and greener method than the tedious procedures described in the literature, and it has permitted to obtain water-soluble complexes with good yields in a short period of time. A synthetic study has been implemented to find the best experimental conditions to prepare compounds 1–7. Two different types of ligands, formamidinate and amidate, have been used to check the generality of the method for the preparation of monosubstituted complexes. Five new compounds (2–6) have been obtained using a formamidinate ligand, the synthesis of the previously described compound 1 has been improved, and an unprecedented monoamidate complex has been achieved (7). The crystal structures of compounds 3 and 7 have been solved by single crystal X-ray diffraction. These compounds show the typical paddlewheel structure with three acetate ligands and one formamidinate (3) or amidate (7) bridging ligand at the equatorial positions. The axial positions are occupied by the chloride ligand giving rise to one-dimensional polymer structures that were previously unknown for monosubstituted compounds.     

Confinement and migration of radionuclides in a nuclear waste deep repository

The safety of the geological disposal of nuclear waste is evaluated, among other factors, through the ability of radionuclides to be confined, first by waste packages then by engineered barriers and host rocks. Deep underground conditions favour the immobilisation of most radionuclides by sorption or precipitation, which means that mobile radionuclides, such as ¹²⁹I or ³⁶Cl, may contribute to most of the ultimate dose release during up to a million years. However, degraded evolution scenarios must be taken into account (oxygen intrusion, faults, …) to assess earlier dose releases. To cite this article: P. Toulhoat, C. R. Physique 3 (2002) 975–986.     

Quantum Cascade Lasers: the quantum technology for semiconductor lasers in the mid-far-infrared

The quantum cascade laser is a new light source based on resonant tunnelling and optical transitions between quantised conduction band states. In these semiconductor devices the principles of operation arise from the quantum engineering of electronic energy levels and tailoring of their wavefunctions. In recent years the performance of these devices has improved markedly and this semiconductor technology is now an attractive choice for the fabrication of mid-far infrared lasers in a very wide spectral range (3–80 μm). At present, quantum cascade lasers are capable of continuous-wave room temperature operation and can deliver 200–300 mW of average power (at λ∼9 μm) operating on a Peltier cooler. To cite this article: C. Sirtori, J. Nagle, C. R. Physique 4 (2003).     

Stresses in compressed bubble rafts

We present a simple geometric method to determine the stress field in a compressed bubble raft. We show that bubble rafts exhibit arches phenomena as do granular materials, and examine the relaxation of stresses following a T₁ transformation. To cite this article: C. Ybert, J.-M. di Meglio, C. R. Physique 3 (2002) 555–559.     

Effects of ageing on the electrical characteristics of Cd/CdS/n-Si/Au–Sb structure deposited by SILAR method

Cd/CdS/n-Si/Au–Sb structure has been fabricated by the Successive Ionic Layer Adsorption and Reaction (SILAR) method and the influence of the time dependent or ageing on the characteristic parameters are examined. The current–voltage (I–V), capacitance–voltage (C–V) and capacitance–frequency (C–f) characteristics of the structure have been measured immediately, 1, 3, 5, 15, 30, 45, 60, 75, 90, 105, 120, 135, 150 and 165 days after fabrication of the structure. The characteristic parameters of the structure such as barrier height, ideality factor, series resistance are calculated from the I–V measurements and the barrier height, carrier concentration values are calculated from reverse bias C^?2–V measurements at 500 kHz and room temperature. Furthermore, the density distribution and time constant of the interface states have been calculated from the C–f measurements using the Schottky Capacitance Spectroscopy method as a function of ageing time. It has been seen that the changes of characteristic parameters such as barrier height, ideality factor and series resistance of Cd/CdS/n-Si/Au–Sb structure have lightly changed with increasing ageing time. At the same time, the rectifying ratio of the device increases with ageing time. It can be clearly said that the I–V characteristics of device get better with time.     

Séparation physique de molécules chirales

One examines the order of magnitude of the speed of separation of optically active molecules bearing a permanent dipole under the effect of a rotating electric field. To cite this article: Y. Pomeau, C. R. Physique 3 (2002) 1269–1271.     

Is the chiral Luttinger liquid exponent universal?

We present experimental evidence from electron tunneling measurements that the chiral Luttinger liquid power-law exponent, α, for tunneling into the fractional quantum Hall edge deviates substantially from the universal behavior predicted by theory. Our results suggest that the existing standard analyses based on effective Chern–Simon field theories deserve careful reexamination when applied to the dynamics at the Hall fluid edge. To cite this article: A.M. Chang, C. R. Physique 3 (2002) 677–684.     

Voltage addressable nanomemories in DNA?

Short single-stranded DNA (or RNA) molecules can be designed to have several long lived (> hours) secondary structures. In principle, such molecules could be used as nanomemories if they could be easily induced to switch between trapped states. We propose here that the necessary work required to drive the molecule into one particular trapped state can be provided by its own synthesis. Following this idea, we argue that a low voltage (<1 V) may induce a bistable DNA molecule to switch structure at will, by forcing it to thread through a nanopore and refold alternatively from either of its ends. To cite this article: H. Isambert, C. R. Physique 3 (2002) 391–396.     

The LEP collider

The LEP collider and the performances which have been achieved are presented in simple terms. Some basic facts of electron circular machine physics are recalled. The ambitious and very successful programmes undertaken to maximize LEP luminosity and energy are described in detail. To cite this article: R. Bailey et al., C. R. Physique 3 (2002) 1107–1120.     

High-efficiency degradation catalytic performance of a novel Angelica sinensis polysaccharide-silver nanomaterial for dyes by ultrasonic cavitation

Currently, the polluted wastewater discharged by industry accounts for the major part of polluted bodies of water. As one of the industrial wastewaters, dye wastewater is characterized by high toxicity, wide pollution, and difficulty in decolorization degradation. In this paper, a novel composite nanomaterial catalyst of silver was prepared by using Angelica sinensis polysaccharide (ASP) as a reducing and stabilizing agent. And the optimum reaction conditions explored are V_AgNO3 = 5 mL (300 mM) and v_ASP = 7% (w/v) for 6 h at 90 °C. In addition, the ASP-Ag nanocatalyst was characterized by several techniques. The results demonstrated that ASP-Ag nanoparticles were successfully synthesized. Degradation rate, which provides a numerical visualization of the percentage reduction in pollutant concentration. With the wrapping of ASP, the ultrasonic catalytic degradation rates of different organic dyes including rhodamine B (RB), methylene blue (MB), and methyl orange (MO) were from 88.2%, 88.7%, and 85.2% to 96.1%, 95.2% and 93.5% at room temperature, respectively. After the experiments, when c_dyes = 10 mg/L, the highest degradation rate can be observed under c_APS-AgNPs = 10 mg/L with the most powerful cavitation frequency f = 59 kHz. The effect of ultrasonic frequency on the acoustic pressure distribution in the reactor was investigated by using COMSOL Multiphysis^@ software to propose the mechanism of ultrasonic degradation and the mechanism was confirmed by OH radical trapping experiments. It indicates that OH produced by the ultrasonic cavitation effect plays a determinant role in the degradation. And then, the intermediate products of the dye degradation process were analyzed by gas chromatography and mass spectrometry (GC–MS), and the possible degradation processes of dyes were proposed. The resulting products of degradation are SO₄²⁻, NH₄⁺, NO₃⁻, N₂, CO₂ and H₂O. Finally, the recycling degradation experiments showed that catalyst maintains a high degradation rate within reusing 5 cycles. Thus, this catalyst is highly efficient and recyclable.     

Nonlinear optical activity in chiral molecules: surface second harmonic generation and nonlinear circular dichroism

Nonlinear optical activity in chiral molecules is investigated. We first examine the importance of the nonlocality of the light–matter interaction in optical activity and extend this concept to second-order (surface second harmonic generation) and third-order (nonlinear circular dichroism) nonlinear optical phenomena. Microscopic models are also discussed. Various phenomena derived from these considerations are demonstrated experimentally with specially-synthesized chiral molecules. To cite this article: F. Hache et al., C. R. Physique 3 (2002) 429–437.