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.

Spontaneous Deracemizations.

Spontaneous deracemizations is a challenging, multidisciplinary subject in current chirality research. In the absence of any chiral inductors, an achiral substance or a racemic composition is driven into an enantioenriched or even homochiral state through a selective energy input, e.g., chemical potential, photoirradiation, mechanical grinding, ultrasound waves, thermal gradients, etc. The most prominent examples of such transformations are the Soai reaction and the Viedma deracemization. In this review, we track the most recent developments in this topic and recall that many other deracemizations have been reported for solutions from mesophases to conglomerate crystallizations. A compiled set of simply available achiral organic, inorganic, organometallic, and MOF compounds, yielding conglomerate crystals, should give the impetus to realize new experiments on spontaneous deracemizations. Taking into account thermodynamic constraints, modeling efforts have shown that structural features alone are not sufficient to describe spontaneous deracemizations. As a guideline of this review, particular attention is paid to the physicochemical origin and symmetry requirements of such processes.

Chiral selectivity vs. noise in spontaneous mirror symmetry breaking.

Mirror symmetry breaking bifurcations, that occur in nonlinear chemical systems leading to final chiral states with very large enantiomeric excess, can be exploited as an efficient chiral signal selector for even the smallest chiral polarizations. This effect of the chiral polarization requires the system's capacity for overcoming thermal noise, which is manifested as fluctuating reaction rate constants. Therefore, we investigate the chiral selectivity across a range of tiny parity-violating energy differences (PVED) in the presence of inevitable non-equilibrium temperature fluctuations. We use a stochastic differential equation simulation methodology (Ito process) that serves as a valuable tool in open systems for identifying the thresholds at which the chiral force induces chiral selectivity in the presence of non-equilibrium temperature fluctuations. This approach enables us to include and analyze chiral selectivity in the presence of other types of fluctuations, such as perturbations in the rate of fluid flow into and out of the reactor and in the clamped input concentrations. These concepts may be of practical interest (i.e., spontaneous deracemizations) but are also useful for a better understanding of the general principles governing the emergence of biological homochirality.

Spontaneous Emergence of Transient Chirality in Closed, Reversible Frank-like Deterministic Models.

To explore abiotic theories related to the origin of biomolecular homochirality, we analyze two entirely reversible kinetic models composed of an enantioselective autocatalysis with limited stereoselectivity that is coupled to an enantiomeric mutual inhibition (Frank-like models). The two models differ in their autocatalytic steps in respect to the formation of monomer species in one model and of dimer species in the other. While fully reversible and running in a closed system, spontaneous mirror symmetry breaking (SMSB) gives rise to transient chiral excursions, even when starting from a strictly achiral situation. Before the SMSB, the two models differ in the main dissipative processes. At the SMSB, the entropy production rate reaches its maximum in both models. Here it is the enantioselective autocatalysis with retention of the winner enantiomer that dominates. During the terminal phase, the enantioselective autocatalysis with inversion prevails, while the entropy production rate vanishes, thus fulfilling the conditions of microscopic reversibility. SMSB does not occur if the autocatalytic rate constant is too strong or too weak. However, when the autocatalysis is relatively weak, the temporary chiral excursions last for long periods of time and could be the starting point of a cascade of asymmetric reactions. The realism of such Frank-like models is discussed from the viewpoint of their relevance to prebiotic chemistry.

Non-stochastic behavior in sodium chlorate crystallization.

NaClO3 is achiral in solution. If crystallization is performed under a static set-up, it is recognized that the stochastic nucleation probability results in a racemic mixture of the conglomerate. In this paper, we report a reexamination of the crystallization of NaClO3 from static solution in petri dishes that was conducted over a number of years and is based on the count and analysis of several thousand d- vs. l-NaClO3 crystals. Remarkably, instead of an expected nearly 50/50 coin-tossing situation for the d/l crystal frequency, in most of our experiments a statistically significant bias in favor of d- over l-NaClO3 crystals was found. The experiments also showed that the NaClO3 system was relatively insensitive regarding the intentional addition of a variety of optically active agents. Only in some cases, the persisting d-bias observed in the unseeded experiments slightly increased upon the presence of such additives. Nevertheless, experiments in plastic petri dishes or in presence of fungal spores were able to reverse this bias. A literature survey shows that mainly d-directed non-stochastic behavior in the NaClO3 system has been previously observed in other laboratory settings and by the application of different crystallization techniques. So far, the kind of chiral influence that could be at the origin of the observed bias remains unknown. After the examination of several possible chiral influences of physical, chemical and biological origin, we carefully consider the presence of bio-contaminants as most likely for the cause of this effect.

A photochemical determination of luminescence efficiency of upconverting nanoparticles.

Upconverting nanoparticles are a rising class of non-linear luminescent probes burgeoning since the beginning of the 2000's, especially for their attractiveness in theranostics. However, the precise quantification of the light delivered remains a hot problem in order to estimate their impact on the biological medium. Sophisticated photophysical measurements under near infrared excitation have been developed only by few teams. Here, we present the first attempt towards a simple and cheap photochemical approach consisting of an actinometric characterization of the green emission of NaYF4:Yb,Er nanoparticles. Using the recently calibrated actinometer 1,2-bis(2,4-dimethyl-5-phenyl-3-thienyl)-3,3,4,4,5,5-hexafluoro-1-cyclopentene operating in the green region of the visible spectra, we propose a simple photochemical experiment to get an accurate estimation of the efficiency of these green-emitting "nanolamps". The agreement of the collected data with the previous published results validates this approach.

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.

Photoswitchable assembly of long-lived azobenzenes in water using visible light.

HYPOTHESIS: Switchable assemblies relevant for bio-applications may be accessed from water-soluble tetra-ortho-substituted azobenzenes that reversibly self-assemble and form complexes with ß-cyclodextrin under visible light. EXPERIMENTS: Two azobenzenes bearing either four fluorines or two chlorines and two fluorines in the ortho positions were synthesised with short poly(ethylene oxide) tails for water solubility. Photophysical properties were determined by UV-vis and 1H NMR spectroscopies, complexation with ß-cyclodextrin was assessed by 1H NMR spectroscopy, and self-assembly in water was investigated by static and dynamic light scattering. FINDINGS: Both molecules underwent trans-cis isomerization at 530 nm and cis-trans isomerization at 415 nm, with the cis forms exhibiting thermal half-lives > 300 days at room temperature. Both molecules formed inclusion complexes with ß-cyclodextrin in water, with cis-4F-AZO-PEO binding 3-fold stronger than trans, and 2Cl2F-AZO-PEO binding significantly weaker. Self-assembly of pure 2Cl2F-AZO-PEO in water showed an open association process regardless of configuration, while 4F-AZO-PEO showed an open association process for cis (Nagg increasing from 30 to 1000) but a closed association process for trans (Nagg stable at âˆ¼ 170). Aqueous solutions of 2Cl2F-AZO-PEO showed cloud points close to 45 °C, while the 4F-AZO-PEO isomers presented well-separated cloud points allowing reversible and all-visible transition between clear and turbid states at room temperature.

Gated photochromism and acidity photomodulation of a diacid dithienylethene dye.

The present study quantitatively analyses the gated photochromism and the acidity photomodulation properties of a diacid dithienylethene compound. Photoisomerisation between the open and closed isomers was investigated by UV/visible and (1)H NMR spectroscopy. It was found that the photocyclisation quantum yield of the diacid form was remarkably high (around 90%). Partial neutralisation of the open isomer revealed a gated photochromism as the photocyclisation quantum yield of the mono- and dianion were 50 and 67%, respectively. A considerable photomodulation of the acidity was observed: the closed isomer is more acid than the open one by more than one pK(a) unit. This effect has been shown to be exploitable for a reversible photo-acid generation. This is the first time that a complete quantitative investigation that allows for the determination of the main photochromic, spectral and thermodynamic parameters of a base-sensitive photochromic diarylethene has been carried out.

Amplification of enantiomeric excess, mirror-image symmetry breaking and kinetic proofreading in Soai reaction models with different oligomeric orders.

A comprehensive kinetic analysis of three prototypical autocatalytic cycle models based on the absolute asymmetric Soai reaction is presented. The three models, which can give rise to amplification of enantiomeric excess and mirror-image symmetry breaking, vary by their monomeric, dimeric or trimeric order of the assumed catalytic species. Our numerical approach considered the entire chiral combinatorics of the diastereomeric interactions in the models as well as the multiplicity of coupled reversible reactions without applying fast equilibration or quasi-steady state approximations. For the simplest monomeric model, an extensive range of parameters was explored employing a random grid parameter scanning method that revealed the influence of the parameter values on the product distribution, the reaction-time, the attenuation or amplification of enantiomeric excess as well as on the presence or absence of mirror-image symmetry breaking. A symmetry breaking test was imposed on the three models showing that an increase in the catalytic oligomer size from one to three leads to a higher tolerance to poorer chiral recognition between the diastereoisomers and identifies the greater impact of the diastereoisomeric energy difference over an imperfect stereoselectivity in the catalytic step. This robustness is understood as a particular case of so-called kinetic proofreading in asymmetric autocatalysis.

Photochromism and metal complexation of a macrocyclic styryl naphthopyran.

A macrocyclic benzo-15-crown-5 ether unit tethered to a photochromic naphthopyran by a styryl spacer (MEN) is shown to form a 1:1 complex with magnesium(II). The structure and dynamics of the specific host-metal interactions were investigated by PFG-NMR analysis. A combination of UV/Vis and variable temperature multi-dimensional (1)H NMR photokinetic analysis of the crown-containing styryl naphthopyran and its metal complex was used to probe the effect of metal complexation on the photochromism.

Metal ions drive thermodynamics and photochemistry of the bis(styryl) macrocyclic tweezer.

UV/Vis and NMR spectroscopy were used for the structural elucidation and thermodynamic and photochemical studies of the metal-coordinated crown-containing macrocyclic tweezer (E,E)-1. The bis(styryl) tweezer (E,E)-1 formed two types of complexes with magnesium(II): a 1:1 intramolecular asymmetric sandwich complex [(E,E)-1].Mg(2+) and a 1:2 complex [(E,E)-1].(Mg(2+))(2). In the former case, there is direct cation intramolecular exchange (0.299 s(-1), DeltaG(++)=69.4 kJ mol(-1)) between two parts of the bis(styryl) tweezer (E,E)-1. Addition of barium(II) to the bis(styryl) tweezer (E,E)-1 led to an intramolecular centrosymmetric sandwich 1:1 complex [(E,E)-1].Ba(2+). Irradiation of [(E,E)-1]Ba(2+) afforded reversible intramolecular [2pi+2pi] photocyclization with excellent stereoselectivity and quantitative yield. In contrast, irradiation of [(E,E)-1].(Mg(2+))(2) resulted in reversible stepwise E,Z-isomerization.

Quantitative investigations of cation complexation of photochromic 8-benzothiazole-substituted benzopyran: towards metal-ion sensors.

The photochromic, thermochromic and metallochromic behaviour of a series of three spiro[indoline-8-(benzothiazol-2-yl)-benzopyrans] has been investigated. The thermodynamic and kinetic parameters of their thermal equilibrium between the ring-closed (spiro) and ring-opened (merocyanine) isomeric forms have been determined using UV-Vis absorption and (1)H NMR spectroscopies. By adding Co(ii) and Ni(ii) ions in acetonitrile solution, 1 : 1 and 1 : 2 metal : merocyanine complexes are formed simultaneously. Using appropriate numerical methods, the kinetic analysis of the complexation allowed us to determine accurately key thermodynamic and spectroscopic parameters of the metal complexes. Results showed that the complexation strength is very sensitive to the size of the indoline nitrogen substituent. Complexation can be reversed by shining white light on the coloured complexes which regenerates the inactive spiropyran form, and releases the metallic ion; hence, these systems display fully reversible negative photochromism. The Zn(ii) complexes exhibit intense fluorescence in the 600-800 nm wavelength range. All these behaviours make these spiropyrans bearing benzothiazole heterocycles promising building blocks for the future construction of photodynamic chemosensors for transition metal ions.

Partition and water/oil adsorption of some surfactants.

Adsorption isotherms have been determined at the water/oil interface for five biphasic systems involving surfactants (non-ionic and ionic) present in both phases at partition equilibrium. The systems studied were polyoxyethylene(23)lauryl ether (Brij35) in water/hexane and four ionic surfactants, hexadecyltrimethylammonium bromide (CTAB), and a series of three tetraalkylammonium dodecylsulfate (TEADS, TPADS, and TBADS) in water/CH 2Cl 2. Interfacial tension measurements performed at the water/air and water/oil interfaces provided all the necessary information for the determination of the adsorption parameters by taking partition into account. These measurements also allowed the comparison of the adsorption properties at both interfaces which showed an increase of the adsorption equilibrium constant and a decrease of the maximum surface concentration at the water/oil interface compared to water/air. The values of the critical aggregation concentration showed, in all cases, that only the surfactant dissolved in the aqueous phase contribute to the decrease of the water/oil interfacial tension. In the case of the four ionic surfactants, the critical aggregation concentration obtained in biphasic conditions were lowered because of the formation of mixed surfactant-CH 2Cl 2 aggregates.

Transient absorption studies of the photochromic behavior of 3H-naphtho[2,1-b]pyrans linked to thiophene oligomers via an acetylenic junction.

The photophysical and photochemical properties of four 3,3-diphenyl-3H-naphtho[2,1- b]pyrans substituted, via an acetylenic junction, to (thiophene) n oligomers (n = 0-3 units) were investigated by transient absorption in the femtosecond to microsecond time domain and by stationary absorption and fluorescence. The decay of the initially produced excited S1(pi pi*) state is found to occur via three competing processes: fluorescence, intersystem crossing, and a ring-opening reaction leading to a colored merocyanine product, with relative yields varying drastically with n. Whereas ultrafast (sub-picosecond) reaction dynamics and high product quantum yield are observed for n = 0 and 1, the reaction is considerably slowed down on going to the n = 2 (105 ps) compound and does not occur for n = 3. A reaction scheme that accounts for this behavior is proposed and the effect of the oligothiophenic chain length on the photoinduced properties is discussed. It is suggested that increasing the chain length from 1 to 3 thiophene units stabilizes the S1(pi pi*) state by pi conjugation and induces an excited-state potential barrier along the reaction pathway.

Terahertz Time-Domain Spectroscopy of Thermoresponsive Polymers in Aqueous Solution.

The behavior of highly concentrated aqueous solutions of two thermoresponsive polymers poly(N-isopropylacrylamide) (PNIPAm) and poly(N-vinylcaprolactam) (PVCL) have been investigated by terahertz time-domain spectroscopy (THz-TDS). Measurements have been performed for concentrations up to 20 wt %, over a frequency range from 0.3 to 1.5 THz and for temperatures from 20 to 45 °C including the zone for lower critical solution temperature (LCST). THz-TDS enables the study of the behavior of water present in the solution (i.e., free or bound to the polymer). From these measurements, in addition to phase transition temperature, thermodynamic data such as variation of enthalpy and entropy can be inferred. Thanks to these data, further insights upon the mechanism involved during the dehydration phenomenon were obtained. These results were compared to the ones issued from dynamic light scattering, spectroscopy, or microscopy techniques to underline the interest to use THz-TDS as a powerful tool to characterize the behavior of thermoresponsive polymers in highly concentrated solutions.

Periodic marangoni instability in surfactant (CTAB) liquid/liquid mass transfer.

Periodic Marangoni convective instability has been observed in a biphasic system during the mass transfer of cetyltrimethylammonium bromide (CTAB) from an aqueous to a dichloromethane organic phase. Visualization of the convective fluxes was possible thanks to the CTAB crystals that are formed in the aqueous phase at a temperature below the Krafft point. Surface tension and electrical potential oscillations have been shown to be correlated with the fluid motion. Surface tension measurements, representative of the adsorption state, showed fast adsorption during the convective stage, followed by a slower desorption process in the quiet stage. To account for the electrical potential data, two components need to be taken into account. In the quiet stage, the signal was comparable to surface tension, and the main contribution would result from the electrical double layer formed at the interface by charged surfactants. In the convective stage, the electrical potential was furthermore related to the velocity of the fluid in the aqueous layer. Perturbations of the charge distribution in the Gouy-Chapman layer due to tangential flows could be at the origin of the phenomenon.

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.

Kinetic analysis of artificial peptide self-replication. Part I: the homochiral case.

Computational kinetic analysis of a lately discovered homochiral peptide self-replicator is presented. A 6-step kinetic model was designed that addresses the main reactions and hydrophobic interactions involved in this template-directed, autocatalytic system and that gave rise to excellent fitting of 4 previously published independent experimental series. The model sheds light on the mechanistic principle of the reaction system and illustrates directly a number of dynamic properties such as the observed autocatalytic efficiency. It was found that the dynamics are basically governed by two reversible hydrophobic interactions: between the template and a peptide fragment and between two template species. The later association was determined to be considerably more favored, which leads to the predominant presence of the catalytically inactive template dimer in the reaction system. Our results show that the involvement of a template trimer is not necessary to obtain the observed fittings.