The Small Ubiquitin-like Modifier (SUMO) is a crucial post-translational modifier of proteins, playing a key role in various cellular functions. All SUMOs are synthesized as precursor proteins that must be proteolytically processed. However, the maturation process of cleaving the extending C-terminal tail, preceding SUMOylation of substrates, remains poorly understood, especially within cellular environments. Chemical protein synthesis coupled with cell delivery offers great opportunities to prepare SUMO analogues to investigate this process in vitro and in live cells. Applying this unique combination we show that SUMO2 analogues containing the native tail undergo rapid cleavage and nuclear localisation, while a Gly93Ala mutation impairs cleavage and alters localisation. Tail mutations (Val94Glu, Tyr95Ala) affected cleavage rates, highlighting roles in SUMO-SENP protease interactions. In cells, analogoues containing tail mutations underwent cleavage and subsequently incorporated into PML-NBs. These findings advance our understanding of SUMO2 maturation and provide a foundation for future studies of this process for different SUMO paralogues in various cell lines and tissues.

Considering the potential advantages of minimally sized corroles for diverse applications, this study reports a facile access to cyano-substituted derivatives via a rare CF₃/CN conversion. Investigation of the fully characterized gallium, phosphorus, and cobalt complexes discloses multiple effects of the meso-nitrile groups attached to the macrocycle. This corrole appears to be the most electron poor derivative which comes into play in the redox potentials of the corresponding complexes. Compared to its precursor, both the absorption and emission are strongly red shifted and the fluorescence lifetime and quantum yield are much larger. The coordination chemistry is affected as well, by virtue of axial ligands being perpendicular rather than parallel relative to each other.

Halide perovskites (HPs) are crystalline solids that feature a unique softness, absent in conventional semiconducting materials. In recent years, this softness has been pivotal to many properties in these materials, in both static and dynamic regimes. Here, we focus on the two-dimensional (2D) (PEA)₂PbI₄ crystal. We employ extensive density functional theory calculations and structural analysis to uncover a rich mosaic of ground-state configurations, identifying several stable configurations with distinct electronic properties. Our study uncovers an intrinsic Rashba effect within a structure traditionally considered as globally centrosymmetric, presenting a challenge to conventional understanding in the field. The observed effect emerges from a local symmetry-breaking induced by specific spatial orientations of the organic PEA molecules. This intrinsic Rashba effect, observed in select configurations, underscores the nuanced symmetrical complexities of 2D HPs and highlights their potential for spin-related applications. Additionally, our investigation demonstrates the exceptional flexibility of 2D HPs, as evidenced by an observed significant tolerance toward single-molecule rotations. This flexibility suggests potential pathways for smoother transitions between different molecular domains within these materials. Overall, our findings emphasize the intricate interplay between the organic/inorganic counterparts and the electronic properties in 2D HPs, paving the way for further exploration and exploitation of their unique characteristics in various optoelectronic and spintronic applications.

Magnetic 2D materials enable interesting tuning options of magnetism. As an example, the van der Waals material FePS₃, a zig-zag-type intralayer antiferromagnet, exhibits very strong magnetoelastic coupling due to the different bond lengths along different ferromagnetic and antiferromagnetic coupling directions enabling elastic tuning of magnetic properties. The likely cause of the length change is the intricate competition between direct exchange of the Fe atoms and superexchange via the S and P atoms. To elucidate this interplay, we study the band structure of exfoliated FePS₃ by μm scale ARPES (angular resolved photoelectron spectroscopy), both, above and below the Néel temperature T_N. We found three characteristic changes across T_N. They involve S 3p-type bands, Fe 3d-type bands and P 3p-type bands, respectively, as attributed by comparison with density functional theory calculations (DFT + U). This highlights the involvement of all the atoms in the magnetic phase transition providing independent evidence for the intricate exchange paths.

New sources of parity and time-reversal violation are predicted by well motivated extensions of the Standard Model and can be effectively probed by precision spectroscopy of atoms and molecules. Chiral molecules have distinguished enantiomers which are related by parity transformation. Thus they are promising candidates to search for parity violation at molecular scales, which has yet to be observed. In this work, we show that precision spectroscopy of the hyperfine structure of chiral molecules is sensitive to new physics sources of parity and time-reversal violation. In particular, such a study can be sensitive to regions unexplored by terrestrial experiments of a new chiral spin-1 particle that couples to nucleons. We explore the potential to hunt for time-reversal violation in chiral molecules and show that it can be a complementary measurement to other probes. We assess the feasibility of such hyperfine metrology and project the sensitivity in CHDBrI⁺.

Diamond single crystals could be an attractive nonlinear THz source due to the materials high damage threshold, high transparency and THz-NIR phase matching ability. However, the buildup of second order nonlinear fields is restricted due to the centrosymmetric structure of the crystal. Here, we demonstrate nonlinear broadband THz emission due to optical rectification from diamond single crystals induced by embedded symmetry breaking nitrogen vacancy (NV) centers. The nonlinear temporal and spectral emission properties of the crystal are examined using THz time domain spectroscopy after pumping with NIR femtosecond pulses. The diamond-NV cell structure was also examined using density functional theory (DFT). The results show the potential of NV centers in diamond as a new nonlinear platform for broadband efficient THz generation.

Herein we report a general rhodium-catalyzed asymmetric intermolecular dearomative cyclopropanation of indoles using trifluoromethyl N-triftosylhydrazones as carbene precursors. The reaction enables the rapid construction of diverse cyclopropane-fused indolines bearing a trifluoromethylated quaternary stereocenter with high enantioselectivity (up to 99 % ee). This mild method exhibits broad substrate scope, tolerating various functional groups, and can even be utilized for the late-stage diversification of complex bioactive molecules. DFT calculations suggest that the formation of a key zwitterionic intermediate is responsible for the chiral induction. Overall, this approach opens up new possibilities for asymmetric cyclopropanation of challenging aromatic heterocyclic compounds.

Coherent control of ultrafast molecule making from colliding reactants is crucial for realizing coherent control of binary photoreactions (CCBP). To handle diverse excitation scenarios, feasibility with both weak and strong fields is essential. We experimentally demonstrate here the weak-field feasibility, achieving it even under thermally hot conditions typical of chemical reactions. The making of KAr complexes from hot pairs of colliding K and Ar atoms via resonance-mediated two-photon excitation is controlled by weak linearly chirped femtosecond pulses. Negative chirps enhance the yield. Our experimental and ab initio theoretical results are in excellent agreement. New routes to CCBP are opened.

Conservation laws are some of the most generic and useful concepts in physics. In nonlinear optical parametric processes, conservation of photonic energy, momenta and parity often lead to selection rules, restricting the allowed polarization and frequencies of the emitted radiation. Here we present a scheme to derive conservation laws in optical parametric processes in which many photons are annihilated and a single photon is emitted. We first rederive with it the known nonlinear optical conservation laws, and then utilize it to predict and explore conservations of reflection parity and space-time parity. Conservation of reflection-parity arises from a generalized reflection symmetry of the polarization in a superspace, analogous to the superspace employed in the study of quasicrystals. Conservation of space-time parity similarly arises from space-time reversal symmetry in superspace. We explore these conservation laws numerically in the context of high-harmonic generation and outline experimental setups where they can be tested.

Ultrashort laser pulses are unique tools to trigger and probe the fastest charge dynamics in matter, allowing the investigation of fundamental physical phenomena with unprecedented resolution in space, time and energy. One of the most fascinating opportunities that ultrashort pulses offer is the possibility of modulating and investigating symmetries by tailoring the properties of the laser beam in the spatial and polarization domains, effectively controlling symmetry breaking on multiple levels. In particular, this allows the probing of chiral matter and ultrafast chiral dynamics. In recent years, the development of highly sensitive approaches for studying chirality has been a hot topic in physics and chemistry that has developed largely separately from the field of tailored light. This Perspective discusses the individual and joint evolution of these fields, with an emphasis on how the fields have already cross-fertilized, opening new opportunities in science. We outline a future outlook of how the topics are expected to fully merge and mutually evolve, emphasizing open issues.