A Resin‐Linker‐Vector Approach to Radiopharmaceuticals Containing 18F: Application in the Synthesis of O‐(2‐[18F]‐Fluoroethyl)‐L‐tyrosine

A Resin‐linker‐vector (RLV) strategy is described for the radiosynthesis of tracer molecules containing the radionuclide ¹⁸F, which releases the labelled vector into solution upon nucleophilic substitution of a polystyrene‐bound arylsulfonate linker with [¹⁸F]‐fluoride ion. Three model linker‐vector molecules 7 a – c containing different alkyl spacer groups were assembled in solution from (4‐chlorosulfonylphenyl)alkanoate esters, exploiting a lipase‐catalysed chemoselective carboxylic ester hydrolysis in the presence of the sulfonate ester as a key step. The linker‐vector systems were attached to aminomethyl polystyrene resin through amide bond formation to give RLVs 8 a – c with acetate, butyrate and hexanoate spacers, which were characterised by using magic‐angle spinning (MAS) NMR spectroscopy. On fluoridolysis, the RLVs 8 a , b containing the longer spacers were shown to be more effective in the release of the fluorinated model vector (4‐fluorobutyl)phenylcarbamic acid tert‐butyl ester ( 9 ) in NMR kinetic studies and gave superior radiochemical yields (RCY≈60 %) of the ¹⁸F‐labelled vector. The approach was applied to the synthesis of the radiopharmaceutical O‐(2‐[¹⁸F]‐fluoroethyl)‐L ‐tyrosine ([¹⁸F]‐FET), delivering protected [¹⁸F]‐FET in >90 % RCY. Acid deprotection gave [¹⁸F]‐FET in an overall RCY of 41 % from the RLV.     

Three‐Dimensional Architectures Incorporating Stereoregular Donor–Acceptor Stacks

We report the synthesis of two [2]catenane‐containing struts that are composed of a tetracationic cyclophane (TC⁴⁺) encircling a 1,5‐dioxynaphthalene (DNP)‐based crown ether, which bears two terphenylene arms. The TC⁴⁺ rings comprise either 1) two bipyridinium (BIPY²⁺) units or 2) a BIPY²⁺ and a diazapyrenium (DAP²⁺) unit. These degenerate and nondegenerate catenanes were reacted in the presence of Cu(NO₃)₂?2.5 H₂O to yield Cu‐paddlewheel‐based MOF‐1050 and MOF‐1051. The solid‐state structures of these MOFs reveal that the metal clusters serve to join the heptaphenylene struts into grid‐like 2D networks. These 2D sheets are then held together by infinite donor–acceptor stacks involving the [2]catenanes to produce interpenetrated 3D architectures. As a consequence of the planar chirality associated with both the DNP and hydroquinone (HQ) units present in the crown ether, each catenane can exist as four stereoisomers. In the case of the nondegenerate (bistable) catenane, the situation is further complicated by the presence of translational isomers. Upon crystallization, however, only two of the four possible stereoisomers—namely, the enantiomeric RR and SS forms—are observed in the crystals. An additional element of co‐conformational selectivity is present in MOF‐1051 as a consequence of the substitution of one of the BIPY²⁺ units by a DAP²⁺ unit: only the translational isomer in which the DAP²⁺ unit is encircled by the crown ether is observed. The overall topologies of MOF‐1050 and MOF‐1051, and the selective formation of stereoisomers and translational isomers during the kinetically driven crystallization, provide evidence that weak noncovalent bonding interactions play a significant role in the assembly of these extended (super)structures.     

Synthesis of sugar oxime ether surfactants

A straightforward synthesis of a novel class of sugar surfactants is described. The key step is the chemoselective condensation of a hydrophobic alkoxyamine with the resident aldehyde/ketone moiety on a hydrophilic sugar. Neither protection/deprotection of the sugars nor extensive product purification is required. The method allows for the facile adjustment of hydrophobic and hydrophilic domains of the sugar oxime ether surfactant and uses inexpensive, readily accessible, and renewable materials.     

Production of ball-lightning-like luminous balls by electrical discharges in silicon

We performed electric arc discharges in pure Si to generate luminous balls with lifetime in the order of seconds and several properties usually reported for natural ball lightning. This simple experiment does not rely on energy sources and excitation mechanisms that are improbable in the natural phenomenon and clearly demonstrates the role of vaporization and oxidation of Si, as proposed by the Abrahamson-Dinniss theory for ball-lightning formation.     

Nucleophilic Reactivity of a Copper(II)–Superoxide Complex

Metal‐bound superoxide intermediates are often implicated as electrophilic oxidants in dioxygen‐activating metalloenzymes. In the nonheme iron α‐ketoglutarate dependent oxygenases and pterin‐dependent hydroxylases, however, Fe^III–superoxide intermediates are postulated to react by nucleophilic attack on electrophilic carbon atoms. By reacting a Cu^II–superoxide complex ( 1 ) with acyl chloride substrates, we have found that a metal–superoxide complex can be a very reactive nucleophile. Furthermore, 1 was found to be an efficient nucleophilic deformylating reagent, capable of Baeyer–Villiger oxidation of a number of aldehyde substrates. The observed nucleophilic chemistry represents a new domain for metal–superoxide reactivity. Our observations provide support for the postulated role of metal–superoxide intermediates in nonheme iron α‐ketoglutarate dependent and pterin‐dependent enzymes.     

Water‐Stable Zirconium‐Based Metal–Organic Framework Material with High‐Surface Area and Gas‐Storage Capacities

We designed, synthesized, and characterized a new Zr‐based metal–organic framework material, NU‐1100 , with a pore volume of 1.53 ccg^?1 and Brunauer–Emmett–Teller (BET) surface area of 4020 m²g^?1; to our knowledge, currently the highest published for Zr‐based MOFs. CH₄/CO₂/H₂ adsorption isotherms were obtained over a broad range of pressures and temperatures and are in excellent agreement with the computational predictions. The total hydrogen adsorption at 65 bar and 77 K is 0.092 g g^?1, which corresponds to 43 g L^?1. The volumetric and gravimetric methane‐storage capacities at 65 bar and 298 K are approximately 180 v_STP/v and 0.27 g g^?1, respectively.     

Simple but Precise Engineering of Functional Nanocapsules through Nanoprecipitation

A general, rapid, and undemanding method to generate at will functional oil‐filled nanocapsules through nanoprecipitation is reported. On the basis of polymer and hexadecane/water/acetone phase diagrams, the composition can be set so that polymer chains preferentially stick at the interface of the oil droplets to create nanocapsules. The nanocapsules can be decorated with biorelevant molecules (biotin, fluorescent tags, metal nanoparticles) within the shell and loaded with hydrophobic molecules in a simple one‐pot procedure.     

Strong and Superhydrophobic Wood with Aligned Cellulose Nanofibers as a Waterproof Structural Material†

Lightweight structural materials are important for the energy efficiency of applications, particularly those in the building sector. Here, inspired by nature, we developed a strong, superhydrophobic, yet lightweight material by simple in situ growth of nano‐SiO₂ and subsequent densification of the wood substrate. In situ generation of SiO₂ nanoparticles both inside the wood channels and on the wood surfaces gives the material superhydrophobicity, with static and dynamic contact angles of 159.4^o and 3^o, respectively. Densification of the wood to remove most of the spaces among the lumen and cell walls results in a laminated, dense structure, with aligned cellulose nanofibers, which in turn contributes to a high mechanical strength up to 384.2 MPa (7‐times higher than natural wood). Such treatment enables the strong and superhydrophobic wood (SH‐Wood) to be stable and have excellent water, acid, and alkaline resistance. The high mechanical strength of SH‐Wood combined with its excellent structural stability in harsh environments, as well its low density, positions the strong and superhydrophobic wood as a promising candidate for strong, lightweight, and durable structural materials that could potentially replace steel.