Enzyme-like Acyl Transfer Catalysis in a Bifunctional Organic Cage.

Amide-based organic cage cavities are, in principle, ideal enzyme active site mimics. Yet, cage-promoted organocatalysis has remained elusive, in large part due to synthetic accessibility of robust and functional scaffolds. Herein, we report the acyl transfer catalysis properties of robust, hexaamide cages in organic solvent.

Programmable synthesis of organic cages with reduced symmetry.

Integrating symmetry-reducing methods into self-assembly methodology is desirable to efficiently realise the full potential of molecular cages as hosts and catalysts. Although techniques have been explored for metal organic (coordination) cages, rational strategies to develop low symmetry organic cages remain limited. In this article, we describe rules to program the shape and symmetry of organic cage cavities by designing edge pieces that bias the orientation of the amide linkages.

Access to Amide-Linked Organic Cages by in situ Trapping of Metastable Imine Assemblies: Solution Phase Bisamine Recognition.

Molecular cages are sought after as receptors and catalysts. However, typical dynamic covalent chemistry approaches restrict the shape-persistence, solubility and stability of self-assembled organic cages. As a result, organic cages occupy a narrow chemical and functional space, and solution-phase applications and studies remain rare.

TrackInk: An IoT-Enabled Real-Time Object Tracking System in Space.

Nowadays, there is tremendous growth in the Internet of Things (IoT) applications in our everyday lives. The proliferation of smart devices, sensors technology, and the Internet makes it possible to communicate between the digital and physical world seamlessly for distributed data collection, communication, and processing of several applications dynamically. However, it is a challenging task to monitor and track objects in real-time due to the distinct characteristics of the IoT system, e.

A practical catalytic reductive amination of carboxylic acids.

We report reductive alkylation reactions of amines using carboxylic acids as nominal electrophiles. The two-step reaction exploits the dual reactivity of phenylsilane and involves a silane-mediated amidation followed by a Zn(OAc)-catalyzed amide reduction. The reaction is applicable to a wide range of amines and carboxylic acids and has been demonstrated on a large scale (305 mmol of amine).

Redox-neutral organocatalytic Mitsunobu reactions.

Nucleophilic substitution reactions of alcohols are among the most fundamental and strategically important transformations in organic chemistry. For over half a century, these reactions have been achieved by using stoichiometric, and often hazardous, reagents to activate the otherwise unreactive alcohols. Here, we demonstrate that a specially designed phosphine oxide promotes nucleophilic substitution reactions of primary and secondary alcohols in a redox-neutral catalysis manifold that produces water as the sole by-product.

A practical and catalyst-free trifluoroethylation reaction of amines using trifluoroacetic acid.

Amines are a fundamentally important class of biologically active compounds and the ability to manipulate their physicochemical properties through the introduction of fluorine is of paramount importance in medicinal chemistry. Current synthesis methods for the construction of fluorinated amines rely on air and moisture sensitive reagents that require special handling or harsh reductants that limit functionality. Here we report practical, catalyst-free, reductive trifluoroethylation reactions of free amines exhibiting remarkable functional group tolerance.

A more critical role for silicon in the catalytic Staudinger amidation: silanes as non-innocent reductants.

A revised pathway for the catalytic Staudinger amidation reaction is presented that involves the intervention of in situ-generated silyl esters as the species responsible for amidation.

Catalytic reductive N-alkylation of amines using carboxylic acids.

We report a catalytic reductive alkylation reaction of primary or secondary amines with carboxylic acids. The two-phase process involves silane mediated direct amidation followed by catalytic reduction.

PragmatiX: An Interactive Tool for Visualizing the Creation Process Behind Collaboratively Engineered Ontologies.

With the emergence of tools for collaborative ontology engineering, more and more data about the creation process behind collaborative construction of ontologies is becoming available. Today, collaborative ontology engineering tools such as Collaborative Protégé offer rich and structured logs of changes, thereby opening up new challenges and opportunities to study and analyze the creation of collaboratively constructed ontologies. While there exists a plethora of visualization tools for ontologies, they have primarily been built to visualize aspects of the final product (the ontology) and not the collaborative processes behind construction (e.

Structural assignment of a bis-cyclopentenyl-β-cyanohydrin formed via alkene metathesis from either a triene or a tetraene precursor.

The identity of the major product of Ru-catalysed alkene metathesis of two polyene substrates has been determined using density functional theory (DFT) NMR prediction, a (1)H-(1)H Total Correlated Spectroscopy (TOCSY) NMR experiment and ultimately by single-crystal X-ray crystallography. The substrates were designed as those that would potentially allow expedient access to the trans-decalin skeleton of the natural product (-)-euonyminol, but the product was found to be a bis-cyclopentenyl-β-cyanohydrin [1-(1-hydroxycyclopent-3-en-1-yl)cyclopent-3-ene-1-carbonitrile, C11H13NO] rather than the trans-2,3,6,7-dehydrodecalin-β-cyanohydrin.

Improving the accuracy of computed 13C NMR shift predictions by specific environment error correction: fragment referencing.

The accuracy of both Gauge-including atomic orbital (GIAO) and continuous set of gauge transformations (CSGT) (13)C NMR spectra prediction by Density Functional Theory (DFT) at the B3LYP/6-31G** level is shown to be usefully enhanced by employing a 'fragment referencing' method for predicting chemical shifts without recourse to empirical scaling. Fragment referencing refers to a process of reducing the error in calculating a particular NMR shift by consulting a similar molecule for which the error in the calculation is easily deduced. The absolute accuracy of the chemical shifts predicted when employing fragment referencing relative to conventional techniques (e.

Randomized control of extracorporeal shock wave therapy versus placebo for chronic decubitus ulceration.

Objective: To assess whether extracorporeal shock wave therapy increases the rate of healing in chronic decubitus ulceration.

Design: Double-blind randomized cross-over study.

Setting: A large, long-stay hospital specializing in the management of people with complex neurological disabilities.

Rehabilitation practice following profound brain damage.

The rehabilitation of the person with profound brain damage is a complex process requiring the skills of a true interdisciplinary team. The process is as much about the ability to: assess and diagnose; provide the optimal environment for recovery; prevent and treat secondary complications; support the family; and modify the environment as it is about a formal rehabilitation programme. Ideally these should be seamless but each contains many challenges, including the experience and skills of the observer, the ability to communicate with members of the family, and the ability to work within an interdisciplinary team.

Behavioral evaluation of consciousness in severe brain damage.

This paper reviews the current state of bedside behavioral assessment in brain-damaged patients with impaired consciousness (coma, vegetative state, minimally conscious state). As misdiagnosis in this field is unfortunately very frequent, we first discuss a number of fundamental principles of clinical evaluation that should guide the assessment of consciousness in brain-damaged patients in order to avoid confusion between vegetative state and minimally conscious state. The role of standardized behavioral assessment tools is particularly stressed.

Medical decision making in the vegetative state: withdrawal of nutrition and hydration.

Withdrawal of nutrition and hydration, is a difficult and sensitive issue for all those working with people in the vegetative state. There are arguments against the decision to withdraw any treatment that might result in the patient deteriorating or dying. These arguments include the view that all life is worth having, that we can never be certain that the patient is not aware, and concerns that there may be new scientific developments in the future from which the patient would benefit.

Clinical approaches to the withdrawal of nutrition and hydration.

The request for withdrawal of nutrition and hydration from the vegetative patient is rare, but when it occurs it causes considerable anxiety for the clinical team. This anxiety is exacerbated by the need to seek a declaration from court that withdrawal of treatment would be legal. This paper discusses the process from the time of the request to the withdrawal of the tube feeding, and the actions the clinical team needs to take.