Orthogonality of non-coaxial Laguerre-Gaussian beams.

The conventional orthogonality of Laguerre-Gaussian (LG) beams is widely recognized and serves as the fundamental basis for mode division multiplexing utilizing LG beams as channels. However, this conventional orthogonality holds true only when two LG beams share the same axis. Whether non-coaxial LG beams, with parallel axes separated by a distance, are orthogonal to each other remains an open question. To address this issue and reveal the orthogonality of non-coaxial LG beams, we analytically derive the projection of one LG beam onto another. This projection exhibits a helical phase and a rotationally symmetric amplitude with dark rings present. These dark rings indicate that two non-coaxial LG beams are indeed orthogonal to each other when their axes are appropriately separated. Furthermore, any pair of non-coaxial LG beams within a set also exhibit orthogonality when their axes are fixed at a certain separation distance. This novel form of orthogonality predicts an innovative compound multiplexing technique that simultaneously combines mode and space, enabling more efficient packing of multiple LG beams within a single transmission aperture while maintaining parallel and closely spaced beam axes.

Photoswitchable Radical State in Nanoporous Metal-Organic Framework Films with Embedded Hexaarylbiimidazole.

Photoresponsive materials enable dynamic remote control of their fundamental properties. The incorporation of photochromic molecules in nanoporous metal-organic frameworks (MOFs) provides a unique opportunity to tailor the material properties, including the interaction between the MOF host and guest molecules in the pores. Here, a MOF film of type HKUST-1 with embedded hexaarylbiimidazole (HABI), undergoing reversible light-induced reactions between the stable dimer state and the metastable radical state, is presented. The switching between the dimer and radical form is shown by infrared, UV-vis, and electron paramagnetic resonance (EPR) spectroscopy. By transient uptake experiments with ethanol and methanol as probe molecules, we show that the dimer-radical switching impacts the host-guest interaction and, in particular, modifies the uptake amount and diffusion coefficient of the guest molecules. For ethanol, the diffusion slows down by 75%. This research presents the first MOF material with photoswitchable (meta)stable dimer and radical molecules, and it contributes to the advancement of photoresponsive nanoporous materials.

Precise treatment of pelvic fracture urethral injury associated with urethrorectal fistula.

OBJECTIVE: To evaluate the effect of a new strategy of transperineal anastomotic urethroplasty (TAU) with proximal transection in treating pelvic fracture urethral injury (PFUI) associated with urethrorectal fistula (URF). PATIENTS AND METHODS: A retrospective review of all patients treated by TAU with proximal transection and fistula repair for PFUI associated with URF was performed between August 2013 and July 2022. Information on demographics, peri-operative variables, and postoperative follow-up outcomes was collected. Successful surgery was defined as restoration of a uniform urethral calibre using flexible cystoscopy (third postoperative month) without strictures or leakage, with no further interventions required. Functional outcomes, including erectile function (assessed using the five-item International Index of Erectile Function) and urinary continence, were assessed. RESULTS: Forty patients diagnosed with PFUI associated with URF and treated by TAU with proximal transection and rectal fistula repair were enrolled. Six patients (15.0%) had a history of failed urethral reconstruction. The mean stenosis length and fistula diameter were 2.9 cm and 1.2 cm, respectively. All patients underwent faecal diversion before urethroplasty. After a median (range) follow-up of 45 (3-115) months, the final success rate was 90.0% (36/40). Postoperative complications included haematoma in three patients, epididymo-orchitis in three, wound infection in one, wound bleeding in one, delayed wound healing in three, and wound numbness in three. The overall incidence of postoperative erectile dysfunction reached 75.0%, with a median (range) score of 9 (0-19). Normal continence was achieved in 31 patients (77.5%). Occasional incontinence without the need for urinal pads occurred in eight patients, whereas one patient required urinal pads. CONCLUSIONS: Transperineal anastomotic urethroplasty with proximal transection is a precise and effective surgical strategy for treating PFUI associated with URF. This strategy ensures a high success rate and improves surgical efficiency.

Enantioselective Synthesis of Atropisomers via Vinylidene ortho-Quinone Methides (VQMs).

Atropisomers, arising from conformational restriction, are inherently chiral due to the intersecting dissymmetric planes. Since there are numerous applications of enantiopure atropisomers in catalyst design, drug discovery, and material science, the asymmetric preparation of these highly prized molecules has become a flourishing field in synthetic chemistry. A number of catalysts, synthetic procedures, and novel concepts have been developed for the manufacture of the atropisomeric molecules. However, due to the intrinsic properties of different types of atropisomers featuring biaryl, hetero-biaryl, or non-biaryl architectures, only very few methods pass the rigorous inspection and are considered generally applicable. The development of a broadly applicable synthetic strategy for various atropisomers is a challenge. In this Account, we summarize our recent studies on the enantioselective synthesis of atropisomers using the vinylidene ortho-quinone methides (VQMs) as pluripotent intermediates.The most appealing features of VQMs are the disturbed aromaticity and axial chirality of the allene fragment. At the outset, the applications of VQMs in organic synthesis have been neglected due to their principal liabilities: ephemeral nature, extraordinary reactivity, and multireaction sites. The domestication of this transient intermediate was demonstrated by in situ catalytic asymmetric generation of VQMs, and the reactivity and selectivity were fully explored by judiciously modifying precursors and tuning catalytic systems. A variety of axially chiral heterocycles were achieved through five-, six-, seven- and nine-membered ring formation of VQM intermediates with different kinds of branched nucleophilic functional groups. The axially chiral C-N axis could be constructed from VQM intermediates via N-annulation or desymmetrization of preformed C-N scaffolds. We take advantage of the high electrophilicity of VQMs toward a series of sulfur and carbon based nucleophiles leading to atropisomeric vinyl arenes. Furthermore, chiral helical compounds were realized by cycloaddition or consecutive annulation of VQM intermediates. These achievements demonstrated that the VQMs could work as a nuclear parent for the collective synthesis of distinct and complex optically active atropisomers. Recently, we have realized the isolation and structural characterization of the elusive VQMs, which were questioned as putative intermediates for decades. The successful isolation of VQMs provided direct evidence for their existence and an unprecedented opportunity to directly investigate their reactivity. The good thermal stability and reserved reactivity of the isolated VQMs demonstrated their great potential as synthetic reagents and expanded the border of VQM chemistry.

WRKY15 Suppresses Tracheary Element Differentiation Upstream of VND7 During Xylem Formation.

Formation of the vascular cylinder, a structure critical to water and nutrient transport in higher plants, is highly regulated. Here we identify WRKY15 as an important regulator that suppresses tracheary element (TE) differentiation in Arabidopsis (Arabidopsis thaliana). Overexpression of WRKY15 resulted in discontinuous protoxylem vessel files and TEs with reduced spiral wall thickening/lignification. Expression of a dominant-negative WRKY15 variant, WRKY15-EAR, led to extra protoxylem vessels and ectopic TEs with increased spiral wall thickening/lignification. Ectopic TE formation in the root cortex and hypocotyl/leaf epidermis reveals that the suppression of WRKY15 is sufficient to trigger the transdifferentiation of other types of cells to TEs. Expression profiling, RT-qPCR, and reporter analyses revealed that WRKY15 suppresses the expression of VASCULAR-RELATED NAC DOMAIN7 (VND7), a master transcriptional regulator that promotes TE differentiation. We propose that WRKY15 negatively regulates VND7 expression indirectly based on (1) the absence of a W-box in the promoter of VND7 and (2) the observation that WRKY15 and VND7 are expressed in different cells in the vascular cylinder, with WRKY15 expressed in the procambial cells and VND7 in the protoxylem poles of procambium and differentiating TEs. Future research is needed to reveal the details underlying the interaction of WRKY15 and VND7 in plant vascular development.

Inhibition of Kv7/M Channel Currents by Fangchinoline.

INTRODUCTION: Voltage-gated Kv7/M potassium channels play an essential role in the control of membrane potential and neuronal excitability. Fangchinoline, a bisbenzylisoquinoline alkaloid, displays extensive biological activities including antitumor, anti-inflammatory, and antihypertension effects. In this study, we investigated the effects of fangchinoline on Kv7/M channels. METHODS: A perforated whole-cell patch technique was used to record Kv7 currents from HEK293 cells and M-type currents from mouse dorsal root ganglion (DRG) neurons. RESULTS: Fangchinoline inhibited Kv7.2/Kv7.3 currents in a concentration-dependent manner, with an IC50 of 9.5 ± 1.2 µM. Fangchinoline significantly inhibited Kv7.1, Kv7.2, Kv7.3, Kv7.4, and Kv7.3/Kv7.5 channels without selective effects. Furthermore, fangchinoline significantly slowed the activation of Kv7.1-Kv7.5 channels and inhibited native M-channel currents of DRG neurons. CONCLUSION: Taken together, our findings indicate that fangchinoline concentration-dependently inhibited Kv7/M channel currents.

Substrate-Bound Diarylethene-Based Anisotropic Metal-Organic Framework Films as Photoactuators with a Directed Response.

Molecular machines and responsive materials open a plethora of new opportunities in nanotechnology. We present an oriented crystalline array of diarylethene (DAE)-based photoactuators, arranged in a way to yield an anisotropic response. The DAE units are assembled, together with a secondary linker, into a monolithic surface-mounted metal-organic framework (SURMOF) film. By Infrared (IR) and UV/Vis spectroscopy as well as by synchrotron X-ray diffraction, we show that the light-induced extension changes of the molecular DAE linkers multiply to yield mesoscopic and anisotropic length changes. Due to the special architecture and substrate-bonding of the SURMOF, these length changes are transferred to the macroscopic scale, leading to the bending of a cantilever and performing work. This research shows the potential of assembling light-powered molecules into SURMOFs to yield photoactuators with a directed response, presenting a path to advanced actuators.

Generalized Newton's rings with vortex beams.

The Newton's rings are interference patterns with concentric rings, and Newton's rings experiment is one of the most famous classic optics experiments. Here, we show that if we use a vortex beam, we can obtain generalized Newton's rings. Unlike traditional Newton's rings, the generalized ones are no longer concentric rings but spiral arms, and fork-shaped dislocations appear in spiral arms. More interesting, we reveal that both the number of spiral arms and the number of fork-shaped dislocations are equal to the value of topological charge of incident vortex beams. Our theoretical results are demonstrated experimentally. This novel interference pattern can be used for measuring the topological charge of vortex beams.

Overlapping functions of YDA and MAPKKK3/MAPKKK5 upstream of MPK3/MPK6 in plant immunity and growth/development.

Arabidopsis MITOGEN-ACTIVATED PROTEIN KINASE3 (MAPK3 or MPK3) and MPK6 play important signaling roles in plant immunity and growth/development. MAPK KINASE4 (MKK4) and MKK5 function redundantly upstream of MPK3 and MPK6 in these processes. YODA (YDA), also known as MAPK KINASE KINASE4 (MAPKKK4), is upstream of MKK4/MKK5 and forms a complete MAPK cascade (YDA-MKK4/MKK5-MPK3/MPK6) in regulating plant growth and development. In plant immunity, MAPKKK3 and MAPKKK5 function redundantly upstream of the same MKK4/MKK5-MPK3/MPK6 module. However, the residual activation of MPK3/MPK6 in the mapkkk3 mapkkk5 double mutant in response to flg22 pathogen-associated molecular pattern (PAMP) treatment suggests the presence of additional MAPKKK(s) in this MAPK cascade in signaling plant immunity. To investigate whether YDA is also involved in plant immunity, we attempted to generate mapkkk3 mapkkk5 yda triple mutants. However, it was not possible to recover one of the double mutant combinations (mapkkk5 yda) or the triple mutant (mapkkk3 mapkkk5 yda) due to a failure of embryogenesis. Using the clustered regularly interspaced short palindromic repeats (CRISPR) - CRISPR-associated protein 9 (Cas9) approach, we generated weak, N-terminal deletion alleles of YDA, yda-del, in a mapkkk3 mapkkk5 background. PAMP-triggered MPK3/MPK6 activation was further reduced in the mapkkk3 mapkkk5 yda-del mutant, and the triple mutant was more susceptible to pathogen infection, suggesting YDA also plays an important role in plant immune signaling. In addition, MAPKKK5 and, to a lesser extent, MAPKKK3 were found to contribute to gamete function and embryogenesis, together with YDA. While the double homozygous mapkkk3 yda mutant showed the same growth and development defects as the yda single mutant, mapkkk5 yda double mutant and mapkkk3 mapkkk5 yda triple mutants were embryo lethal, similar to the mpk3 mpk6 double mutants. These results demonstrate that YDA, MAPKKK3, and MAPKKK5 have overlapping functions upstream of the MKK4/MKK5-MPK3/MPK6 module in both plant immunity and growth/development.

Organocatalytic Asymmetric Multicomponent Cascade Reaction for the Synthesis of Contiguously Substituted Tetrahydronaphthols.

Isobenzopyrylium ions are unique, highly reactive, aromatic intermediates which are largely unexplored in asymmetric catalysis despite their high potential synthetic utility. In this study, an organocatalytic asymmetric multicomponent cascade via dienamine catalysis, involving a cycloaddition, a nucleophilic addition, and a ring-opening reaction, is disclosed. The reaction furnishes chiral tetrahydronaphthols containing four contiguous stereocenters in good to high yield, high diastereoselectivity (up to >20:1), and excellent enantioselectivity (93-98% ee). The obtained products are important synthetic intermediates, and it is demonstrated that they can be used for the generation of frameworks such as octahydrobenzo[h]isoquinoline and [2.2.2]octane scaffolds. Furthermore, mechanistic experiments involving oxygen-18-labeling studies and density functional theory calculations provide a vivid picture of the reaction mechanism. Finally, the bioactivity of 16 representative tetrahydronaphthol compounds has been evaluated in U-2OS cancer cells with some compounds showing a unique profile and a clear morphological change.