A general strategy for the synthesis of 2N,4N'-disubstituted glycoluril enantiomers on a multigram scale using orthogonal protection is reported. The use of these glycolurils is demonstrated in the synthesis of enantiomerically pure bambus[6]uril macrocycles. Moreover, the deprotection of (S)-1-phenylethyl substituents on the macrocycle was achieved, opening access to various chiral bambus[6]urils via post-macrocyclization modification strategy.
Organolithium reagents are a vital tool in modern organic chemistry, enabling the synthesis of carbon-carbon bonds. However, due to their high reactivity, low temperatures, inert atmospheres and strictly dried solvents are usually necessary for their use. Here we report an encapsulating method for the stabilization of sensitive organolithium reagents-PhLi, n-BuLi and s-BuLi-in a low-cost hexatriacontane (C36H74) organogel. The use of this technology is showcased in nucleophilic addition reactions under ambient conditions, low-temperature bromine-lithium exchange, ortho-lithiation and C-H functionalization. The gel substantially enhances organolithium stability, allows simple storage, handling and delivery, and enables reproducible reagent portioning. The use of gels as easily divided delivery vehicles for hazardous organometallics has the potential to transform this area of synthetic chemistry, making these powerful reactions safer and more accessible to non-specialist researchers, and enabling the more widespread use of these common synthetic methods.
Bambusurils are macrocyclic molecules that are known for their high binding affinity and selectivity toward anions. Here, we present the preparation of two bambusurils bearing fluorinated substituents and one carboxylic function. These monofunctionalized bambusurils were conjugated with crown ether and cholesterol units. The resulting conjugates were successfully tested in liquid-liquid extraction of inorganic salts and chloride/bicarbonate transport across lipid bilayers.
Chlorides , Crown Ethers , Anions/chemistry , Chlorides/chemistry , Lipid Bilayers/chemistry
With the goal of imposing shape and structure on supramolecular gels, we combine a low-molecular-weight gelator (LMWG) with the polymer gelator (PG) calcium alginate in a hybrid hydrogel. By imposing thermal and temporal control of the orthogonal gelation methods, the system either forms an extended interpenetrating network or core-shell-structured gel beads-a rare example of a supramolecular gel formulated inside discrete gel spheres. The self-assembled LMWG retains its unique properties within the beads, such as remediating PdII and reducing it inâ situ to yield catalytically active Pd0 nanoparticles. A single PdNP-loaded gel bead can catalyse the Suzuki-Miyaura reaction, constituting a simple and easy-to-use reaction-dosing form. These uniquely shaped and structured LMWG-filled gel beads are a versatile platform technology with great potential in a range of applications.
The meta-bridged calixarenes possess a rigidified and highly distorted cavity, where the additional single-bond bridge imposes an extreme internal strain on the whole system. As a consequence, these compounds exhibit a reasonably amended reactivity, compared with common calix[4]arene derivatives, which is governed by the release of internal strain. This can be documented by the reaction of the bridged calix[4]arene with P2O5 or Nafion-H, leading (apart from polymers) to a macrocyclic product with a rearranged basic skeleton. The methylene bridge next to the fluorene moiety is intramolecularly shifted from position 2 to position 4 of the phenolic subunit to minimize the tension. As revealed by single-crystal X-ray analysis and by application of the residual dipolar coupling method, the rearrangement occurs without altering the original conformation.
1,3:2,4-Dibenzylidene-d-sorbitol (DBS), a simple, commercially relevant compound, was found to self-assemble as a result of intermolecular noncovalent interactions into supramolecular gels in deep eutectic solvents (DESs) based on choline chloride combined with alcohols/ureas. DBS formed gels at a loading of 5 % w/v. Rheology confirmed the gel-like nature of the materials, electron microscopy and X-ray diffraction indicated underpinning nanofibrillar DBS networks, and differential scanning calorimetry showed the DES nature of the liquid-like phase was retained. The ionic conductivities of the gels were similar to those of the unmodified DESs, thus proving the deep eutectic nature of the ionic liquid-like phase. Gelation was tolerant of ionic additives Li+ , Mg2+ , and Ca2+ ; the resulting gels had similar conductivities to electrolyte dissolved in the native DES. The low-molecular-weight gelator DBS is thus a low-cost additive that forms gels in DESs from readily available constituents, with conductivity levels suitable for practical applications.
[This corrects the article DOI: 10.1039/C8SC04561E.].
A hybrid hydrogel based on 1,3:2,4-dibenzylidene sorbitol (DBS) modified with acyl hydrazides combined with agarose was used for in situ reduction and binding of palladium from aqueous mixtures without the need for an external reducing agent. Palladium uptake was monitored and the formation of Pd nanoparticles (PdNPs) trapped within the gel and located close to the nanofibres was confirmed. This gel effectively scavenges palladium from solution to concentrations < 0.04 ppm - well below the recommended limits for pharmaceutical products. The resulting hybrid hydrogel with embedded PdNPs was used as a catalyst for Suzuki-Miyaura cross-coupling reactions. The gel network stabilises PdNPs, preventing aggregation/leaching and giving excellent catalytic lifetimes. The gel acts as a simple reaction dosing form, being simply added to reactions performed in green solvents in air. Once reactions are complete, the gel can be simply removed, recycled and reused (>10 times). Reactions were purified by simple washing protocols, and leaching of Pd from the gels is limited (<1 ppm). The gels were also used in flow-through mode, giving efficient, rapid reactions, with easy work-up. These catalytic gels combine advantages of homogeneous and heterogeneous catalysts - they are solvent compatible with the reaction taking place in a solution-like environment, while the solid-like gel network enables catalyst recycling. In summary, these hydrogels scavenge 'waste' palladium and convert it into gel 'wealth' capable of efficient, environmentally-friendly Suzuki-Miyaura catalysis.
The mercuration of calix[4]arene immobilized in the cone conformation allowed the introduction of an amino group at the meta position of the basic skeleton. Acylation and subsequent intramolecular Bischler-Napieralski-type cyclization led to a novel type of bridged calixarene containing a seven-membered ring. These compounds with an enlarged and rigidified cavity represent a unique and inherently chiral system that may potentially be applicable for the design of chiral receptors. The absolute configuration of one enantiomer, obtained by resolution of the racemate using chiral HPLC, was assigned by single-crystal structure determination.
Direct mercuration of calix[4]arene immobilized in the partial cone conformation led to the meta-substituted isomer which was subsequently subjected to Pd-catalysed coupling (C-H activation) with the neighbouring aromatic subunit. Regioselective mercuration thus enabled access to a novel type of inherently chiral calixarenes with a highly distorted cavity potentially applicable to the design of new chiral receptors.
Rotacatenane is an interlocked compound composed of two mechanically interlocked macrocyclic components, i.e., a [2]catenane, and one axle component. In this paper we describe the selective synthesis of isomeric rotacatenanes. Two [2]rotaxanes with different phenanthroline moieties were synthesized by the oxidative coupling of an alkyne with a bulky blocking group, which proceeded in the cavity of the macrocyclic phenanthroline-Cu complex. The metal template method was used to install another cyclic component: the tetrahedral Cu(I) complex, which was composed of a [2]rotaxane and an acyclic phenanthroline derivative, was synthesized, and the cyclization of the phenanthroline derivative gave the rotacatenane. The sequential isomers of rotacatenanes were distinguished by (1)H and (13)C NMR spectroscopy.
Regioselective derivatization via an organomercury intermediate allowed for the introduction of carboxylic acid functionality into the meta position of the calix[4]arene skeleton. Intramolecular Friedel-Crafts cyclization led to a novel type of calixarene containing a ketone bridging moiety. Subsequent attack of the ketone by organometallic compounds occurred selectively from outside providing tertiary alcohols with the OH group oriented inside the cavity. These compounds can complex neutral molecules both in the solid state (X-ray) and in solution (NMR) using the cooperative effect of hydrogen bonding (OH) and CH-π interactions from within the cavity.
The meta-iodo derivative, fixed in the cone conformation, enables the gram-scale preparation of a meta-bridged calix[4]arene. This intermediate, possessing a fluorene moiety within the macrocyclic skeleton, can be regioselectively alkylated on the corresponding methylene bridge to form a unique substitution pattern in classical calixarene chemistry.
A direct mercuration reaction combined with a subsequent Pd-catalyzed arylation was used to introduce the aryl moiety into the meta position of the calix[4]arene skeleton. The application of organomercurial intermediates thus allows the straightforward formation of meta-aryl-substituted derivatives representing a unique substitution pattern in calixarene chemistry.
The regioselective mercuration of tetraalkylated calix[4]arenes with Hg(OCOCF3)2 leads to the formation of meta-substituted products which enabled Pd-catalysed intramolecular bridging within the calixarene skeleton. Bridged derivatives represent a completely novel substitution pattern in calixarene chemistry with extremely distorted cavities and possible applications in supramolecular chemistry.
Bloodstain pattern analysis (BPA) is a valid forensic method which belongs to the category of biological methods using trigonomic models. Despite its development through the years, the method has been re-formulated a standard one and globally used, recognized in standard sheets. This method permits exact analysis of the dynamic and characteristic properties of bloodstains after impact on surfaces such as floors, walls, and ceilings, various exterior and interior items, and clothes. It is also possible to determine the characteristics of blood from the outer part of the body. According to the presence of blood and its quantity, it is also possible to use this method for verification of reconstruction of criminal acts, while being tested for its validity with primary conditions of preserved and readable traces of blood. Even though this method is not considered as the major one or the only one information obtained in this way can be used for judicial. In our research, we tested the validity of this method in an experimental model using firearms. We compared measurements of the lengths of trajectory of impact and the height of the blood sprayed upwards from a distance of 1, 3, 5 and 10 meters. The experiment was based on two main presumptions. The first was the knowledge of the value of the distance and the angle of impact of the bloodstain, the second, the ability of the blood to reach a certain height and the angle of its impact. In accordance with trigonometric formulas, both the impact of the selected distance of drops of blood, and the height of the selected bloodstain could be determined without any verification of the flight trajectory and the distance of bloodstains. The results indicate that the method for these requirements differs from the real values, while increasing the measurements with the indicated spot of the shot. Aside from the unique values which were calculated, other results of the impact of the distance of drops of bloodstain were considered of lower value, and the values concerning the height of the bloods stains after the shot higher than real values. In spite of the lack of total accuracy, we recommend using this method widely and more often for investigation and verification of individual acts in criminal and forensic practice.
Blood Stains , Forensic Ballistics , Animals , Cattle , Forensic Medicine/methods , In Vitro Techniques , Mathematics
Electrophilic aromatic substitution in the calix[n]arene series is a well-established procedure leading exclusively to para-substituted derivatives. An unprecedented regioselectivity of the mercuration reaction leading to the meta-substituted calix[4]arenes is described. These compounds represent a new type of substitution pattern in classical calixarene chemistry and open the door for the straightforward synthesis of inherently chiral receptors based on calixarenes.
Calixarenes/chemistry , Mercury Compounds/chemistry , Magnetic Resonance Spectroscopy , Molecular Structure , Stereoisomerism
BACKGROUND: Selenium (Se) is important for the postnatal development of the calf. In the first weeks of life, milk is the only source of Se for the calf and insufficient level of Se in the milk may lead to Se deficiency. Maternal Se supplementation is used to prevent this.We investigated the effect of dietary Se-enriched yeast (SY) or sodium selenite (SS) supplements on selected blood parameters and on Se concentrations in the blood, colostrum, and milk of Se-deficient Charolais cows. METHODS: Cows in late pregnancy received a mineral premix with Se (SS or SY, 50 mg Se per kg premix) or without Se (control--C). Supplementation was initiated 6 weeks before expected calving. Blood and colostrum samples were taken from the cows that had just calved (Colostral period). Additional samples were taken around 2 weeks (milk) and 5 weeks (milk and blood) after calving corresponding to Se supplementation for 6 and 12 weeks, respectively (Lactation period) for Se, biochemical and haematological analyses. RESULTS: Colostral period. Se concentrations in whole blood and colostrum on day 1 post partum and in colostrum on day 3 post partum were 93.0, 72.9, and 47.5 microg/L in the SY group; 68.0, 56.0 and 18.8 microg/L in the SS group; and 35.1, 27.3 and 10.5 microg/L in the C group, respectively. Differences among all the groups were significant (P < 0.01) at each sampling, just as the colostrum Se content decreases were from day 1 to day 3 in each group. The relatively smallest decrease in colostrum Se concentration was found in the SY group (P < 0.01).Lactation period. The mean Se concentrations in milk in weeks 6 and 12 of supplementation were 20.4 and 19.6 microg/L in the SY group, 8.3 and 11.9 microgg/L in the SS group, and 6.9 and 6.6 microgg/L in the C group, respectively. The values only differed significantly in the SS group (P < 0.05). The Se concentrations in the blood were similar to those of cows examined on the day of calving. The levels of glutathione peroxidase (GSH-Px) activity were 364.70, 283.82 and 187.46 microgkat/L in the SY, SS, and C groups, respectively. This was the only significantly variable biochemical and haematological parameter. CONCLUSION: Se-enriched yeast was much more effective than sodium selenite in increasing the concentration of Se in the blood, colostrum and milk, as well as the GSH-Px activity.
Cattle/metabolism , Colostrum/metabolism , Milk/metabolism , Selenium/administration & dosage , Animals , Cattle/blood , Dietary Supplements , Female , Lactation , Pregnancy , Selenium/metabolism
