Biomolecular condensates can function as inherent catalysts.

We report the discovery that chemical reactions such as ATP hydrolysis can be catalyzed by condensates formed by intrinsically disordered proteins (IDPs), which themselves lack any intrinsic ability to function as enzymes. This inherent catalytic feature of condensates derives from the electrochemical environments and the electric fields at interfaces that are direct consequences of phase separation. The condensates we studied were capable of catalyzing diverse hydrolysis reactions, including hydrolysis and radical-dependent breakdown of ATP whereby ATP fully decomposes to adenine and multiple carbohydrates. This distinguishes condensates from naturally occurring ATPases, which can only catalyze the dephosphorylation of ATP. Interphase and interfacial properties of condensates can be tuned via sequence design, thus enabling control over catalysis through sequence-dependent electrochemical features of condensates. Incorporation of hydrolase-like synthetic condensates into live cells enables activation of transcriptional circuits that depend on products of hydrolysis reactions. Inherent catalytic functions of condensates, which are emergent consequences of phase separation, are likely to affect metabolic regulation in cells.

A General Strategy for the Asymmetric Preparation of α-Stereogenic Allyl Silanes, Germanes, and Boronate Esters via Dual Copper Hydride- and Palladium-Catalysis.

α-Stereogenic allyl metalloids are versatile synthetic intermediates which can undergo various stereocontrolled transformations. Most existing methods to prepare α-stereogenic allyl metalloids involve multi-step sequences that curtail the number of compatible substrates and are limited to the synthesis of boronates. Here, we report a general method for the enantioselective preparation of α-stereogenic allyl metalloids utilizing dual CuH- and Pd-catalysis. This approach leverages a stereoretentive Cu-to-Pd transmetalation of an in situ generated alkyl copper species to allow access to enantioenriched allyl silanes, germanes, and boronate esters with broad functional group compatibility.

A Dual CuH- and Pd-Catalyzed Stereoselective Synthesis of Highly Substituted 1,3-Dienes.

Conjugated dienes are versatile building blocks and prevalent substructures in synthetic chemistry. Herein, we report a method for the stereoselective hydroalkenylation of alkynes, utilizing readily available enol triflates. We leveraged an in situ-generated and geometrically pure vinyl-Cu(I) species to form the Z,Z- or Z,E-1,3-dienes in excellent stereoselectivity and yield. This approach allowed for the synthesis of highly substituted Z-dienes, including pentasubstituted 1,3-dienes, which are difficult to prepare by existing approaches.

Quantum Yields and N2O Formation from Photolysis of Solid Films of Neonicotinoids.

Neonicotinoids (NN), first introduced in 1991, are found on environmental surfaces where they undergo photolytic degradation. Photolysis studies of thin films of NN were performed using two approaches: (1) transmission FTIR, in which solid films of NN and the gas-phase products were analyzed simultaneously, and (2) attenuated-total-reflectance FTIR combined with transmission FTIR, in which solid films of NN and the gas-phase products were probed in the same experiment but not at the same time. Photolysis quantum yields using broadband irradiation centered at 313 nm were (2.2 ± 0.9) × 10-3 for clothianidin (CLD), (3.9 ± 0.3) × 10-3 for thiamethoxam (TMX), and (3.3 ± 0.5) × 10-3 for dinotefuran (DNF), with all errors being ±1 s. At 254 nm, which was used to gain insight into the wavelength dependence, quantum yields were in the range of (0.8-20) × 10-3 for all NNs, including acetamiprid (ACM) and thiacloprid (TCD). Nitrous oxide (N2O), a potent greenhouse gas, was the only gas-phase product detected for the photolysis of nitroguanidines, with yields of ΔN2O/ΔNN > 0.5 in air at both 313 and 254 nm. The atmospheric lifetimes with respect to photolysis for CLD, TMX, and DNF, which absorb light in the actinic region, are estimated to be 15, 10, and 11 h, respectively, at a solar zenith angle of 35° and 12, 8, and 10 h at a solar zenith angle of 15°.