Drug resistance: a periplasmic ménage à trois

The paradigm tripartite efflux transporter AcrA-AcrB-TolC confers multiple drug resistance to Escherichia coli. Tikhonova et?al. (2011) now examine how the three components connect to unity and highlight the critical role of AcrA membrane proximal domain conformation for successful assembly.     

Presence and absence of excited state intramolecular charge transfer with the six isomers of dicyano-N,N-dimethylaniline and dicyano-(N-methyl-N-isopropyl)aniline

The excited state behavior of the six m,n-dicyano-N,N-dimethylanilines (mnDCDMA) and m,n-dicyano-(N-methyl-N-isopropyl)anilines (mnDCMIA) is discussed as a function of solvent polarity and temperature. The dicyano moiety in these electron donor (D)/acceptor (A) molecules has a considerably larger electron affinity than the benzonitrile subgroup in 4-(dimethylamino)benzonitrile (DMABN). Nevertheless, the fluorescence spectra of the mnDCDMAs and mnDCMIAs in n-hexane all consist of a single emission originating from the locally excited (LE) state, indicating that a reaction from LE to an intramolecular charge transfer (ICT) state does not take place. The calculated energies E(ICT), obtained by employing the reduction potential of the dicyanobenzene subgroups and the oxidation potential of the amino substituents trimethylamine (N(Me)(3)) and isopropyldimethylamine (iPrNMe(2)), are lower than E(LE). The absence of an LE → ICT reaction therefore makes clear that the D and A units in the dicyanoanilines are not electronically decoupled. In the polar solvent acetonitrile (MeCN), dual (LE + ICT) fluorescence is found with 24DCDMA and 34DCDMA, as well as with 24DCMIA, 25DCMIA, and 34DCMIA. For all other mnDCDMAs and mnDCMIAs, only LE emission is observed in MeCN. The ICT/LE fluorescence quantum yield ratio Φ'(ICT)/Φ(LE) in MeCN at 25 °C is larger for 24DCDMA (1.2) than for 34DCDMA (0.35). The replacement of methyl by isopropyl in the amino substituent leads to a considerable increase of Φ'(ICT)/Φ(LE), 8.8 for 24DCMIA and 1.4 for 34DCMIA, showing that the LE ? ICT equilibrium has shifted further toward ICT. The appearance of an ICT reaction with the 2,4- and 3,4-dicyanoanilines is caused by a relatively small energy gap ΔE(S(1),S(2)) between the two lowest excited singlet states as compared with the other m,n-dicyanoanilines, in accordance with the PICT model. The observation that the ICT reaction is more efficient for 24DCMIA and 34DCMIA than for their mnDCDMA counterparts is mainly caused by the fact that iPrNMe(2) is a better electron donor than N(Me)(3): E(D/D(+)) = 0.84 against 1.05 V vs SCE. That ICT also occurs with 25DCMIA, notwithstanding its large ΔE(S(1),S(2)), is due to the substantial amino twist angle θ = 42.6°, which leads to partial electronic decoupling of the D and A subgroups. The dipole moments μ(e)(ICT) range between 18 D for 34DCMIA and 12 D for 25DCMIA, larger than the corresponding μ(e)(LE) of 16 and 11 D. The difference between μ(e)(ICT) and μ(e)(LE) is smaller than with DMABN (17 and 10 D) because of the noncollinear arrangement of the amino and cyano substituents (different dipole moment directions). The dicyanoanilines that do not undergo ICT, have LE dipole moments between 9 and 16 D. From plots of ln(Φ'(ICT)/Φ(LE)) vs 1000/T, the (rather small) ICT reaction enthalpies ΔH could be measured in MeCN: 5.4 kJ/mol (24DCDMA), 4.7 kJ/mol (24DCMIA), and 3.9 kJ/mol (34DCMIA). With the mnDCDMAs and mnDCMIAs only showing LE emission, the fluorescence decays are single exponential, whereas for those undergoing an LE → ICT reaction the LE and ICT picosecond fluorescence decays are double exponential. In MeCN at 25 °C, the decay times τ(2) have values between 1.8 ps for 24DCMIA and 4.6 ps for 34DCMIA at 25 °C. Longer times are observed at lower temperatures. Arrhenius plots of the forward and backward ICT rate constants k(a) and k(d) of 25DCMIA in tetrahydrofuran, obtained from the LE and ICT fluorescence decays, give the activation energies E(a) = 4.5 kJ/mol and E(d) = 11.9 kJ/mol, i.e., ΔH = -7.4 kJ/mol. From femtosecond transient absorption spectra of 24DCDMA and 34DCDMA at 22 °C, ICT reaction times τ(2) = 1/(k(a) + k(d)) of 1.8 and 3.1 ps are determined. By combining these results with the data for the fluorescence decays and Φ'(ICT)/Φ(LE), the values k(a) = 49 × 10(10) s(-1) (24DCDMA) and k(a) = 23 × 10(10) s(-1) (34DCDMA) are calculated. An LE and ICT excited state absorption is present even at a pump/probe delay time of 100 ps, showing that an LE ? ICT equilibrium is established.     

Fermion-boson coupling model (QCVM) applied to odd Zn isotopes

Low lying energy levels and transition probabilities of^63,65,67Zn are calculated in the Quasicluster-vibration model (QCVM). This model is an extension of the Clustervibration model (CVM) for three-particle-cluster vibration coupling. Instead of a three-particle cluster, now a one broken pair (number projected three quasiparticle) cluster is coupled to phonon states. It turns out that the sequence of isotopes may be described with one set of parameters, along the same line as previously used in the CVM. The resulting spectra and electromagnetic properties, for positive and negative parity states of odd Zn isotopes, compare with experimental data equally well as large shell-model calculations; this seems to justify the extension of the CVM to these nuclei with more than three particles or holes beyond a closed shell.     

An efficient and expeditious route to stannylallenes

(Triphenylstannyl)allenes (2) are formed in excellent yield by reacting 3-chloro-1-triphenylstannyl-1-propynes (1) with several alkylcopper(I) species RCu. An 1-alkynyl group could be introduced by using instead of RCu the zinc reagent and Pd[PPh₃]₄ as catalyst.     

Antipairing and antistretching in 22Ne

The ground state rotational band of ²²Ne has been investigated with the angular momentum and particle number projected Hartree-Bogoliubov theory. Variation before projections was performed in the framework of the constrained Hartree-Bogoliubov theory with the quadrupole moment and the degree of pairing as constraints. It is shown that there is a clear decrease of the pairing correlations (antipairing) and a decrease of the quadrupole deformation (antistretching) with increasing angular momentum. The antipairing effect appears to be essential to reproduce the experimentally known deviation of the spectrum from the J(J + 1) rule. The antistretching indicated by the B(E2) values is much stronger than that indicated by the calculated static quadrupole moments. This amounts to a breakdown of the rotational picture which is possibly connected with the low band cut-off values in the sd shell. The antipairing effect decreases the antistretching only slightly. The interaction between the pairing and quadrupole degrees of freedom is found to be too weak to change the earlier conclusions concerning antipairing and antistretching in the whole sd shell. No inert core was assumed in the calculations. The effective G-matrix elements of the Hamada-Johnston potential were used as an interaction.     

Influence of an enlargement of the model space on number projected quasiparticle calculations

Results of number projected quasiparticle calculations for Sn isotopes in large and in small model spaces are compared when the force strengths and single-particle energies are determined consistently within each model space. When extending the model space, one observes that the model parameters extracted from the odd nuclei become more satisfactory. For even nuclei the collective states are not lowered in energy although electromagnetic transition rates increase considerably. Spectroscopic factors for one-nucleon transfer reactions change noticeably only for shells close to the Fermi level. Two-nucleon transfer cross-sections are strongly increased for ground state to ground state transitions only. We criticize a usual approximation formula for theL=0 two-nucleon transfer cross-section.     

Synthesis of bis(tetramethylstibonium)tetracyclopentadienylstannate a novel type of organotin(II) compound

Reaction of dicyclopentadienyltin(II) with pentamethylantimony gives [Me₄Sb]₂⁺[(C₅H₅)₄Sn]^2?, the first example of an anionic organotin(II) species.     

Measuring charge transport from transient photovoltage rise times. A new tool to investigate electron transport in nanoparticle films

Charge transport rate at open-circuit potential (V(oc)) is proposed as a new characterization method for dye-sensitized (DS) and other nanostructured solar cells. At V(oc), charge density is flat and measurable, which simplifies quantitative comparison of transport and charge density. Transport measured at V(oc) also allows meaningful comparison of charge transport rates between different treatments, temperatures, and types of cells. However, in typical DS cells, charge transport rates at V(oc) often cannot be measured by photocurrent transients or modulation techniques due to RC limitations and/or recombination losses. To circumvent this limitation, we show that charge transport at V(oc) can be determined directly from the transient photovoltage rise time using a simple, zero-free-parameter model. This method is not sensitive to RC limitation or recombination losses. In trap limited devices, such as DS cells, the comparison of transport rates between different devices or conditions is only valid when the Fermi level in the limiting conductor is at the same distance from the band edge. We show how to perform such comparisons, correcting for conduction band shifts using the density of states (DOS) distribution determined from the same photovoltage transients. Last we show that the relationship between measured transport rate and measured charge density is consistent with the trap limited transport model.