Dalton Transactions

Liu, Bei; Duan, Huijuan; Liu, Zechao; Liu, Yuechen; Chu, Hongqian

doi: 10.1039/d3dt03614fpmid: 38108230

The conjugation of DNA molecules with metal or metal-containing nanoparticles (M/MC NPs) has resulted in a number of new hybrid materials, enabling a diverse range of novel biological applications in nanomaterial assembly, biosensor development, and drug/gene delivery. In such materials, the molecular recognition, gene therapeutic, and structure-directing functions of DNA molecules are coupled with M/MC NPs. In turn, the M/MC NPs have optical, catalytic, pore structure, or photodynamic/photothermal properties, which are beneficial for sensing, theranostic, and drug loading applications. This review focuses on the different DNA functionalization protocols available for M/MC NPs, including gold NPs, upconversion NPs, metal–organic frameworks, metal oxide NPs and quantum dots. The biological applications of DNA-functionalized M/MC NPs in the treatment or diagnosis of cancers are discussed in detail.

Wang, Cheng; Fei, Zhenghao; Wang, Yanqing; Ren, Fangfang; Du, Yukou

doi: 10.1039/d3dt03636gpmid: 38054822

The precise design and development of high-performing oxygen evolution reaction (OER) for the production of industrial hydrogen gas through water electrolysis has been a widely studied topic. A profound understanding of the nature of electrocatalytic processes reveals that Ni-based catalysts are highly active toward OER that can stably operate at a high current density for a long period of time. Given the current gap between research and applications in industrial water electrolysis, we have completed a systematic review by constructively discussing the recent progress of Ni-based catalysts for electrocatalytic OER at a large current density, with special focus on the morphology and composition regulation of Ni-based electrocatalysts for achieving extraordinary OER performance. This review will facilitate future research toward rationally designing next-generation OER electrocatalysts that can meet industrial demands, thereby promoting new sustainable solutions for energy shortage and environment issues.

Suga, Yuto; Sunada, Yusuke

doi: 10.1039/d3dt03788fpmid: 37987085

An Fe(ii) bromide complex supported by a bidentate phosphine ligand and an η1(C)-coordinated six-membered silacycle-bridged biphenyl-based ligand is converted upon reduction into an Fe(i) complex in which the hapticity of the silacycle-based ligand increases from η1 to η5.

Huang, Yi; Chu, Dongdong; Hou, Xueling; Li, Guangmao; Zhang, Yong

doi: 10.1039/d3dt03637epmid: 38099922

Designing wide-bandgap chalcogenides is one of the most important ways of obtaining high-performance infrared (IR) functional materials. In this work, two Mg-based metal thiophosphates, namely Na6Mg3P4S16 (NMPS) and RbMg2PS4Cl2 (RMPSC), were successfully obtained by introducing [MgS6] and [MgSxCl6−x] octahedra into thiophosphates. In addition, their crystal structures were determined, a first for Mg-containing [PS4]-based thiophosphates to the best of our knowledge. Their bandgaps were investigated in theoretical ways and verified by taking experimental measurements, and determined to be 3.80 eV for NMPS and 3.93 eV for RMPSC, values greater than those of the other investigated thiophosphate halides. The wide bandgaps of NMPS and RMPSC were attributed, based on theoretical calculations, to the [MgSxCl6−x] (x = 0–6) octahedron.

Orihashi, Kana; Yamauchi, Akio; Inoue, Miku; Parmar, Bhavesh; Fujiwara, Saiya; Kimizuka, Nobuo; Asada, Mizue; Nakamura, Toshikazu; Yanai, Nobuhiro

doi: 10.1039/d3dt03959epmid: 38164969

A series of metal–organic frameworks (MOFs) assembled with diazatetracene (DAT)-based linkers were synthesized and characterized. Despite different chromophore orientations and spacings, photoinduced persistent radicals were generated in all the MOFs, and their spin–lattice relaxation time (T1) and spin–spin relaxation time (T2) were found to be relatively long even at room temperature. The generality of long T1 and T2 values of photogenerated radicals in the chromophore-assembled MOFs provides a new platform towards quantum sensing applications.

Wu, Tingting; Zhang, Fengyu; Wang, Jingxuan; Liu, Xiaoxu; Tian, Ye; Chu, Ke

doi: 10.1039/d3dt03808dpmid: 38131476

Electrocatalytic NO2− reduction to NH3 (NO2RR) is an appealing approach for mitigating NO2− pollution and for the synthesis of valuable NH3, and so the exploration for high-performance NO2RR catalysts is pivotal yet remains challenging. Herein, amorphous MoO3 nanosheets (am-MoO3) were designed as a high-performance NO2RR electrocatalyst, delivering a maximum NO2−-to-NH3 faradaic efficiency of 94.8% and NH3 yield rate of 480.4 μmol h−1 cm−2 at −0.6 V vs. RHE. Theoretical computations revealed that the largely enhanced NO2RR activity of am-MoO3 originated from the amorphization-induced O-vacancies, which could enhance the NO2−-to-NH3 reaction energetics and hamper the competitive hydrogen evolution.

Hadlington, Terrance J.

doi: 10.1039/d3dt03976epmid: 38168968

Heteroleptic hydride complexes of the group 2 metals have seen considerable attention as Earth-abundant synthetic tools, yet anionic derivatives are exceedingly rare. We described the facile synthesis and in-depth characterisation of an anionic beryllium hydride dimer, featuring a dynamic [Be2H3] cluster at its core with a short Be⋯Be distance. Despite this, there is no formal Be–Be bond in this complex, with only hydride bridging interactions leading to this remarkable structural attribute.

Peng, Yan; Braun, Jonas; Schulze, Michael; Kaemmerer, Hagen; Schneider, Yannik F.; Anson, Christopher E.; Wernsdorfer, Wolfgang; Powell, Annie K.

doi: 10.1039/d3dt04141gpmid: 38167674

The 20-nuclearity compound [Fe8Dy12(tea)8(teaH)12(NO3)12]·8MeCN (where teaH3 = triethanolamine) was synthesised and characterised through single crystal X-ray diffraction and magnetic measurements. The shape of the magnetic hysteresis in the microSQUID measurements was rationalised using the MAGELLAN program.

Nandi, Sunny; Phukon, Hirdoyjit; Kalita, Dipul; Das, Shyamal K.

doi: 10.1039/d3dt02844epmid: 38167683

We report the electrochemistry of Al3+ ion storage in copper tetrathiovanadate (Cu3VS4) in an aqueous electrolyte for the first time. It is found that Cu3VS4 could deliver an initial discharge capacity of 111 mA h g−1 at a current rate of 0.5 A g−1 and 77 mA h g−1 up to the 300th cycle at 2 A g−1 along with an excellent rate capability. The better electrochemical performance may be attributed to the high theoretical capacity of sulfur and the superior conductivity of copper which allows facile Al3+ ion diffusion in Cu3VS4. The electrochemical mechanism of Al3+ ion storage is also illustrated.

Lal, Sohan; Staples, Richard J.; Shreeve, Jean'ne M.

doi: 10.1039/d3dt03954dpmid: 38170466

Nitroimino (R = N-NO2) energetic material is a unique class of high energy density materials (HEDM). Synthesis and characterization of insensitive nitroimino compounds are a major challenge. Here triazole-based nitroimino compounds and their high-nitrogen green energetic salts in excellent yields are described. These materials exhibit high positive heats of formation (7.84 to 735.29 kJ mol−1), good densities (1.66 to 1.98 g cm−3), suitable detonation properties (P = 22.02 to 31.88 GPa; D = 7472 to 8936 ms−1) and high ballistic properties (Isp 205.66 to 295.35 s; C* = 1065 to 1832 ms−1) with good thermal (Td = 136–378 °C) and mechanical stabilities (IS = 10–40 J and FS = 120–360 N).