Proton Conducting Metal-Organic Frameworks (MOFs) via Post Synthetic Transmetallation and Water Induced Structural Transformations.

Post Synthetic Modification (PSM) of Metal-Organic Frameworks (MOFs) is a crucial strategy for developing new MOFs with enhanced functional properties compared to their parent one. PSM can be accomplished through various methods:1) modification of organic linkers; 2) exchange of metal ions or nodes; and 3) inclusion or exchange of solvent/guest molecules. Herein, PSM of bimetallic and monometallic MOFs containing biphenyl dinitro-tetra-carboxylates (NCA) are demonstrated. The tetra carboxylate NCA, produces monometallic Cd-MOF-1 and Cu-MOF-1 and bimetallic CoZn-MOF in solvothermal reactions with the corresponding metal salts. The CoZn-MOF undergoes post-synthetic transmetallation with Cd(NO3)2 and Cu(NO3)2 in aqueous solution to yield Cd-MOF-2 and Cu-MOF-2, respectively. Additionally, green crystals of Cu-MOF-1 found to undergo a single-crystal-to-single-crystal (SCSC) transformation to blue crystals of Cu-MOF-3 upon dipped into water at room temperature. These MOFs demonstrate notable proton conductivities ranging from 10-3 to 10-4 S cm-1 under variable temperatures and humidity levels. Among them, Cu-MOF-3 achieves the highest proton conductivity of 1.36 × 10-3 S cm-1 at 90 °C and 98% relative humidity, attributed to its continuous and extensive hydrogen bonding network, which provides effective proton conduction pathways within the MOF. This work highlights a convenient strategy for designing proton-conducting MOFs via post-synthetic modification.

Design of a polymer-based cladding mode stripper with a distributed temperature profile.

An optimized polymer-based fiber cladding mode stripper (CMS) is presented experimentally. A unique partial fiber stripping method is introduced in CMS fabrication to enable distributed power extraction and temperature along the length of the CMS. The designed CMS based on a 400 µm double-clad fiber (DCF) extracts 300 W of inner cladding power, with an attenuation coefficient of 18.8 dB along with a temperature gradient of 0.17°C/watt. The fabricated CMS is used to develop an all-fiber 150 W thulium fiber laser at 1.94 µm.

Regio- and Diastereoselective Rhodium-Catalyzed Allylic Substitution with Unstabilized Benzyl Nucleophiles.

We have developed a highly regio- and diastereoselective rhodium-catalyzed allylic substitution of challenging alkyl-substituted secondary allylic carbonates with benzylzinc reagents, which are prepared from widely available benzyl halides. This process utilizes rhodium(III) chloride as a commercially available, high-oxidation state and bench-stable pre-catalyst to provide a rare example of a regio- and diastereoselective allylic substitution in the absence of an exogenous ligand. This reaction tolerates electronically diverse benzylzinc nucleophiles and an array of functionalized and/or challenging aliphatic allylic electrophiles. Finally, the configurational fluxionality of the rhodium-allyl intermediate is exploited to develop a novel diastereoselective process for the construction of vicinal acyclic ternary/ternary stereogenic centers, in addition to a cyclic ternary/quaternary derivative.

Ex vivo testing of air-cooled CW/modulated 30 W thulium fiber laser for lithotripsy.

A diode-pumped, air-cooled, all-fiber, quasi-continuous-wave thulium laser at an operating wavelength of 1.94 µm has been designed to study the performance of the laser parameter on the rate of fragmentation and its dependence on stone composition, fragmented particle size, as well as the retropulsion effect. The optimized laser cavity with an active fiber core/cladding diameter of 10/130 µm under a counter-propagating pump provides a stable laser power of 30 W at a slope efficiency of 50% and wall plug efficiency of 17%. The rate of fragmentation along with the retropulsion effect has been studied with human calcium oxalate monohydrate (COM) urinary stones (N=36) of different composition by using the designed laser and 200-µm-core low OH silica delivery fiber. The thulium fiber laser setting of 2.7 J pulse energy at the pulse rate of 10 Hz, pulse width of 90 ms, and peak power of 30 W is successful in breaking human COM stones in a controlled manner at a fragmentation rate of 0.8±0.4 mg/s, with almost uniform fragments of particle size less than 1.6 mm. During the stone fragmentation, the stone displacement (retropulsion effect) is less than 15 mm, even for the fragmented stone mass of 15±5 mg.

Regioselective Synthesis of Fused Furans by Decarboxylative Annulation of α,ß-Alkenyl Carboxylic Acid with Cyclic Ketone: Synthesis of Di-Heteroaryl Derivatives.

α,ß-Alkenyl carboxylic acids undergo CuII -mediated decarboxylative annulation reactions with aliphatic cyclic ketones to provide synthetically valuable di-heterocycles. The annulation process tolerates a variety of aliphatic ketones and heterocyclic alkenyl carboxylic acids, producing substituted fused furan derivatives with complete regioselectivity. The current protocol offers a synthetically applicable pathway to construct a variety of oligo-heterocycles through Cu-mediated single-electron transfer and decarboxylation. Notably, synthesis of relatively inaccessible di-heterocycles has been achieved successfully using this protocol.

Hybrid pumped gain-switched thulium fiber laser at a high repetition rate.

A gain-switched all-fiber thulium laser at 2 µm with high repetition rate has been demonstrated under a hybrid pumping scheme combined of a pulsed pump at 1.56 µm and CW pump at 793 nm. The in-band pulsed pump at 1.56 µm triggers the gain-switching pulses while the CW pump at 793 nm facilitates the energy storage. Therefore, the seed cavity delivers high energy pulses allowing the elimination of multistage amplification. Such hybrid pump configuration is effective for generating gain-switched pulses of high average power with better slope efficiency and pulse width of a few hundreds of a nanosecond. The optimized cavity under such hybrid pump configuration provides output power of 5.92 W from the gain-switched oscillator with slope efficiency of 60% and pulse width of 300 ns at a repetition rate of 344 kHz. Maximum pulse energy of 17.2 µJ and peak power of 53.9 W has been achieved at this repetition rate. Stable gain-switched pulses at reduced pump pulse energy have been achieved by the use of a CW pump at 793 nm. This novel pump configuration facilitates gain switch at higher repetition rates where enough pump pulse energy may not be available. The gain-switched laser also operates at 520 kHz and 1.3 MHz repetition rate by changing the 1.56 µm pulsed pump and cavity length.

High repetition rate gain-switched 1.94 µm fiber laser pumped by 1.56 µm dissipative soliton resonance fiber laser.

A dissipative soliton resonance (DSR) mode-locked Er:Yb fiber laser has been used to pump a thulium fiber laser to generate gain-switched pulses at high repetition rates. Here 412 ns long DSR pulses with a center wavelength of around 1.56 µm at a repetition rate of 410 kHz have been fed to a thulium fiber laser, resulting in generation of gain-switched pulses at 1.94 µm. The minimum pulse width achieved was 256 ns with an average power of 4.6 W at 66% slope efficiency. Gain-switched pulses at 520 kHz and 750 kHz were generated through changing the pump pulse repetition rate by modifying the DSR cavity. To the best of our knowledge, this is the first demonstration of a high repetition rate gain-switched thulium fiber laser pumped by a DSR mode-locked fiber laser. As DSR pulses can be generated with high seed average power and energy independent of the operating wavelength regime as well as mode-locking technique, the proposed method can be applied to generate gain-switched pulses at high repetition rates and various wavelengths without the need of any optical or electrical modulators.

Rhodium-Catalyzed meta-C-H Functionalization of Arenes.

Rhodium-catalyzed ortho-C-H functionalization is well known in the literature. Described herein is the Xphos-supported rhodium catalysis of meta-C-H olefination of benzylsulfonic acid and phenyl acetic acid frameworks with the assistance of a para-methoxy-substituted cyano phenol as the directing group. Complete mono-selectivity is observed for both scaffolds. A wide range of olefins and functional groups attached to arene are tolerated in this protocol.

Continuous-wave and quasi-continuous wave thulium-doped all-fiber laser: implementation on kidney stone fragmentations.

A continuous-wave (CW) as well as quasi-continuous wave (QCW) thulium-doped all-fiber laser at 1.94 µm has been designed for targeting applications in urology. The thulium-doped active fiber with an octagonal-shaped inner cladding is pumped at 793 nm to achieve stable CW laser power of 10 W with 32% lasing efficiency (against launched pump power). The linear variation of laser power with pump offers a scope of further power scaling. A QCW operation with variation of duty cycle from 0.5% to 90%, repetition rate from 0.1 Hz to 1 kHz, and pulse width from 40 µs to 2 s has been presented. Laser power of 9.5 W in CW mode of operation and average power of 5.2 W with energy range of 10.4-104 mJ in QCW mode of operation has been employed to fragment calcium oxalate monohydrate kidney stones (size of 1.5-4 cm) having different colors and composition. Dependence of ablation threshold, ablation rate, and average fragmented particle size on the average power and energy has been studied. One minute of laser exposure results in fragmentation of a stone surface with ablation rate of 8 mg/min having minimum particle size of 6.54 µm with an average size of 20-100 µm ensuring the natural removal of fragmented parts through the urethra.