ICT-based fluorescent nanoparticles for selective cyanide ion detection and quantification in apple seeds.

In this report, we successfully engineered a novel probe based on an acceptor-donor-acceptor (A-D-A) architecture featuring dicyanovinyl-substituted thieno[3,2-]thiophene, termed DCVTT. The designed probe self-assembles into luminous nanoparticles (DCVTT NPs) upon introducing mixed aqueous solutions. These fluorescent nanostructures served as a ratiometric probe for detecting cyanide (CN) ions in aqueous-based environments, owing to the robust Intramolecular Charge Transfer (ICT) characteristics of DCVTT.

The seventh blind test of crystal structure prediction: structure generation methods.

A seventh blind test of crystal structure prediction was organized by the Cambridge Crystallographic Data Centre featuring seven target systems of varying complexity: a silicon and iodine-containing molecule, a copper coordination complex, a near-rigid molecule, a cocrystal, a polymorphic small agrochemical, a highly flexible polymorphic drug candidate, and a polymorphic morpholine salt. In this first of two parts focusing on structure generation methods, many crystal structure prediction (CSP) methods performed well for the small but flexible agrochemical compound, successfully reproducing the experimentally observed crystal structures, while few groups were successful for the systems of higher complexity. A powder X-ray diffraction (PXRD) assisted exercise demonstrated the use of CSP in successfully determining a crystal structure from a low-quality PXRD pattern.

Dynamic Covalent Chemistry of Enamine-Ones: Exploring Tunable Reactivity in Vitrimeric Polymers and Covalent Organic Frameworks.

Dynamic covalent chemistry (DCC) has revolutionized the field of polymer science by offering new opportunities for the synthesis, processability, and recyclability of polymers as well as in the development of new materials with interesting properties such as vitrimers and covalent organic frameworks (COFs). Many DCC linkages have been explored for this purpose, but recently, enamine-ones have proven to be promising dynamic linkages because of their facile reversible transamination reactions under thermodynamic control. Their high stability, stimuli-responsive properties, and tunable kinetics make them promising dynamic cross-linkers in network polymers.

Quantifying CO-release from a photo-CORM using F NMR: An investigation into light-induced CO delivery.

Carbon monoxide (CO) is an innate signaling molecule that can regulate immune responses and interact with crucial elements of the circadian clock. Moreover, pharmacologically, CO has been substantiated for its therapeutic advantages in animal models of diverse pathological conditions. Given that an excessive level of CO can be toxic, it is imperative to quantify the necessary amount for therapeutic use accurately.

Surface Engineering of the Mechanical Properties of Molecular Crystals via an Atomistic Model for Computing the Facet Stress Response of Solids.

Dynamic molecular crystals are an emerging class of crystalline materials that can respond to mechanical stress by dissipating internal strain in a number of ways. Given the serendipitous nature of the discovery of such crystals, progress in the field requires advances in computational methods for the accurate and high-throughput computation of the nanomechanical properties of crystals on specific facets which are exposed to mechanical stress. Here, we develop and apply a new atomistic model for computing the surface elastic moduli of crystals on any set of facets of interest using dispersion-corrected density functional theory (DFT-D) methods.

In Situ Growth of Interfacially Nanoengineered 2D-2D WS/TiCT MXene for the Enhanced Performance of Hydrogen Evolution Reactions.

In line with current research goals involving water splitting for hydrogen production, this work aims to develop a noble-metal-free electrocatalyst for a superior hydrogen evolution reaction (HER). A single-step interfacial activation of TiCT MXene layers was employed by uniformly growing embedded WS two-dimensional (2D) nanopetal-like sheets through a facile solvothermal method. We exploited the interactions between WS nanopetals and TiCT nanolayers to enhance HER performance.

Unveiling the topology of partially disordered micro-crystalline nitro-perylenediimide with X-aggregate stacking: an integrated approach.

Profound knowledge of the molecular structure and supramolecular organization of organic molecules is essential to understand their structure-property relationships. Herein we demonstrate the packing arrangement of partially disordered nitro-perylenediimide (NO-PDI), revealing that the perylenediimide units exhibit an X-shaped packing pattern. The packing of NO-PDI is derived using a complementary approach that utilises solid-state NMR (ssNMR) and 3D electron diffraction (3D ED) techniques.

Mechanical properties and peculiarities of molecular crystals.

In the last century, molecular crystals functioned predominantly as a means for determining the molecular structures X-ray diffraction, albeit as the century came to a close the response of molecular crystals to electric, magnetic, and light fields revealed that the physical properties of molecular crystals were as rich as the diversity of molecules themselves. In this century, the mechanical properties of molecular crystals have continued to enhance our understanding of the colligative responses of weakly bound molecules to internal frustration and applied forces. Here, the authors review the main themes of research that have developed in recent decades, prefaced by an overview of the particular considerations that distinguish molecular crystals from traditional materials such as metals and ceramics.

Elastic organic semiconducting single crystals for durable all-flexible field-effect transistors: insights into the bending mechanism.

Although many examples of mechanically flexible crystals are currently known, their utility in all-flexible devices is not yet adequately demonstrated, despite their immense potential for fabricating high performance flexible devices. Here, we report two alkylated diketopyrrolopyrrole (DPP) semiconducting single crystals, one of which displays impressive elastic mechanical flexibility whilst the other is brittle. Using the single crystal structures and density functional theory (DFT) calculations, we show that the methylated diketopyrrolopyrrole (DPP-diMe) crystals, with dominant π-stacking interactions and large contributions from dispersive interactions, are superior in terms of their stress tolerance and field-effect mobility ( ) when compared to the brittle crystals of the ethylated diketopyrrolopyrrole derivative (DPP-diEt).

Exceptionally high work density of a ferroelectric dynamic organic crystal around room temperature.

Dynamic organic crystals are rapidly gaining traction as a new class of smart materials for energy conversion, however, they are only capable of very small strokes (<12%) and most of them operate through energetically cost-prohibitive processes at high temperatures. We report on the exceptional performance of an organic actuating material with exceedingly large stroke that can reversibly convert energy into work around room temperature. When transitioning at 295-305 K on heating and at 265-275 K on cooling the ferroelectric crystals of guanidinium nitrate exert a linear stroke of 51%, the highest value observed with a reversible operation of an organic single crystal actuator.

Mechanosynthesis of Higher-Order Cocrystals: Tuning Order, Functionality and Size in Cocrystal Design*.

The ability to rationally design and predictably construct crystalline solids has been the hallmark of crystal engineering research. To date, numerous examples of multicomponent crystals comprising organic molecules have been reported. However, the crystal engineering of cocrystals comprising both organic and inorganic chemical units is still poorly understood and mostly unexplored.

Mechanically robust amino acid crystals as fiber-optic transducers and wide bandpass filters for optical communication in the near-infrared.

Organic crystals are emerging as mechanically compliant, light-weight and chemically versatile alternatives to the commonly used silica and polymer waveguides. However, the previously reported organic crystals were shown to be able to transmit visible light, whereas actual implementation in telecommunication devices requires transparency in the near-infrared spectral range. Here we demonstrate that single crystals of the amino acid L-threonine could be used as optical waveguides and filters with high mechanical and thermal robustness for transduction of signals in the telecommunications range.

Efficient Screening for Ternary Molecular Ionic Cocrystals Using a Complementary Mechanosynthesis and Computational Structure Prediction Approach.

The discovery of molecular ionic cocrystals (ICCs) of active pharmaceutical ingredients (APIs) widens the opportunities for optimizing the physicochemical properties of APIs whilst facilitating the delivery of multiple therapeutic agents. However, ICCs are often observed serendipitously in crystallization screens and the factors dictating their crystallization are poorly understood. We demonstrate here that mechanochemical ball milling is a versatile technique for the reproducible synthesis of ternary molecular ICCs in less than 30 min of grinding with or without solvent.

Towards the systematic crystallisation of molecular ionic cocrystals: insights from computed crystal form landscapes.

The underlying molecular and crystal properties affecting the crystallisation of ionic cocrystals (ICCs) with the general formula A-B+N (A- = anion, B+ = cation and N = neutral acid molecule; 1 : 1 : 1 stoichiometry) are reported for a limited set of known crystal structures determined following the cocrystallisation of either 4-aminopyridine (which forms salts) or 4-dimethylaminopyridine (which forms salts and ICCs) with the same set of monoprotic acids with a single hydroxy or halogen substitution at the ortho or para position. Periodic density functional theory calculations (PBE + D2) on the energetic driving force for ICC crystallisation for a set of known crystal structures with well characterised acid, salt and ICC structures show that all but 1 of the 7 experimental ICC structures surveyed were more stable than the sum of their component salt and acid structures with 4 displaying relative stabilities (ΔEICC) ranging from 2.47-8.

Solvent inclusion in the crystal structure of bis-[(adamantan-1-yl)methanaminium chloride] 1,4-dioxane hemisolvate monohydrate explained using the computed crystal energy landscape.

Repeated attempts to crystallize 1-adamantane-methyl-amine hydro-chloride as an anhydrate failed but the salt was successfully crystallized as a solvate (2CHN·2Cl·0.5CHO·HO), with water and 1,4-dioxane playing a structural role in the crystal and engaging in hydrogen-bonding inter-actions with the cation and anion. Computational crystal-structure prediction was used to rationalize the solvent-inclusion behaviour of this salt by computing the solvent-accessible voids in the predicted low-energy structures for the anhydrate: the global lattice-energy minimum structure, which has the same packing of the ions as the solvate, has solvent-accessible voids that account for 3.