Additional Reaction Products Research Articles

Intramolecular Click Cycloaddition Reactions: Synthesis of 1,2,3-Triazoles.

Click Chemistry, as a powerful tool, has been used for the synthesis of a variety of 1,2,3-triazoles. Among click cycloaddition reactions, intramolecular click reactions carried out in azido-alkyne precursors has not been thoroughly reviewed. Hence, in this review, we have summarized and categorised the recent literature (from 2012 on) based on the azidoalkynyl precursor's type and a brief and concise description of the involved mechanisms is presented. Accordingly, we have classified the relevant literature into three categories: (1) substitution precursors (2) addition and (3) multi-component reaction (MCR) products.

Visualizing anions by color changing response: Exploitation of pyrimidine-based probe for simultaneous detection of CN− and F− ions

An easily scalable pyrimidine-based charge-transfer probe has been synthesized that can be utilized for simultaneous detection of both CN− and F− ions. The orange-colored solution of compound turns into yellow upon addition of F− ion, while the spiking of CN- ion leads to a colorless solution. Such color-changes have also been noticed on solid-supported materials, such as modified paper strips. Interestingly, the interaction with F- is found to be rapid as well as reversible (checked against water), while for cyanide ion, the scenario is completely opposite, the interaction is rather slow (∼10 min incubation time), and irreversible. The detailed spectroscopic investigation indicated that F−, being basic in nature, participates in the hydrogen bonding interaction. However, CN− ion, due to its highly nucleophilic character, formed Michael addition reaction product. Both these interactions substantially curtail the extent of intramolecular charge transfer and thereby resulting distinct changes in visible color. Detection of multiple anions via distinct naked-eye color changing response is not very common in the literature and therefore will be beneficial for future development of new sensory systems.

Does the radical GPRI strongly depend on the population scheme? A comparative study to predict radical attack on unsaturated molecules with the radical general-purpose reactivity indicator.

The reactivity of 22 unsaturated molecules undergoing attack by a methyl radical (⋅CH3) have been elucidated using the condensed radical general-purpose reactivity indicator (condensed radical GPRI) appropriate for relatively nucleophilic or electrophilic molecules. Using the appropriate radical GPRI equation for electrophilic attack or nucleophilic radical attack, seven different population schemes were used to assign the most reactive atoms in each of the 22 molecules. The results show that the condensed radical GPRI is sensitive to the population scheme chosen, but less sensitive than the radical Fukui function. Therefore, the reliability of these methods depends on the population scheme. Our investigation indicates that the condensed radical GPRI is most accurate in predicting the dominant products of the methyl radical addition reactions on a variety of unsaturated molecules when the Hirshfeld, Merz-Singh-Kollman, or Voronoi deformation density population schemes are used. Furthermore, for all populations schemes in the majority of instances where the radical Fukui function failed the radical GPRI was able to identify the most reactive atom under certain reactivity conditions.

Reaction dynamics of S(3P) with 1,3-butadiene and isoprene: crossed-beam scattering, low-temperature flow experiments, and high-level electronic structure calculations.

Sulfur atoms serve as key players in diverse chemical processes, from astrochemistry at very low temperature to combustion at high temperature. Building upon our prior findings, showing cyclization to thiophenes following the reaction of ground-state sulfur atoms with dienes, we here extend this investigation to include many additional reaction products, guided by detailed theoretical predictions. The outcomes highlight the complex formation of products during intersystem crossing (ISC) to the singlet surfaces. Here, we employed crossed-beam velocity map imaging and high-level ab initio methods to explore the reaction of S(3P) with 1,3-butadiene and isoprene under single-collision conditions and in low-temperature flows. For the butadiene reaction, our experimental results show the formation of thiophene via H2 loss, a 2H-thiophenyl radical through H loss, and thioketene through ethene loss at a slightly higher collision energy compared to previous observations. Complementary Chirped-Pulse Fourier-Transform mmWave spectroscopy (CP-FTmmW) measurements in a uniform flow confirmed the formation of thioketene in the reaction at 20 K. For the isoprene reaction, we observed analogous products along with the 2H-thiophenyl radical arising from methyl loss and C3H4S (loss of ethene or H2 + acetylene). CP-FTmmW detected the formation of thioformaldehyde via loss of 1,3-butadiene, again in the 20 K flow. Coupled-cluster calculations on the pathways found by the automated kinetic workflow code KinBot support these findings and indicate ISC to the singlet surface, leading to the generation of various long-lived intermediates, including 5-membered heterocycles.

Sulfur (3P) Reaction with Conjugated Dienes Gives Cyclization to Thiophenes under Single Collision Conditions.

We combine crossed-beam velocity map imaging with high-level ab initio/transition state theory modeling of the reaction of S(3P) with 1,3-butadiene and isoprene under single collision conditions. For the butadiene reaction, we detect both H and H2 loss from the initial adduct, and from reaction with isoprene, we see both H loss and methyl loss. Theoretical calculations confirm these arise following intersystem crossing to the singlet surface forming long-lived intermediates. For the butadiene reaction, these lose H2 to form thiophene as the dominant channel, H to form the detected 2H-thiophenyl radical, or ethene, giving thioketene. For isoprene, additional reaction products are suggested by theory, including the observed H and methyl loss radicals, but also methyl thiophene, thioformaldehyde, and thioketene. The results for S(3P) + 1,3-butadiene, showing direct cyclization to the aromatic product and yielding few bimolecular product channels, are in striking contrast to those for the analogous O(3P) reaction.

Investigating the retarding effect of CAC in alkali-activated cements

This paper discusses the design of hybrid alkali-activated binders at ambient temperature, specifically the development of mixes based on ground granulated blast-furnace slag (GGBFS) with calcium aluminate cement (CAC) as an additive, aiming to obtain high early strength binders with optimised Al incorporation, increased crosslinking and degree of polymerisation. The effects of 10 wt% CAC replacement of GGBFS, activated with sodium silicate with varying modulus (SiO2/Na2O molar ratio) or with sodium hydroxide, on fresh and hardened properties are investigated. The inclusion of CAC in GGBFS mixtures activated using sodium silicate results in an unexpected retardation of the polycondensation reactions required to form the main calcium aluminosilicate hydrate gel phase. This is due to incomplete dissolution of the GGBFS precursor, inhibited by the rapid formation of additional reaction products (especially cubic aluminate hydrates, C3AH6) resulting in lowered reaction kinetics, and thus delayed setting and hardening times. For sodium silicate activators, this retarding effect appears to be only slightly dependent on the activator solution modulus. When activating with 4 M NaOH, the retarding effect is reduced, along with the incorporation of CAC in the C-A-S-H gel, increasing the amount of reactive aluminium present in the binder to form a more compact gel product. Increasing the molarity of NaOH solutions results in a similar delay in reaction kinetics. The results suggest the existence of only a limited pH range in which the addition of CAC can promote the formation of a binding gel with enhanced mechanical properties, whilst other factors including the effect of sodium silicate inclusion in CAC systems are still unclear. The typical hydration products of CAC were not detected in this study.

Curing and thermal comparative study of rosin epoxy thermosets with bio-based imidoamines and commercial curing agents

This paper includes the curing of previously synthesized multifunctional bio-based epoxy resins (PEMPAE/TMPAE) with rosin-based imidoamine curing agents (IAMDK/IASDK/IAEDK) which are nucleophilic addition reaction products of diamino diphenyl ether (DDE) and dimaleopimaryl ketone (DMPK), a dehydrodecarboxylated derivative of MPA. Curing dynamics of rosin-based epoxy resins (PEMPAE/TMPAE) with rosin-based imidoamine curing agents (IAMDK/IASDK/IAEDK) were evaluated using differential scanning calorimetry. For comparison, the bio-based epoxy resins were also cured with rosin derivative dimaleopimaryl ketone (DMPK) and commercial-based diamino diphenyl ether (DDE). The universal testing machine and thermogravimetric analyzer) were used to measure the mechanical properties and thermal stability of the cured epoxy samples. The samples’ chemical resistance was assessed by calculating the weight loss in percent after they were submerged in solutions of NaOH, HCl, and NaCl. We also used scanning electron microscopy (SEM) to examine the morphological changes. Rosin-based epoxy cured with imidoamine curing agents outperformed the commercial epoxy in terms of performance.

Ar-Matrix Studies of the Photochemical Reaction between CS2 and ClF: Prereactive Complexes and Bond Isomerism of the Photoproducts

In this work, prereactive complexes, reaction products, and conformational preferences derived from the photochemical reaction between CS2 and ClF were analyzed following the codeposition of the reactants trapped in argon matrices at cryogenic temperatures. After codeposition of CS2 and ClF diluted in Ar, the formation of van der Waals complexes is observed. When the mixture is subsequently irradiated by means of broad-band UV-visible light (225 ≤ λ ≤ 800 nm), fluorothiocarbonylsulfenyl chloride (FC(S)SCl) and chlorothiocarbonylsulfenyl fluoride (ClC(S)SF) are produced. These species exist as two stable planar anti- and syn-conformers (anti- and syn- of the C=S double bond with respect to the S–Cl or S–F single bond, respectively). For both novel molecules, anti-FC(S)SCl and anti-ClC(S)SF are the lowest-energy computed rotamers. As expected due to the photochemical activity of these species, additional reaction products due to alternative or subsequent photochannels are formed during this process.

Therapeutic Potential of Schiff and Mannich Bases of 2-Substituted Benzimidazole Analogues

Heterocyclic scaffolds reveal extensive biological profiles, and several drugs were employed therapeutically which possess heterocyclic framework. Likewise, 2-substituted benzimidazoles play a significant role in novel drug development. In addition, Mannich and schiff base derivatives of benzimidazole acknowledged them as favorable anti-inflammatory, antimicrobial, anticancer, anthelmintic, antiviral scaffolds. Schiff bases in innumerable organic reactions show affirmative catalytic activity. The current scenario also emphasizes the spectacular activity displayed by schiff bases in the biochemical, coordination and analytical industry. Similarly, aminoalkyl reactions are revealed by mannich bases as they enclose amino alkyl chain which is imperative for its therapeutic action. Mannich bases are the products of nucleophilic addition reaction with the elimination of hydrogen atom of the amine radical for its biological venture. From the latest era, the efficacy of mannich bases as ligands and in the petroleum and leather industry were perceptible. The entire review expounds the therapeutic profile of mannich and schiff bases of 2-substituted benzimidazoles as competent biologically dynamic hybrids. Neoteric analogues of mannich and schiff bases of 2-substituted benzimidazoles with their patents in diverse fields have also been summarized.

A universal free energy relationship for both hard and soft radical addition in water

AbstractPrioritization of (eco)toxicological risks and technological endpoints among 100,000+ potential substances, conditions and mechanisms requires computationally ‘inexpensive’ and accurate tools to ‘screen’ reactivity and identify reaction products. Such prediction tools are very scarce. Left unresolved, charge‐transfer and hydration complicate predictions. Based on experimental reaction of radicals (3O2, CH3•, CO3•− etc.) with organic substrates, we hypothesized that a universal linear free energy relationship (LFER) can rationalize these reactions to accurately predict addition rates.We calculated free energies of forming charge‐separated intermediates from explicit descriptions of addition reaction products. We combined these energies, via a thermodynamic cycle, with electron transfer energies to calculate product formation energies. All energies include consideration of hydration effects by water. We ascribe feasibilities of ‘hard’ (ionic) and ‘soft’ (covalent) mechanisms to the relevance of the charge‐separated intermediate.Analysis shows that activation energies effectively relate to a combination of product formation energies and charge‐separation energies. The relative importance of these is determined by a mixing parameter, which is mostly constant for a given radical (substrate). Via the Eyring equation, our universal LFER explains up to 94% of the variance in data for rate constants. Prediction error is a factor 5 (2 SD), only slightly larger than variation in experimentation, particularly sensitive to varying reaction conditions.Minimal parametrization ensures that our new framework for calculating reactivity of radical addition is accurate, robust and with satisfactory rational. Calculation time for 100 reactions is <1 h on a standard desktop PC. In anticipation of underpinning with an even wider range of reagents, this ‘inexpensive’ calculus can more easily assess a greater domain of structures and extrapolate to new structures. This helps to better assess and select favourable non‐toxic, environmentally friendly and technologically superior chemical (sub)structures.

From electronic structure to combustion model application for acrolein chemistry part I: Acrolein + H reactions and related chemistry

Detailed reaction kinetics of acrolein + H and related chemistry and its influence on the ignition delay time prediction of acrolein has been studied theoretically in this work. The geometry optimization and vibrational frequency calculations for every stationary point were performed at the BH&HLYP/6–311++G(d,p) level of theory, with one-dimensional hindered rotation treatments applied for low-frequency torsional modes determined by using BH&HLYP/6–31G(d). Electronic energies for all species were calculated at the ROCCSD(T)/cc-pVQ,TZ levels of theory. The kinetics and thermochemistry data were calculated and compared with existing literature results, where good agreement was observed. The branching ratios of the crucial products vary in the pressure range of 0.01–100 atm and temperatures from 298 to 2000 K. Taking 1 atm as an example, at temperatures above 1000 K, the main addition reaction products of acrolein + H are ethylene + formyl radical, while at lower temperatures, the formation of the resonantly stabilized radical, CH3ĊHCHO, is important. The dominant H-atom abstraction reaction channel by H atom proceeds at the α carbon atom of the aldehyde group of acrolein. However, the H-atom abstraction reactions are overwhelmed by the addition reactions. Decomposition reactions of four C3H3O radicals were calculated and analysed. Temperature-dependent thermochemical properties for all species in the reaction system and the pressure-dependent rate constants for each reaction pathway were incorporated into two acrolein combustion kinetic mechanisms, as well as two widely used mechanisms, AramcoMech 3.0 and JetSurF 2.0, to test the influence of the newly calculated data on acrolein oxidation. Some critical reactions for acrolein oxidation were highlighted by performing sensitivity and flux analyses.

Effect of chemical exposure on mechanical properties and microstructure of lightweight polymer composites containing solid waste fillers

This paper presents the effect of sulphuric acid (H2SO4), magnesium sulphate (MgSO4) and sodium chloride (NaCl) solutions on mechanical properties and microstructure of lightweight polymer composites containing recycled Polyethylene terephthalate (PET) flakes, recycled tyre crumb rubber (CR) and fly ash (FA) as fillers. The lightweight polymer composites are exposed to 1 mol H2SO4, 1 mol MgSO4 and 0.5 mol NaCl solutions for one to six months. Compressive strength, density, flexural strength and microstructural analysis are conducted to evaluate the residual behaviour of the composites after their respective exposure duration. Based on test results, it is found that most of the developed lightweight polymer composites exhibited better residual compressive strength after exposure to above chemical solutions. Mixed results are obtained in the case of residual flexural strength. No significant change in density of the polymer composite is observed in all composites at different exposure periods and solutions. The microstructural analysis revealed no deterioration of the composite nor any additional reaction products formed in the composites after exposing to those aggressive solutions.

Influence of seawater on alkali-activated slag concrete

This study examines the use of natural seawater as mixing water for alkali-activated slag concrete and reports the characteristics of alkali-activated slag concrete with exposure to seawater. Preliminary experiments were conducted on pastes in order to measure pH and select optimum activator content under the experimental conditions. Wet-sieved pastes from fresh concrete were used to evaluate the mineralogical and microstructural characteristics of reaction products. Compressive strengths and chloride contents were measured with the hardened concrete samples. The activators used in alkali-activated slag concrete were sodium hydroxide (5% weight of slag) and liquid sodium silicate (5% weight of slag). The alkali-activated slag samples showed the carbonation of calcium silicate hydrate (C–S–H), which resulted in the reduction in strength with time. The seawater-mixed alkali-activated slag samples produced additional reaction products, C4AH13, and chloride-bearing hydrocalumite, and they improved the strength. The seawater-mixed alkali-activated slag samples exposed in seawater exhibited improved mechanical performance compared to other samples. C–S–H carbonation did not occur, refinement of the pore structure was confirmed, and the compressive strength increased after exposure to seawater. The release of partial chloride ions, which were bound in solid phases, occurred; however, such slight leaching did not affect the strength of the samples. The investigation within the experimental conditions of this study showed a positive result regarding the use of seawater as mixing water in alkali-activated slag concrete.

Photooxidation of pinonaldehyde at ambient conditions investigated in the atmospheric simulation chamber SAPHIR

Abstract. The photooxidation of pinonaldehyde, one product of the α-pinene degradation, was investigated in the atmospheric simulation chamber SAPHIR under natural sunlight at low NO concentrations (<0.2 ppbv) with and without an added hydroxyl radical (OH) scavenger. With a scavenger, pinonaldehyde was exclusively removed by photolysis, whereas without a scavenger, the degradation was dominated by reaction with OH. In both cases, the observed rate of pinonaldehyde consumption was faster than predicted by an explicit chemical model, the Master Chemical Mechanism (MCM, version 3.3.1). In the case with an OH scavenger, the observed photolytic decay can be reproduced by the model if an experimentally determined photolysis frequency is used instead of the parameterization in the MCM. A good fit is obtained when the photolysis frequency is calculated from the measured solar actinic flux spectrum, absorption cross sections published by Hallquist et al. (1997), and an effective quantum yield of 0.9. The resulting photolysis frequency is 3.5 times faster than the parameterization in the MCM. When pinonaldehyde is mainly removed by reaction with OH, the observed OH and hydroperoxy radical (HO2) concentrations are underestimated in the model by a factor of 2. Using measured HO2 as a model constraint brings modeled and measured OH concentrations into agreement. This suggests that the chemical mechanism includes all relevant OH-producing reactions but is missing a source for HO2. The missing HO2 source strength of (0.8 to 1.5) ppbv h−1 is similar to the rate of the pinonaldehyde consumption of up to 2.5 ppbv h−1. When the model is constrained by HO2 concentrations and the experimentally derived photolysis frequency, the pinonaldehyde decay is well represented. The photolysis of pinonaldehyde yields 0.18 ± 0.20 formaldehyde molecules at NO concentrations of less than 200 pptv, but no significant acetone formation is observed. When pinonaldehyde is also oxidized by OH under low NO conditions (maximum 80 pptv), yields of acetone and formaldehyde increase over the course of the experiment from 0.2 to 0.3 and from 0.15 to 0.45, respectively. Fantechi et al. (2002) proposed a degradation mechanism based on quantum-chemical calculations, which is considerably more complex than the MCM scheme and contains additional reaction pathways and products. Implementing these modifications results in a closure of the model–measurement discrepancy for the products acetone and formaldehyde, when pinonaldehyde is degraded only by photolysis. In contrast, the underprediction of formed acetone and formaldehyde is worsened compared to model results by the MCM, when pinonaldehyde is mainly degraded in the reaction with OH. This shows that the current mechanisms lack acetone and formaldehyde sources for low NO conditions like in these experiments. Implementing the modifications suggested by Fantechi et al. (2002) does not improve the model–measurement agreement of OH and HO2.

Role of glutathione on acrylamide inhibition: Transformation products and mechanism

Glutathione (GSH) is a potential inhibitor for acrylamide (AA) in heated food. In the present study, the inhibition pathways of GSH on AA were investigated in the asparagine(Asn)/glucose(Glc)/GSH model system. In comparison to the Asn/Glc model system, three unique molecular ions (m/z 470, 379, and 193) were identified in the Asn/Glc/GSH model system. Those molecular ions were confirmed as the Amadori rearrangement products which formed in the reaction between Glc and GSH, as well as the addition reaction products between AA and the sulfhydryl group (-SH) of GSH and cysteine (Cys). The competition between Asn and GSH for Glc in the competitive reactions was assumed to be the major pathway. Additionally, the elimination reaction between AA and GSH or between AA and Cys also played a minor role in the inhibition of AA. The variances of precursors, intermediates, and final products provided quantitative evidence for the above pathways.

Solid-State NMR Techniques for the Structural Characterization of Cyclic Aggregates Based on Borane-Phosphane Frustrated Lewis Pairs.

Modern solid-state NMR techniques offer a wide range of opportunities for the structural characterization of frustrated Lewis pairs (FLPs), their aggregates, and the products of cooperative addition reactions at their two Lewis centers. This information is extremely valuable for materials that elude structural characterization by X-ray diffraction because of their nanocrystalline or amorphous character, (pseudo-)polymorphism, or other types of disordering phenomena inherent in the solid state. Aside from simple chemical shift measurements using single-pulse or cross-polarization/magic-angle spinning NMR detection techniques, the availability of advanced multidimensional and double-resonance NMR methods greatly deepened the informational content of these experiments. In particular, methods quantifying the magnetic dipole–dipole interaction strengths and indirect spin–spin interactions prove useful for the measurement of intermolecular association, connectivity, assessment of FLP–ligand distributions, and the stereochemistry of adducts. The present review illustrates several important solid-state NMR methods with some insightful applications to open questions in FLP chemistry, with a particular focus on supramolecular associates.

A simple ratiometric fluorescent sensor selectively compatible of different combinations of characteristic groups for identification of glutathione, cysteine and homocysteine

Simultaneous detection of biothiols would be helpful for understanding their biological functions and pathological study of related diseases. The structural similarities of biothiols present a great challenge to achieve their selective detection. Herein, we report a simple acrylate-substituted fluorescent sensor BTHA with one recognition site and an assisted neighboring hydroxy group for this purpose. BTHA exhibited an emission band at 507 nm with a 147 nm Stokes shift. Upon addition of glutathione (GSH) or cysteine (Cys), deacrylate product was obtained and new fluorescent band at 459 nm occurred. The addition reaction product with decreased fluorescence was achieved as BTHA was treated with homocysteine (Hcy). BTHA acts with the mercapto group of Cys, the mercapto and amino group of Hcy, and the mercapto and carboxyl group of GSH, respectively. Correspondingly, different ratiometric fluorescence changes (I459/I507) with these biothiols was produced. Using the two-dimensional map with two channel signals, BTHA can simultaneous distinguish GSH, Cys and Hcy. The sensor BTHA can also be used for exogenous and endogenous GSH imaging with ratiometric fluorescence response in live cells.

Development of [131I]I-EOE-TPZ and [131I]I-EOE-TPZMO: Novel Tirapazamine (TPZ)-Based Radioiodinated Pharmaceuticals for Application in Theranostic Management of Hypoxia.

Introduction: Benzotriazine-1,4-dioxides (BTDOs) such as tirapazamine (TPZ) and its derivatives act as radiosensitizers of hypoxic tissues. The benzotriazine-1-monoxide (BTMO) metabolite (SR 4317, TPZMO) of TPZ also has radiosensitizing properties, and via unknown mechanisms, is a potent enhancer of the radiosensitizing effects of TPZ. Unlike their 2-nitroimidazole radiosensitizer counterparts, radiolabeled benzotriazine oxides have not been used as radiopharmaceuticals for diagnostic imaging or molecular radiotherapy (MRT) of hypoxia. The radioiodination chemistry for preparing model radioiodinated BTDOs and BTMOs is now reported. Hypothesis: Radioiodinated 3-(2-iodoethoxyethyl)-amino-1,2,4-benzotriazine-1,4-dioxide (I-EOE-TPZ), a novel bioisosteric analogue of TPZ, and 3-(2-iodoethoxyethyl)-amino-1,2,4-benzotriazine-1-oxide (I-EOE-TPZMO), its monoxide analogue, are candidates for in vivo and in vitro investigations of biochemical mechanisms in pathologies that develop hypoxic microenvironments. In theory, both radiotracers can be prepared from the same precursors. Methods: Radioiodination procedures were based on classical nucleophilic [131I]iodide substitution on Tos-EOE-TPZ (P1) and by [131I]iodide exchange on I-EOE-TPZ (P2). Reaction parameters, including temperature, reaction time, solvent and the influence of pivalic acid on products’ formation and the corresponding radiochemical yields (RCY) were investigated. Results: The [131I]iodide labeling reactions invariably led to the synthesis of both products, but with careful manipulation of conditions the preferred product could be recovered as the major product. Radioiodide exchange on P2 in ACN at 80 ± 5 °C for 30 min afforded the highest RCY, 89%, of [131I]I-EOE-TPZ, which upon solid phase purification on an alumina cartridge gave 60% yield of the product with over 97% of radiochemical purity. Similarly, radioiodide exchange on P2 in ACN at 50 ± 5 °C for 30 min with pivalic acid afforded the highest yield, 92%, of [131I]I-EOE-TPZMO exclusively with no trace of [131I]I-EOE-TPZ. In both cases, extended reaction times and/or elevated temperatures resulted in the formation of at least two additional radioactive reaction products. Conclusions: Radioiodination of P1 and P2 with [131I]iodide leads to the facile formation of [131I]I-EOE-TPZMO. At 80 °C and short reaction times, the facile reduction of the N-4-oxide moiety was minimized to afford acceptable radiochemical yields of [131I]I-EOE-TPZ from either precursor. Regeneration of [131I]I-EOE-TPZ from [131I]I-EOE-TPZMO is impractical after reaction work-up.

Micromechanics-based investigation of the elastic properties of polymer-modified cementitious materials using nanoindentation and semi-analytical modeling

Cementitious materials are modified by the addition of polymers in order to improve the durability and the adhesive strength. However, polymer-modified mortars and concretes exhibit lower elastic moduli in comparison to unmodified systems. The macroscopic properties are governed by microstructural changes in the binder matrix, which consists of both cementitious and polymer components. Herein, different polymer-modified cement pastes were characterized using nanoindentation to better understand the microscopic origin of the macroscopic elastic modulus. By means of the statistical nanoindentation technique, the existence of three micromechanical phases in plain and polymer-modified cement pastes with a water-to-cement mass ratio of 0.40 is evidenced, illustrating that the polymer modification does not induce the formation of additional reaction products. Instead, the polymers adsorb on the hydration products as well as on unhydrated clinker grains and decrease the indentation moduli of the micromechanical phases. The link between the microscopic and macroscopic mechanical properties is established by means of a continuum micromechanics approach. A multiscale model aimed at the prediction of the elastic moduli of polymer-modified cementitious materials is developed with input parameters that are partially obtained from the nanoindentation tests. The comparison of the modeling results with the experimentally determined elastic (macroscopic) moduli at the scales of cement paste, mortar, and concrete is satisfactorily good, underlining the predictive capability of the modeling approach. The improvement of prediction models is essential for the application of polymer-modified cementitious materials in construction and will encourage their integration into design guidelines.

Exceptional case of Kasha's rule: Emission from higher-lying singlet electron excited states into ground states in coumarin-based biothiol sensing

A coumarin-based fluorescent sensor (7-Acryloxy-4-methylcoumarin, AMC) for biothiols has been studied by a combination of quantum chemical calculation and experimental investigation. The AMC selectively reacts with mercapto biomolecules via Michael addition, which can be served as a ratiometric fluorescent sensor for thiol-containing biomolecules. The AMC sensor shows a selectivity towards biothiols with sensitivity in the order of cysteine > glutathione > homocysteine. Moreover, the AMC sensor can detect the cysteine concentration within the intracellular level. The results of the theoretical investigations on the electron excited states show that the lack of overlapping between MOs in transitions of the lower-lying singlet electron excited states and the small energy gap between electron excited states are the cause of fluorescence from the higher-lying singlet electron excited states, as an exception from Kasha's rule. The fluorescence from the higher-lying singlet electron excited states leads to marked fluorescence enhancement at long wavelength in the products of addition reaction of biothiols to AMC sensor.