Towards an understanding of the heat capacity of liquids. A simple two-state model for molecular association

A model for the temperature dependence of the isobaric heat capacity of associated pure liquids C(p,m)(o)(T) is proposed. Taking the ideal gas as a reference state, the residual heat capacity is divided into nonspecific C(p) (res,ns) and associational C(p) (res,ass) contributions. Statistical mechanics is used to obtain C(p)(res,ass) by means of a two-state model. All the experimentally observed C(p,m)(o)(T) types of curves in the literature are qualitatively described from the combination of the ideal gas heat capacity C(p)(id)(T) and C(p)(res,ass)(T). The existence of C(p,m)(o)(T) curves with a maximum is predicted and experimentally observed, for the first time, through the measurement of C(p,m)(o)(T) for highly sterically hindered alcohols. A detailed quantitative analysis of C(p,m)(o)(T) for several series of substances (n-alkanes, linear and branched alcohols, and thiols) is made. All the basic features of C(p,m)(o)(T) at atmospheric and high pressures are successfully described, the model parameters being physically meaningful. In particular, the molecular association energies and the C(p)(res,ns) values from the proposed model are found to be in agreement with those obtained through quantum mechanical ab initio calculations and the Flory model, respectively. It is concluded that C(p,m)(o)(T) is governed by the association energy between molecules, their self-association capability and molecular size.     

Brownian dynamics simulations on the self-assembly behavior of AB hybrid dendritic-star copolymers

The micellization behavior of hybrid dendritic-star copolymers with solvophilic dendritic units is studied by means of Brownian dynamics simulations. The critical micelle concentration and the micelle size and shape are examined for different solvophobic/solvophilic ratios r as a function of the number of the dendritic and linear arms. Hybrid dendritic-star copolymers with one dendritic and up to three solvophobic linear branches form spherical micelles with preferential aggregation number. Those with two dendritic arms and three solvophobic branches form micelles with wide aggregation numbers only for small values of r. For hybrid dendritic-star copolymers with three dendritic arms and two or three solvophobic linear arms, micelles with wide aggregation numbers are also formed but for slightly higher values of r. Our results for the aggregation number are compared with existing results of other architectures obtained at the same temperature, and an inequality for the aggregation number is proposed.     

Predicting retrosynthetic pathways using transformer-based models and a hyper-graph exploration strategy

We present an extension of our Molecular Transformer model combined with a hyper-graph exploration strategy for automatic retrosynthesis route planning without human intervention. The single-step retrosynthetic model sets a new state of the art for predicting reactants as well as reagents, solvents and catalysts for each retrosynthetic step. We introduce four metrics (coverage, class diversity, round-trip accuracy and Jensen–Shannon divergence) to evaluate the single-step retrosynthetic models, using the forward prediction and a reaction classification model always based on the transformer architecture. The hypergraph is constructed on the fly, and the nodes are filtered and further expanded based on a Bayesian-like probability. We critically assessed the end-to-end framework with several retrosynthesis examples from literature and academic exams. Overall, the frameworks have an excellent performance with few weaknesses related to the training data. The use of the introduced metrics opens up the possibility to optimize entire retrosynthetic frameworks by focusing on the performance of the single-step model only.

We present an extension of our Molecular Transformer model combined with a hyper-graph exploration strategy for automatic retrosynthesis route planning without human intervention.     

Electronic Structure of Rh(2)(&mgr;-CO)(CO)(2)(H(2)PCH(2)PH(2))(2). An Example of a Non-A-Frame Structure

Calculations based on density functional theory (DFT) and Hartree-Fock configuration interaction (HF-CI) methodology have been carried out to investigate the rhodium-rhodium coupling in Rh(2)(CO)(2)(dppm)(2), 1 (dppm = Ph(2)PCH(2)PPh(2)) and in Rh(2)(&mgr;-CO)(CO)(2)(dppm)(2), 2. DFT geometries, obtained with the Dgauss program, are in good agreement with those determined from X-ray, but HF geometries, calculated using the same basis sets, yield bond distances systematically too long. Calculations indicate that the rhodium atoms in 1 are linked by a single bond. The insertion of a semibridging carbonyl between the two metal atoms leads to a shortening of the rhodium-rhodium distance and also to a noticeable weakening of the metal-metal interaction. Both effects, and also the stabilization of the HOMO of 2, are related to an observed change from square planar to tetrahedral of the ligand environment of the Rh atom proximal to the inserted CO. Both MO analysis and bond characterization from the topology of the charge density confirm the existence of a bonding interaction between the semibridging carbonyl and the distal rhodium atom. The electronic structures of the dicationic complex [Rh(2)(CO)(3)(dppm)(2)](2+) and of the A-frame-like, isoelectronic system Rh(2)Br(2)(&mgr;-CO) (dppm)(2) are also discussed. The electron deformation density is derived from 2 by means of several methodological approaches, namely, HF, HF-CI, DFT, and DFT + gradient corrections. The HF deformation density obtained in the plane containing the metals and the three CO ligands is discussed, as well as the "correlation density" obtained from the difference maps DFT - HF and CI - HF.     

Optimum conditions for the water extraction of L-theanine from green tea

Theanine is a unique non-protein amino acid found in tea (Camellia sinensis). It contributes to the favourable umami taste of tea and is linked to various beneficial effects in humans. There is an increasing interest in theanine as an important component of tea, as an ingredient for novel functional foods and as a dietary supplement. Therefore, optimal conditions for extracting theanine from tea are required for the accurate quantification of theanine in tea and as an efficient first step for its purification. This study examined the effects of four different extraction conditions on the yield of theanine from green tea using water and applied response surface methodology to further optimise the extraction conditions. The results showed that temperature, extraction time, ratio of water-to-tea and tea particle sizes had significant impacts on the extraction yield of theanine. The optimal conditions for extracting theanine from green tea using water were found to be extraction at 80 °C for 30 min with a water-to-tea ratio of 20:1 mL/g and a tea particle size of 0.5-1 mm.     

Water-soluble ABC triblock copolymers based on vinyl ethers: Synthesis by living cationic polymerization and solution characterization

Water-soluble ABC triblock copolymers of methyl vinyl ether (MVE), ethyl vinyl ether (EVE), and methyl tri(ethylene glycol) vinyl ether (MTEGVE) of various block sequences and carrying 20 monomer units in each block were synthesized by living cationic polymerization. In addition to the triblocks, one AB diblock, one BA diblock, and one statistical copolymer of MVE and MTEGVE carrying 20 units of each type of monomer were synthesized as controls. Moreover, three homopolymers each carrying 20 units of MVE and end groups of varying hydrophobicity were synthesized using three different initiators. The molecular weights and molecular weight distributions of all the polymers were determined by gel permeation chromatography (GPC) in tetrahydrofuran (THF). The number average degrees of polymerization (DP_ns) and composition of all the polymers were calculated by proton nuclear magnetic resonance (¹H-NMR) spectroscopy. The molecular weights and degrees of polymerization corresponded to the values expected from the monomer/initiator ratios. The calculated polydispersities were reasonably narrow at 1.3. Aqueous GPC studies at room temperature on the triblock copolymers showed that the polymers exist as isolated chains (unimers) in solution but they tend to assemble and form micelles in the presence of a sufficiently high salt concentration apparently due to the insolubility of the EVE units under the latter conditions. Triblocks with a different block sequence exhibited a different susceptibility to salt-induced micellization, as indicated by the retention volume of the micelles and the relative micelle/unimer peak areas. Similarly, the cloud points of the triblock copolymers covered a relatively wide temperature range from 56 to 72°C. These differences in micellization and cloud points suggest a profound effect of the location of the hydrophilic MTEGVE block on copolymer association. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 1181–1195, 1997     

Simultaneous ultrasound-assisted emulsification-derivatization as a simple and miniaturized sample preparation method for determination of nitrite in cosmetic samples by microvolume UV-vis spectrophotomety

A simple and miniaturized approach based on ultrasound-assisted emulsification-derivatization is proposed for the determination of nitrite in cosmetic samples by UV-vis micro-spectrophotometry. Oil/water emulsions were formed using 15 mg of cosmetic sample and 1 mL of an aqueous medium containing 0.5% w/v SDS and 1% v/v acetic acid. When powerful sonication systems were used to make emulsions, i.e. probe or cup-horn sonoreactor, stable and transparent emulsions were obtained in one or half minute per sample, respectively. The Griess reaction in these special conditions (i.e. sonication and the presence of an organized medium) was investigated. The absence of matrix effects allows external calibration with aqueous standards for nitrite quantification. Analytical features were compared to those of the European official method 82/434/EEC. Detection limit, sample throughput and reagent consumption were significantly improved.     

Molecular mechanism of acid-triggered aryl-halide reductive elimination in well-defined aryl-Cu(III)-halide species

Well-defined aryl-Cu(III)-halide species undergo reductive elimination upon acid addition resulting in the formation of strong aryl-halide bonds. The computationally studied mechanism points towards ligand protonation as the rate-determining step, in agreement with previous experimental data.     

Classification of heterotic Pati–Salam models

We extend the classification of free fermionic heterotic-string models to vacua in which the SO(10)$\mathit{SO}(10)$ GUT symmetry is broken at the string level to the Pati–Salam subgroup. Using our classification method we recently presented the first example of a quasi-realistic heterotic-string vacuum that is free of massless exotic states. Within this method we are able to derive algebraic expressions for the Generalised GSO (GGSO) projections for all sectors that appear in the models. This facilitates the programming of the entire spectrum analysis in a computer code. The total number of vacua in the class of models that we classify is ²⁵¹∼¹⁰¹⁵$2^{51}\sim {10}^{15}$. We perform a statistical sampling in this space of models and extract 10¹¹ GGSO configurations with Pati–Salam gauge group. Our results demonstrate that one in every 10⁶ vacua correspond to a three generation exophobic model with the required Higgs states, needed to induce spontaneous breaking to the Standard Model.     

Finite automata based algorithms on subsequences and supersequences of degenerate strings

In this paper, we present linear-time algorithms for the construction two novel types of finite automata and show how they can be used to efficiently solve the Longest Common Subsequence (LCS), Shortest Common Supersequence (SCS) and Constrained Longest Common Subsequence (CLCS) problems for degenerate strings.