A Complex Reaction Network Model for Spontaneous Mirror Symmetry Breaking in Viedma Deracemizations

Attrition-enhanced chiral symmetry breaking in crystals, known as Viedma deracemization, is a promising method for converting racemic solid phases into enantiomerically pure ones under non-equilibrium conditions. However, many aspects of this process remain unclear. In this study, we present a new investigation into Viedma deracemization using a comprehensive kinetic rate equation continuous model based on classical primary nucleation theory, crystal growth, and Ostwald ripening. Our approach employs a fully microreversible kinetic scheme with a size-dependent solubility following the Gibbs–Thomson rule. To validate our model, we use data from a real NaClO₃ deracemization experiment. After parametrization, the model shows spontaneous mirror symmetry breaking (SMSB) under grinding. Additionally, we identify a bifurcation scenario with a lower and upper limit of the grinding intensity that leads to deracemization, including a minimum deracemization time within this window. Furthermore, this model uncovers that SMSB is caused by multiple instances of concealed high-order autocatalysis. Our findings provide new insights into attrition-enhanced deracemization and its potential applications in chiral molecule synthesis and understanding biological homochirality.     

Quantitative analysis of the dynamic behaviour of photochromic systems

The good understanding of a photochromic reaction mechanism requires the establishment of the list of all the transient species and the definition of their connecting processes. The purpose of kinetic studies is the determination of the main photochromic parameters, such as the quantum yields of photoisomerization, rate constants of thermal relaxation and spectra of transient species. These data allow the establishment of structure properties relationships in order to select the best substituents to improve photochromic performances within a given series. In this review, we describe the dynamic behaviour of various photochromic systems during thermal relaxation after irradiation, from the simplest mono-exponential decay to the more complicated multi-exponential dynamics. Then, we analyse the evolution of the long-lived isomers under continuous irradiation. Several pedagogical examples and tricks to perform easy kinetic analysis are given in the appendices.     

The bistable TPID/CHCl3 photoreaction: Numerical simulation and experimental results

Investigation of the photochromic system TPID/CHCl₃ (TPID = triphenylimidazolyl dimer) in a CSTR provided the first example of isothermal photochemical bistability. The reaction mechanism was established and the relevant kinetic and spectroscopic parameters were estimated experimentally. In order to predict the quantitative dynamic behavior of the TPID/CHCl₃ system these parameters were refined numerically using batch reactor data. The adjusted model simulates very accurately bistability either as a function of residence time τ, or as a function of incident photon flux I₀.     

Unexpected halogen substituent effects on the complex thermal relaxation of naphthopyrans after UV irradiation

The kinetics of the thermal fading of four halogenated naphthopyrans (NP) have been analyzed using NMR spectroscopy in CD(3)CN. Two photomerocyanines (TT and TC) were detected after UV irradiation. The main relaxation process TC --> NP was coupled with TT/TC isomerization. The activation parameters of the various processes were rationalized by considering electronegativity and polarizability of the halogen substituents and their selective solvation by the electronegative nitrogen of acetonitrile.     

Determining the association constant and adsorption properties of ion pairs in water by fitting surface tension data

Association constants and adsorption parameters of tetraalkylammoniumdodecyl sulfate (TAADS) ion pairs in water were determined. We have analyzed water/air surface tension measurements obtained for mixtures of sodium dodecyl sulfate (SDS) and tetraalkylammonium bromide of increasing chain lengths (TMAB, TEAB, TPAB, and TBAB). To reproduce the experimental isotherms, we coupled the association equilibrium of the ion pairs to the equations proposed by Fainerman and co-workers to model the adsorption of binary mixtures of surfactants (SDS and TAADS) with different molar areas at a nonideal surface layer. The parameters found showed that the model is not convenient to describe the effect of the addition of TMAB but a clear coherency was obtained for the three longer compounds. Ranging from TEADS to TBADS increasing hydrophobic interactions give rise to a higher associability but to a lower surface activity. Self-interactions coefficients extracted by the fitting procedure confirmed the importance of attractive interactions between the ion pairs. The calculated surface coverage showed that in every case the compound mainly adsorbed at the interface was the ion pair. For TBADS strong attractive interactions result in a phase transition at very low concentration.     

Hydrotrope-induced autocatalysis in the biphasic alkaline hydrolysis of aromatic esters

The alkaline hydrolysis of aromatic esters exhibits autocatalytic kinetics when performed under two-phase conditions without any mixing solvent. The molecular structures of such aromatic esters determine whether the autocatalysis occurs or not. It has been established that enhancing the solubility of the hydrophobic ester in water by the hydrotropic salts yielded by the hydrolysis itself accelerates the apparent reaction rate. By kinetically independent measurements, the solubilization process of the ester was verified to be the rate-determining step. It has been observed that the solubilization process can be influenced by factors such as the initial addition of hydrotropic salt, the volumetric ratio of the oil/aqueous phase, and the concentration of alkali.     

Decentralized harmonic active vibration control of a flexible plate using piezoelectric actuator-sensor pairs

We have investigated decentralized active control of periodic panel vibration using multiple pairs combining PZT actuators and PVDF sensors distributed on the panel. By contrast with centralized MIMO controllers used to actively control the vibrations or the sound radiation of extended structures, decentralized control using independent local control loops only requires identification of the diagonal terms in the plant matrix. However, it is difficult to a priori predict the global stability of such decentralized control. In this study, the general situation of noncollocated actuator-sensor pairs was considered. Frequency domain gradient and Newton-Raphson adaptation of decentralized control were analyzed, both in terms of performance and stability conditions. The stability conditions are especially derived in terms of the adaptation coefficient and a control effort weighting coefficient. Simulations and experimental results are presented in the case of a simply supported panel with four PZT-PVDF pairs distributed on it. Decentralized vibration control is shown to be highly dependent on the frequency, but can be as effective as a fully centralized control even when the plant matrix is not diagonal-dominant or is not strictly positive real (not dissipative).     

Multinuclear NMR structural characterization of an unprecedented photochromic allene intermediate

[structure: see text] An o-allenyl-p-methoxyphenol intermediate (Int) was for the first time proved to be involved in the photochromic reaction of 2,2-di(4-fluorophenyl)-6-methoxy-2H-1-chromene (FC). Transoid-cis (TC) and transoid-trans (TT) photomerocyanines and the intermediate Int are generated by UV irradiation of FC. Visible light converts TC and TT into Int. The monitoring of the reactions was carried out on the basis of (1)H, (13)C, (19)F, and (2)H NMR spectroscopy.     

Proton Catalysis in the Redox Responsivity of a Mini‐Sized Photochromic Diarylethene

A thermally irreversible dithienylethene (DTE) photochrom can be turned into a thermally reversible one in presence of Cu^II triflate. A ring opening (DTEC closed→DTEO open) occurs through the formation of a copper‐containing fast transient intermediate. Stopped‐flow experiments monitored at 410 and 780 nm have allowed to show that the stoichiometry of this intermediate is DTE/Cu=1:1. At longer monitoring times (i.e., several seconds after mixing), the intermediate undergoes a slow decay while the residual DTEC closed form opens. A joint detailed kinetic and electrochemical analysis has unveiled a proton catalysis scenario in which electron transfer between DTEC and Cu^II, ligand exchange, protonation‐deprotonation equilibria of the cation radicals and ring opening are embedded into two main reaction cycles. At the beginning of the reaction, Cu^II is reduced into Cu^I and DTE is degraded without ring opening. Then, as the reaction progresses, the triflic acid released from the Cu^II reduction switches‐on a propagation cycle during which ring opens without any more Cu^II consumption. Cyclic voltammetry, spectro‐electrochemical measurements, delayed photocoloration experiments in presence of Cu^II and acid–base additions have confirmed the main features of the proton catalysis.