Guest inclusion by native cyclodextrins in solid state and solutions: A review.

In many industrial applications, preparation of cyclodextrin (CD) inclusion complexes with drugs, food additives, dyes and components of essence oils is performed in solid mixtures, slurries or paste-like systems having lack of water to dissolve cyclodextrin and guest completely. Such systems need a different description than supplied by classical analysis of CD complexation in aqueous solutions. The main feature of solid-state guest inclusion is the phase transition from solid CD to solid inclusion compound.

Cyclization of alanyl-valine dipeptides in the solid state. The effects of molecular radiator and heat capacity.

Heating of linear dipeptides above a critical temperature initiates their cyclization even in the solid state. This method of obtaining cyclic dipeptides meets the requirements of "green chemistry", provides a high yield of the main product and releases only water as a by-product of the reaction, and does not require solvents. However, to date, the cyclization of only a small number of dipeptides in the solid state has been studied, and some correlations of the process were discovered.

Multi-functional imidazolium dendrimers based on thiacalix[4]arenes: self-assembly, catalysis and DNA binding.

For the first time, dendrimers based on thiacalix[4]arenes bearing imidazolium dendrons on one side and alkyl fragments on another side of the macrocyclic platform and symmetrical dendrimers with four dendrons on both sides were synthesized. Dendrons consist of gallic acid-based branches functionalized with imidazolium and triazolium groups. The physicochemical properties of the dendrimers such as micellar concentration (CMC), size, and solubilization capacity were measured.

Pluronic P123/DMSO Lyotropic Liquid Crystal for Incorporating Bioactive Substances for Topical Application.

Lyotropic liquid crystals (LLCs) have attracted considerably growing interest in drug delivery applications over the last years. The structure of LLC matrices is complementary to cell membranes and provides an efficient, controlled, and selective release of drugs. In this work, a complex of experimental methods was used to characterize binary LLCs Pluronic P123/DMSO and triple LLC systems Pluronic P123/DMSO/Ibuprofen, which are interesting as transdermal drug delivery systems.

Determination of Melting Parameters of Cyclodextrins Using Fast Scanning Calorimetry.

The first evidence of native cyclodextrins fusion was registered using fast scanning calorimetry (FSC) with heating rates up to 40,000 K s. The endothermal effects, detected at low heating rates, correspond to the decomposition processes. Upon the increase of the heating rate the onset of these effects shifts to higher temperatures, reaching a limiting value at high heating rates.

2D Monomolecular Nanosheets Based on Thiacalixarene Derivatives: Synthesis, Solid State Self-Assembly and Crystal Polymorphism.

Synthetic organic 2D materials are attracting careful attention of researchers due to their excellent functionality in various applications, including storage batteries, catalysis, thermoelectricity, advanced electronics, superconductors, optoelectronics, etc. In this work, thiacalix[4]arene derivatives functionalized by geranyl fragments at the lower rim in and conformations, that are capable of controlled self-assembly in a 2D nanostructures were synthesized. X-ray diffraction analysis showed the formation of 2D monomolecular-layer nanosheets from synthesized thiacalix[4]arenes, the distance between which depends on the stereoisomer used.

Smart Molecular Recognition: From Key-to-Lock Principle to Memory-Based Selectivity.

The formation and decomposition of inclusion compounds with a solid-solid phase transition may be very selective to the guest molecular structure. This selectivity may function in essentially different ways than defined by the classical concept of molecular recognition, which implies the preferential binding of complementary molecules. Solid inclusion compounds may take part as an initial or/and final state in several processes of different types summarized in this review, which selectivity is boosted by cooperativity of participating molecular crystals.

Smart control of guest inclusion by α-cyclodextrin using its hydration history.

Hydration history was found to control the inclusion capacity of α-cyclodextrin (aCD) for volatile organic guests, so that its level may be switched from zero to the stoichiometric value and back by the variation of aCD hydration/dehydration order and direction. Such variation of the inclusion capacity is caused by the balance of two water roles: the activation of guest inclusion and guest/water competition. These observed concurrent roles and the cooperativity of guest inclusion and hydration make possible the smart tuning of the guest inclusion by the subtle change of preparation procedure.

Thermally induced cyclization of -isoleucyl- -alanine in solid state: Effect of dipeptide structure on reaction temperature and self-assembly.

Thermal treatment of short-chain oligopeptides is able to initiate the process of their self-assembly with the formation of organic nanostructures with unique properties. On the other hand, heating can lead to a chemical reaction with the formation of new substances with specific properties and ability to form structures with different morphology. Therefore, in order to have a desired process, researcher needs to find its temperature range.

Role of water in the formation of unusual organogels with cyclo(leucyl-leucyl).

The key role of water in the formation of cyclo(leucyl-leucyl) organogels was demonstrated. The conditions required for preparation of previously unknown gels with aliphatic hydrocarbons at room temperature were determined. Cyclo(leucyl-leucyl) self-assembles to form different structures depending on the medium used.

Size exclusion effect in binary inclusion compounds of α-cyclodextrin.

The size exclusion of guests by α-cyclodextrin (aCD) in binary host-guest systems was observed to be a key structure-property relationship for the choice of this host as a receptor. For this, vapor sorption isotherms of water and volatile organic compounds were determined using dry aCD, which show an inclusion threshold by sorbate activity corresponding to a phase transition of guest (or water) inclusion. These phase transitions were also characterized using X-ray powder diffractograms.

On the Solvation Behavior of Graphene Oxide in Ethylene Glycol/Water Mixtures.

The self-association and solvation pattern of graphene oxide (GO) in water, ethylene glycol (EG), and their mixtures were analyzed by means of UV/Vis spectrophotometry. A careful analysis of the absorbance dependencies vs. the GO concentration shows that self-association of the GO sheets in EG occurs at higher concentration compared to that in water.

Thermally Induced Self-Assembly and Cyclization of l-Leucyl-l-Leucine in Solid State.

Thermal treatment of oligopeptides is one of the methods for synthesis of organic nanostructures. However, heating may lead not only to self-assembly of the initial molecules, but also to chemical reactions resulting in the formation of new unexpected nanostructures or change in the properties of the existing ones. In the present work, the reaction of cyclization of dipeptide l-leucyl-l-leucine in solid state under heating was studied.

Non-zeolitic properties of the dipeptide l-leucyl-l-leucine as a result of the specific nanostructure formation.

The non-zeolitic behavior of l-leucyl-l-leucine and its self-organization in solid state and from solutions with the formation of different nanostructures are reported. This dipeptide forms porous crystals, but does not exhibit molecular sieve effects typical of classical zeolites and biozeolites. The specific sorption properties of l-leucyl-l-leucine result from a change in its crystal packing from channel-type to layered-type, when binding strong proton acceptors or proton donors of molecular size greater than 18-20 cm mol.

A study of the formation of magnetically active solid dispersions of phenacetin using atomic and magnetic force microscopy.

A lot of pharmaceutical substances have a poor solubility that limits their absorption and distribution to the targeted sites to elicit the desired action without causing untoward effects on healthy cells or tissues. For such drugs, new modes of delivery have to be developed for efficient and effective delivery of the drug to the target site. Formation of magnetically active solid dispersion of such drugs could be a useful approach to addressing this problem because they combine targeted delivery and good solubility.

Thermodynamics of dissolution and infrared-spectroscopy of solid dispersions of phenacetin.

In this work enthalpies of dissolution in water of polyethylene glycols (PEGs) having an average molecular weight of 1000 and 1400, Pluronic-F127, phenacetin as well as the composites prepared from them were measured using solution calorimetry at 298.15 K. Intermolecular interaction energies of polymer-phenacetin were calculated on the basis of an additive scheme.

Interaction of L-alanyl-L-valine and L-valyl-L-alanine with organic vapors: thermal stability of clathrates, sorption capacity and the change in the morphology of dipeptide films.

The strong effect of the amino acid sequence in L-alanyl-L-valine and L-valyl-L-alanine on their sorption properties toward organic compounds and water, and the thermal stability of the inclusion compounds of these dipeptides have been found. Generally, L-valyl-L-alanine has a greater sorption capacity for the studied compounds, but the thermal stability of the L-alanyl-L-valine clathrates is higher. Unusual selectivity of L-valyl-L-alanine for vapors of few chloroalkanes was observed.

Unusually high efficiency of β-cyclodextrin clathrate preparation by water-free solid-phase guest exchange.

An effective preparation procedure is offered for β-cyclodextrin (bCD) clathrates with volatile guests of moderate hydrophilicity, which otherwise require a finely tuned optimization of the bCD/water/guest ratio. The proposed procedure includes guest exchange in a water-free bCD matrix. As a result, more stable clathrates with a higher inclusion capacity can be prepared than by direct saturation of dried or hydrated bCD.

Analysis of guest binary mixtures by tert-butylcalix[6]arene using host memory of previously bound guests.

A new principle of quantitative and qualitative analysis of binary organic mixtures is offered, which is based on an ability of calixarene receptor for specific polymorphic transitions related to the composition of the analyzed guest mixture. The ability of tert-butylcalix[6]arene to remember selectively some guests bound from headspace both of pure liquids and their binary mixtures is used. The image of guest mixture remains written in metastable polymorphs of host after partial or complete guest elimination from clathrates.

Unusually high selectivity of guest exchange in tert-butylthiacalix[4]arene clathrate producing more thermostable inclusion and memory of guest.

New properties, earlier unknown for calixarenes, were found for tert-butylthiacalix[4]arene (1) clathrate with 1,2-dichloroethane (DCE). Guest exchange in 1·1.90DCE for vapors of some organic compounds gives clathrates, which are more thermostable at 34-59 °C than those prepared by direct saturation of guest-free 1 with pure guests.

Interaction of L-leucyl-L-leucyl-L-leucine thin film with water and organic vapors: receptor properties and related morphology.

The ability of highly ordered tripeptide structures to keep or change their morphology in contact with organic vapors was studied. A thin film of tripeptide L-leucyl-L-leucyl-L-leucine (LLL) was prepared having microcrystals and nanocrystals on its surface, which are stable upon vacuum drying but become objects of selective morphology change after a contact with vapors of organic solvents. Fine separate LLL crystals and their agglomerates of submicron and larger dimensions were observed by atomic force microscopy and scanning electron microscopy.

Specific vapor sorption properties of phosphorus-containing dendrimers.

Specific combination of guest sorption properties was observed for phosphorus-containing dendrimers, which distinguish them from ordinary polymers and clathrate-forming hosts. The sorption capacity for 30 volatile guests, binding reversibility, guest desorption kinetics and guest exchange, glass transition behavior and ability to be plasticized with guest were studied for phosphorus dendrimers of different generations (G(1)-G(4) and G(9)) using quartz crystal microbalance sensor, FTIR microspectroscopy, atomic force microscopy, simultaneous thermogravimetry and differential scanning calorimetry combined with mass-spectrometry of evolved vapors. The dendrimers were found to have a different selectivity for different homological series of guests, high glass transition points without plasticization with guest even at high temperatures and saturation levels, moderate guest-binding irreversibility and ability both for effective guest exchange and independent guest sorption.

Molecular recognition of organic vapors by adamantylcalix[4]arene in QCM sensor using partial binding reversibility.

The parameters of stability, guest binding reversibility, and Gibbs energy of guest inclusion were determined for clathrates of adamantylcalix[4]arene (1). These data provide a new insight into the structure-property relationships in vapor sensor applications of clathrate-forming hosts. A thin layer of 1, used in the quartz microbalance (QCM) sensor, demonstrates a selectivity for organic vapors, which depends on the regeneration technique after the guest binding.

Metastable tert-butylcalix[6]arene with unusually large tunable free volume for non-threshold enclathration of volatiles.

A metastable material with tunable free volume of molecular size, vapor sorption properties of a porous sorbent and variable thermal stability was prepared from tert-butylcalix[6]arene.

Nonregular structure-property relationships for inclusion parameters of tert-butylcalix[5]arene.

The effect of macrocycle size on the structure-property relationships was studied for inclusion compounds of tert-butylcalix[n]arenes (n=4,5) with volatile organic guests having various molecular size and group composition. Vapor-sorption isotherms, guest-inclusion stoichiometry and Gibbs energy, thermostability parameters and decomposition enthalpies were determined for host-guest compounds (clathrates) obtained using saturation of solid calixarene powder with guest vapor. The increase of the host macrocycle in the studied calixarene pair changes the observed structure-property relationship from the guest-binding selectivity mostly seen in inclusion Gibbs energy to the high sensitivity for guest structure in inclusion stoichiometry.