The post-synthesis modification (PSM) of MOFs for catalysis.

While there are myriad ways to construct metal-organic framework (MOF) based catalysts, the introduction of catalytic functionality via covalent post-synthesis functionalization (PSM) offers multiple advantages: (i) a wide range of different catalyst types are generated from a handful of well-known parent MOFs, (ii) MOF catalyst properties can be systematically tuned while changing few variables, and (iii) catalytically active functional groups that would otherwise interfere with MOF assembly can be introduced facilely. This last advantage is particularly crucial for our quest to generate MOF active sites that are decorated with multiple functional groups capable of cooperative activity, analogous to enzyme active sites.

Hydrogen-Bonding Linkers Yield a Large-Pore, Non-Catenated, Metal-Organic Framework with pcu Topology.

Pillared paddle-wheel-based metal-organic framework (MOF) materials are an attractive target as they offer a reliable method for constructing well-defined, multifunctional materials. A drawback of these materials, which has limited their application, is their tendency to form catenated frameworks with little accessible volume. To eliminate this disadvantage, it is necessary to investigate strategies for constructing non-catenated pillared paddle-wheel MOFs. Hydrogen-bonding substituents on linkers have been postulated to prevent catenation in certain frameworks and, in this work, we present a new MOF to further bolster this theory. Using 2,2'-diamino-[1,1'-biphenyl]-4,4'-dicarboxylic acid, BPDC-(NH2)2, linkers and dipyridyl glycol, DPG, pillars, we assembled a MOF with pcu topology. The new material is non-catenated, exhibiting large accessible pores and low density. To the best of our knowledge, this material constitutes the pcu framework with the largest pore volume and lowest density. We attribute the lack of catenation to the presence of H-bonding substituents on both linkers.

Uniform, Binary Functionalization of a Metal-Organic Framework Material.

General routes to confined spaces of well-defined chemical composition and complex three-dimensional structure have long been sought by materials chemists. Here, we introduce metal-organic framework (MOF) materials as an ideal scaffold upon which such organized complexity can be built. Employing an orthogonal coordination strategy, we constructed a large-pore MOF material with two different modifiable linkers in well-defined positions relative to each other. The independent and quantitative covalent grafting of two distinct chemical groups onto these differently reactive linkers yielded a uniformly bifunctionalized MOF material. Not only does this methodology offer an efficient route via which the properties of well-defined microporous materials can be fine-tuned, but it also creates a solid-state platform for synthetically accessing constructs that better emulate the well-ordered intricacy of biological structures.

Quick Click: The DNA-Templated Ligation of 3'-O-Propargyl- and 5'-Azide-Modified Strands Is as Rapid as and More Selective than Ligase.

The copper(I)-mediated azide-alkyne cycloaddition (CuAAC) of 3'-propargyl ether and 5'-azide oligonucleotides is a particularly promising ligation system because it results in triazole linkages that effectively mimic the phosphate-sugar backbone of DNA, leading to unprecedented tolerance of the ligated strands by polymerases. However, for a chemical ligation strategy to be a viable alternative to enzymatic systems, it must be equally as rapid, as discriminating, and as easy to use. We found that the DNA-templated reaction with these modifications was rapid under aerobic conditions, with nearly quantitative conversion in 5 min, resulting in a kobs value of 1.1 min-1 , comparable with that measured in an enzymatic ligation system by using the highest commercially available concentration of T4 DNA ligase. Moreover, the CuAAC reaction also exhibited greater selectivity in discriminating C:A or C:T mismatches from the C:G match than that of T4 DNA ligase at 29 °C; a temperature slightly below the perfect nicked duplex dissociation temperature, but above that of the mismatched duplexes. These results suggest that the CuAAC reaction of 3'-propargyl ether and 5'-azide-terminated oligonucleotides represents a complementary alternative to T4 DNA ligase, with similar reaction rates, ease of setup and even enhanced selectivity for certain mismatches.

Correction: The presence of a 5'-abasic lesion enhances discrimination of single nucleotide polymorphisms while inducing an isothermal ligase chain reaction.

Correction for 'The presence of a 5'-abasic lesion enhances discrimination of single nucleotide polymorphisms while inducing an isothermal ligase chain reaction' by Abu Kausar et al., Analyst, 2016, 141, 4272-4277.

The presence of a 5'-abasic lesion enhances discrimination of single nucleotide polymorphisms while inducing an isothermal ligase chain reaction.

Lesion-induced DNA amplification (LIDA) has been employed in the detection of single nucleotide polymorphisms (SNPs). Due to the presence of the proximal abasic lesion, T4 DNA ligase exhibits greater intolerance to basepair mismatches when compared with mismatch ligation in the absence of the abasic lesion. Moreover the presence of the abasic group also results in an isothermal ligase chain reaction enabling SNP detection with great discrimination and sensitivity. Specifically, at forty minutes, the ratio of amplified product from the matched and mismatched initiated reactions are 7-12 depending on the mismatch. The ease of implementation of our method is demonstrated by real-time analysis of DNA amplification using a fluorescent plate reader.

Tuning Toehold Length and Temperature to Achieve Rapid, Colorimetric Detection of DNA from the Disassembly of DNA-Gold Nanoparticle Aggregates.

Gold nanoparticles have been widely utilized to achieve colorimetric detection for various diagnostic applications. One of the most frequently used methods for DNA detection involves the aggregation of DNA-modified gold nanoparticles driven by target DNA hybridization. This process, however, is intrinsically slow, limiting its use in rapid diagnostics. Here we take advantage of the reverse process: the disassembly of preformed aggregates triggered by the addition of target DNA via a strand displacement mechanism. A systematic study of the dependence of the disassembly rate on temperature, with and without toeholds, has delivered a system that produces an extremely rapid colorimetric response. Furthermore, using an optimal toehold length of 5 nucleotides, target triggered disassembly is rapid over a wide range of ambient temperatures. Using this overhang system, simple visualization of low picomole amounts of target DNA is possible within 10 min at room temperature.

Self-assembly of a confined rhodium catalyst for asymmetric hydroformylation of unfunctionalized internal alkenes.

A chiral supramolecular ligand has been assembled and applied to the rhodium-catalyzed asymmetric hydroformylation of unfunctionalized internal alkenes. Spatial confinement of the metal center within a chiral pocket results in reversed regioselectivity and remarkable enantioselectivities.

"Cofactor"-controlled enantioselective catalysis.

We report an achiral bisphosphine rhodium complex equipped with a binding site for the recognition of chiral anion guests. Upon binding small chiral guests--cofactors--the rhodium complex becomes chiral and can thus be used for asymmetric catalysis. Screening of a library of cofactors revealed that the best cofactors lead to hydrogenation catalysts that form the products with high enantioselectivity (ee's up to 99%). Interestingly, a competition experiment shows that even in a mixture of 12 cofactors high ee is obtained, indicating that the complex based on the best cofactor dominates the catalysis.

Selective bifunctional modification of a non-catenated metal-organic framework material via "click" chemistry.

A noncatenated, Zn-based metal-organic framework (MOF) material bearing silyl-protected acetylenes was constructed and postsynthetically modified using "click" chemistry. Using a solvent-based, selective deprotection strategy, two different organic azides were "clicked" onto the MOF crystals, resulting in a porous material whose internal and external surfaces are differently functionalized.

A Zn-based, pillared paddlewheel MOF containing free carboxylic acids via covalent post-synthesis elaboration.

A Zn-based, mixed-ligand (pillared paddlewheel), metal-organic framework (MOF) has been covalently and quantitatively decorated with free carboxylic acids to demonstrate the utility of covalent post-synthesis modification in the construction of otherwise inaccessible carboxy-functionalized MOFs.

Substrate encapsulation: an efficient strategy for the RCM synthesis of unsaturated epsilon-lactones.

A facile substrate-encapsulated RCM-based synthesis of 7-membered lactones is reported. Coordination of the alpha,omega-dienyl ester precursor to the bulky Lewis acid (LA) aluminum tris(2,6-diphenylphenoxide) (ATPH) provides a protective extended steric pocket to the olefin moieties, thereby favoring intramolecular RCM over intermolecular ADMET oligomerization. The LA-encapsulated esters undergo ring-closure in the presence of Ru-based olefin metathesis catalysts to give previously difficult-to-access 7-membered beta,gamma- and gamma,delta-unsaturated lactones in good yields.

Covalent surface modification of a metal-organic framework: selective surface engineering via Cu(I)-catalyzed Huisgen cycloaddition.

A Zn-cornered, mixed-ligand, metal-organic framework (MOF) bearing TMS-protected acetylenes has been constructed and its surface decorated with organic molecules via'click chemistry', in a demonstration of selective post-synthesis functionalization.

Ligand-elaboration as a strategy for engendering structural diversity in porous metal-organic framework compounds.

A series of 4,4'-ethynylenedibenzoic acids were synthesized and used in the construction of Zn-based, mixed-ligand metal-organic frameworks; through variation of functionality in the 3- and 3'-positions of these linkers, a collection of MOFs with differing connectivities and varying levels of interpenetration was obtained.

One-pot synthesis of symmetrical and unsymmetrical bisarylethynes by a modification of the sonogashira coupling reaction.

A modification of the Sonogoshira coupling reaction employing an amidine base and a substoichiometric amount of water generates symmetrical and unsymmetrical bisarylethynylenes in one pot through in situ deprotection of trimethylsilylethynylene-added intermediates.