Tailored Cyclic and Linear Polycarbosilazanes by Barium‐Catalyzed N−H/H−Si Dehydrocoupling Reactions

Ba[CH(SiMe₃)₂]₂(THF)₃ catalyzes the fast and controlled dehydrogenative polymerization of Ph₂SiH₂ and p‐xylylenediamine to afford polycarbosilazanes. The structure (cyclic versus linear; end‐groups) and molecular weight of the macromolecules can be tuned by adjusting the Ph₂SiH₂/diamine feed ratio. A detailed analysis of the resulting materials (mol. wt up to ca. 10 000 g mol^?1) is provided.     

Allyl ansa-lanthanidocenes: single-component, single-site catalysts for controlled syndiospecific styrene and styrene-ethylene (Co)polymerization

A series of new neutral allyl Group 3 metal complexes bearing ansa-bridged fluorenyl/cyclopentadienyl ligands [[Flu-EMe(2)-(3-R-Cp)]Ln(eta(3)-C(3)H(5))(THF)] (E=C, R=H, Ln=Y (2), La (3), Nd (4), Sm (5); R=tBu, Ln=Y (8), Nd (9); E=Si, R=H, Ln=Y (12), Nd (13)) were synthesized in good yields via salt metathesis protocols. The complexes were characterized by elemental analysis, NMR spectroscopy for diamagnetic complexes, and single-crystal X-ray diffraction studies for 2, 4, 9 and 12. Some of the allyl ansa-lanthanidocenes, especially 4, are effective single-component catalysts for the polymerization of styrene, giving pure syndiotactic polystyrenes (rrrr > 99 %) with low to high molecular weights (M(n)=6000-135,000 g mol(-1)) and narrow polydispersities (M(w)/M(n)=1.2-2.6). The catalyst systems are remarkably stable, capable of polymerizing styrene up to 120 degrees C with high activities, while maintaining high syndiotacticity via chain-end control as established by a Bernoullian analysis. Highly effective copolymerization of styrene with ethylene was achieved using neodymium complex 4 (activity up to 2530 kg PS-PE mol(-1) h(-1)) to give true copolymers void of homopolymers with M(n)=9000-152,000 g mol(-1) and narrow polydispersities (M(w)/M(n)=1.2-2.5). The nature of the resultant P(S-co-E) copolymers was ascertained by NMR, size-exclusion chromatography/refractive index/UV, temperature rising elusion fractionation, and differential scanning calorimetry. It is shown that, regardless the amount of ethylene incorporated (1-50 mol %), P(S-co-E) copolymers have a microstructure predominantly made of long highly syndiotactic PS sequences separated by single or few ethylene units. Co-monomers feed and polymerization temperature can be used straightforwardly to manipulate with the physical and mechanical characteristics of the P(S-co-E) copolymers (molecular weights and distributions, co-monomer content, microstructure, T(m), T(g), T(c)).     

Polyamines interaction with thylakoid proteins during stress

The involvement of polyamines in plant responses to abiotic stresses is well investigated, while there has been few reports on the specific mode of action of polyamines on the photosynthetic apparatus. The objective of this review is thus to examine the mode of interaction of polyamines with proteins of photosystem II core and LHCII, including methylamine (monoamine) as a simplified model to better understand the mode of action of polyamines. Spectroscopic methods used to determine the binding mode of amines with PSII proteins showed that amines such as spermine, putrescine and methylamine interact with protein (H-bonding) through polypeptide C=O, C-N and N-H groups with major perturbations of protein secondary structure as the concentration of amines was raised. High concentration of amines added to PSII-enriched submembrane fractions causes a significant loss of PSII activity. However, at lower concentration, polyamines, especially spermine, improve the photosynthetic functions under stress. We concluded from this review that besides the conjugation of polyamines with LHC polypeptides, polyamines are likely to interact with extrinsic proteins and the hydrophilic part of intrinsic proteins of PSII by electrostatic interaction. This could stabilize the conformation of proteins under various stresses. However, at high concentration of polyamines a strong inhibition of PSII activity is observed.     

Zinc and magnesium complexes supported by bulky multidentate amino-ether phenolate ligands: potent pre-catalysts for the immortal ring-opening polymerisation of cyclic esters

A family of heteroleptic complexes of zinc and magnesium supported by bulky multidentate amino-ether phenolate ligands has been developed; in combination with external chain transfer agents, they constitute efficient binary catalytic systems for the immortal ring-opening polymerisation of cyclic esters.     

A dual organic/organometallic approach for catalytic ring-opening polymerization

A dual catalytic system combining an original cationic zinc complex and a tertiary amine is shown to promote efficiently the polymerization of lactide under mild conditions.     

Controlled ROP of β‐Butyrolactone Simply Mediated by Amidine,Guanidine, and Phosphazene Organocatalysts

Basic organocatalysts of the guanidine (1,5,7‐triazabicyclo[4.4.0]dec‐5‐ene, TBD), amidine (1,8‐diazabicyclo[5.4.0]‐undec‐7‐ene, DBU), and phosphazene (2‐tert‐butylimino‐2‐diethylamino‐1,3‐dimethylperhydro‐1,3,2diazaphosphorine, BEMP) type do effectively polymerize β‐butyrolactone (BL). Poly(3‐hydroxybutyrate)s (PHBs) with controlled molecular features, that is, controlled molar masses, narrow molar mass distributions, and well‐defined functional end groups are thus formed at 60 °C from bulk monomer, with up to 21 500 g mol⁻¹. The formation of α,ω‐guanidine/amidine/phosphazene,crotonate functionalized PHBs, as demonstrated by NMR, SEC, and MALDI–ToF mass spectrometry analyses, mechanistically suggests the formation of N‐acyl‐α,β‐unsaturated propagating species that originate from 1:1 guanidine/amidine/phosphazene:BL adducts.     

Afterglow thermoluminescence measured in isolated chloroplasts

The thermoluminescence afterglow (AG) measured in plant leaves originates from the S(2)/S(3)Q(B)(-) charge pair recombination in photosystem II (PSII) initiated by reverse electron flow from stromal reductants to PQ and then to the Q(B) site in PSII centers that are in the S(2)/S(3)Q(B) state. In this study, we show that this luminescence, absent in isolated thylakoid membranes, can be measured in intact chloroplasts that retain their stromal content including the electron acceptor pool (oxidized ferredoxin/NADP(+)) of photosystem I. The properties of the chloroplasts AG emission is similar to the AG in leaves in terms of temperature maximum, period-four modulation, far-red light stimulation, and antimycin A inhibition.     

Lattice mediated interactions and ferroelectric anomalies in the crystal (CH3NH3)5Bi2Cl11 (PMACB)

Abstract

A two-sublattice compressible pseudospin model has been constructed to describe the behaviour of the spontaneous polarisation of PMACB in the temperature region comprising the ferroelectric phase transition (T=307K) and the isomorphous anomaly (T= 180 K). A strong coupling of pseudospins with a “pancake” strain ?(2ε₃₃ ? ε₁₁ - ε₂₂) /3 resulting from the comparison of the model with the experimental spontaneous polarisation agrees with the existing data on the dielectric susceptibility, and on the specific heat. The ferroelectric phase transition then turns out to be close to a tricritical point. The numerical values of the parameters of the model show how the ferroelastic phase transition (T=260K) can occur in this crystal without any discernible effect on the specific heat and on the dielectric susceptibility.     

Dynamic consistency for stochastic optimal control problems

For a sequence of dynamic optimization problems, we aim at discussing a notion of consistency over time. This notion can be informally introduced as follows. At the very first time step?t ₀, the decision maker formulates an optimization problem that yields optimal decision rules for all the forthcoming time steps?t ₀,t ₁,??,T; at the next time step?t ₁, he is able to formulate a new optimization problem starting at time?t ₁ that yields a new sequence of optimal decision rules. This process can be continued until the final time?T is reached. A?family of optimization problems formulated in this way is said to be dynamically consistent if the optimal strategies obtained when solving the original problem remain optimal for all subsequent problems. The notion of dynamic consistency, well-known in the field of economics, has been recently introduced in the context of risk measures, notably by Artzner et al. (Ann. Oper. Res. 152(1):5?C22, 2007) and studied in the stochastic programming framework by Shapiro (Oper. Res. Lett. 37(3):143?C147, 2009) and for Markov Decision Processes (MDP) by Ruszczynski (Math. Program. 125(2):235?C261, 2010). We here link this notion with the concept of ??state variable?? in MDP, and show that a significant class of dynamic optimization problems are dynamically consistent, provided that an adequate state variable is chosen.