Beyond Single-Cycle Autonomous Molecular Machines: Light-Powered Shuttling in a Multi-Cycle Reaction Network.

Biomolecular machines autonomously convert energy into functions, driving systems away from thermodynamic equilibrium. This energy conversion is achieved by leveraging complex, kinetically asymmetric chemical reaction networks that are challenging to characterize precisely. In contrast, all known synthetic molecular systems in which kinetic asymmetry has been quantified are well described by simple single-cycle networks. Here, we report on a unique light-driven [2]rotaxane that enables the autonomous operation of a synthetic molecular machine with a multi-cycle chemical reaction network. Unlike all prior systems, the present one exploits a photoactive macrocycle, which features a different photoreactivity depending on the binding sites at which it resides. Furthermore, E to Z isomerization reverses the relative affinity of the macrocycle for two binding sites on the axle, resulting in a multi-cycle network. Building on the most recent theoretical advancements, this work quantifies kinetic asymmetry in a multi-cycle network for the first time. Our findings represent the simplest rotaxane capable of autonomous shuttling developed so far and offer a general strategy to generate and quantify kinetic asymmetry beyond single-cycle systems.

[Trans-Douglas Retzius' space-sparing robot-assisted simple prostatectomy for large-volume benign prostate hyperplasia].

OBJECTIVE: To report the safety and efficacy of trans-Douglas Retzius' space-sparing robot-assisted simple prostatectomy (RSS-RASP) in the treatment of large-volume BPH. METHODS: This retrospective study included 24 cases of large-volume (>80 ml) BPH treated by trans-Douglas RSS-RASP from August 2019 to June 2021. The patients ranged in age from 55 to 80 (mean 68.5) years, with an average body mass index of 25.1 (20.5－34.9) kg/m2 , median prostate volume of 132.4 (85.6－235.7) ml, and preoperative tPSA of 10.8 (0.5－37.9) ng/ml, IPSS of 25 (3－35) and quality of life (QOL) score of 5 (3－8). Before surgery, 12 of the patients received catheterization for urinary retention, 1 underwent cystostomy, 2 were complicated with hydronephrosis, 1 had stones and diverticulum in the bladder, and 14 were excluded from the cases of PCa by prostatic biopsy. The operation time, intraoperative blood loss, hemoglobin level on the first day after surgery, blood transfusion, and intra- and postoperative complications were recorded. The patients were followed up for 3 to 21 months postoperatively. Comparisons were made before and after operation in the IPSS, maximum urinary flow rate (Qmax), postvoid residual volume (PVR), QOL score, IIEF score and Male Sexual Health Questionnaire (MSHQ) score. RESULTS: Trans-Douglas RSS-RASP was successfully completed in all the 24 cases, with a mean operation time of 175 (100－285) min, intraoperative blood loss of 200 (50－800) ml, hemoglobin decrease of 25 (4－57) g/L on the first day after surgery, postoperative drainage tube indwelling of 3 (2－7) d, and urinary catheterization of 12 (4－18) d. Six (25%) of the patients received intraoperative blood transfusion, 1 underwent transurethral electrocoagulation hemostasis 1 month after surgery because of postoperative bleeding, and 1 received transurethral resection of the cicatrical adhesive tissue of the bladder neck 12 months after surgery. No other complications occurred postoperatively. The IPSS (3 ［1－7］), Qmax (19.6 ［9.9－32.1］ ml/s), PVR (0 ［0－34.9］ ml) and QOL score (2 ［0－3］) of the patients were significantly improved after surgery (P < 0.05), but no statistically significant differences were observed in the IIEF (20 ［19－24］) and MSHQ scores (14 ［13－14］) as compared with the baseline (P > 0.05). CONCLUSION: Trans-Douglas RSS-RASP is a safe and effective minimally invasive method for the treatment of large-volume (>80 ml) BPH, which can improve the urinary function of the patient after operation.

Tightly-bound trion and bandgap engineering viaγ-ray irradiation in the monolayer transition metal dichalcogenide WSe2.

Afterγ-ray irradiation treatment, a monolayer tungsten diselenide could be transitioned into an n-doped semiconductor due to the anion vacancies created by the radiation. Transmission electron microscope studies showed clear chemical modulation with atomically sharp interface. Change in the lattice vibrational modes induced by passivation of oxygen is captured by Raman spectroscopy. The frequency shifts in both in-plane and out-of-plane modes are dependent linearly on the oxidation content. We observe a negative trion, which is a neutral exciton bound with an electron, in the photoluminescence spectra. The binding energy of this trion is estimated to be ∼90 meV, making it a tightly bound exciton. The first-principles calculation suggests that an increase in the anion vacancy population is generally accompanied by a transition from a direct gap material to an indirect one. This opens up a new venue to engineer the electronic properties of transition metal dichalcogenides by using irradiation.

Rapid Mold Detection in Chinese Herbal Medicine Using Enhanced Deep Learning Technology.

Mold contamination poses a significant challenge in the processing and storage of Chinese herbal medicines (CHM), leading to quality degradation and reduced efficacy. To address this issue, we propose a rapid and accurate detection method for molds in CHM, with a specific focus on Atractylodes macrocephala, using electronic nose (e-nose) technology. The proposed method introduces an eccentric temporal convolutional network (ETCN) model, which effectively captures temporal and spatial information from the e-nose data, enabling efficient and precise mold detection in CHM. In our approach, we employ the stochastic resonance (SR) technique to eliminate noise from the raw e-nose data. By comprehensively analyzing data from eight sensors, the SR-enhanced ETCN (SR-ETCN) method achieves an impressive accuracy of 94.3%, outperforming seven other comparative models that use only the response time of 7.0 seconds before the rise phase. The experimental results showcase the ETCN model's accuracy and efficiency, providing a reliable solution for mold detection in Chinese herbal medicine. This study contributes significantly to expediting the assessment of herbal medicine quality, thereby helping to ensure the safety and efficacy of traditional medicinal practices.

Trans-rectovesical pouch urethral-sparing robotic-assisted simple prostatectomy: A case series.

Objective: To detail a novel technique of robotic-assisted simple prostatectomy that makes handling the gland protruding into the bladder neck easier and can preserve the urethra and retain ejaculation function as much as possible. Patients and methods: This is a prospective case series. Clinical data of 17 male patients who had large volume (>80 mL) benign prostatic hyperplasia (BPH) were enrolled to undergo trans-rectovesical pouch urethral-sparing robotic-assisted simple prostatectomy (usRASP). We adopted the approach through the space between the bladder neck and seminal vesicle to perform a usRASP that can avoid the detrusor skirt and fibrous matrix area of the retropubic prostate. Between the transitional zone and the peripheral zone of the large prostate, the hyperplastic prostatic gland tissue can be enucleated under direct vision while preserving the prostatic urethra and retaining the ejaculatory duct and bladder neck intact. All preoperative, perioperative and postoperative clinical data were collected, and descriptive analysis was performed. Results: The median intravesical prostatic protrusion was 19.3 mm (8.5-32.2). The median operative time was 100 min (75-140), and the median estimated blood loss was 100 mL (10-500). The median time to catheter removal was 7 days (5-7), with a median postoperative hospital stay of 2 days (2-4). After at least 6-month follow-up, the median maximum urine flow rate and postvoid residual volume were 40.1 mL/s (12.7-52.4) and 15 mL (5-23), respectively; the median International Prostate Symptom Score and Quality of Life score were 0 (0-6.3) and 1 (0-3), respectively; and the median total prostate-specific antigen was 0.84 ng/mL (0.15-1.01). All patients successfully underwent usRASP. Fifty-eight percent of patients with normal ejaculation function before surgery can still retain normal ejaculation function. Conclusion: We described a new approach to performing usRASP. This new method remarkably improved the voiding function, maintained antegrade ejaculation and did not increase the post-operative complications.

Mitochondrial-targeted brequinar liposome boosted mitochondrial-related ferroptosis for promoting checkpoint blockade immunotherapy in bladder cancer.

Checkpoint blockade immunotherapy (CBI) have exhibited remarkable benefits for cancer therapy. However, the low responsivity of CBI hinders its application in treatment of bladder cancer. Ferroptosis shows potential for increasing the responsivity of CBI by inducing immunogenic cell death (ICD) process. Herein, we developed a mitochondrial-targeted liposome loaded with brequinar (BQR) (BQR@MLipo) for enhancing the mitochondrial-related ferroptosis in bladder cancer in situ. It could be found that BQR@MLipo could selectively accumulate into mitochondria and inactivate dihydroorotate dehydrogenase (DHODH), which induced extensive mitochondrial lipid peroxidation and ROS, finally triggering ferroptosis of bladder cancer cells to boost the release of intracellular damage-associated molecular patterns (DAMPs) such as calreticulin (CRT), adenosine triphosphate (ATP), high mobility group box 1 (HMGB1). In addition, BQR@MLipo further promoted the release of mtDNA into the cytoplasm to activate the cGAS-STING pathway for the secretion of IFN-ß, which would increase the cross-presentation of antigens by dendritic cells and macrophage phagocytosis. Furthermore, the in vivo studies revealed that BQR@MLipo could remarkably accumulate into the bladder tumor and successfully initiate the infiltration of CD8+ T cells into tumor microenvironment for enabling efficient CBI to inhibit bladder tumor growth. Therefore, BQR@MLipo may represent a clinically promising modality for enhancing CBI in bladder tumor.

A host-guest interaction activated Bobbitt oxidant for highly efficient oxidation of alcohols.

Host-guest complexation using hydrogen-bonded macrocycles was found to enable activation of the Bobbitt oxidant reagent, which greatly facilitates the highly efficient oxidation of unactivated primary alcohols. This work provides a complementary approach to the activation of Bobbitt's salt with shape-persistent macrocycles in supramolecular catalysis.

γ-Ray irradiation-induced unprecedent optical, frictional and electrostatic performances on CVD-prepared monolayer WSe2.

Distinguishing from traditional working environments, we propose the harsh gamma radiation method to study the stability and reliability of the emerging two-dimensional (2D) quantum material tungsten diselenide (WSe2). Transmission electron microscopy studies showed clear chemical modulation with an atomically sharp interface, indicating that the selenium vacancy content increased with the irradiation dose. The WSe2 crystal could be transitioned into an n-doped semiconductor due to the anion vacancies created by radiation. Changes in the lattice vibrational modes induced by the passivation of oxygen was captured via Raman spectroscopy. The frequency shifts in both in-plane and out-of-plane modes are dependent linearly on the selenium vacancy content. The friction of WSe2 increases with the irradiation dose. Electrostatic properties were investigated by measuring the surface potential via Kelvin probe force microscopy. Due to different environments, molecular collisions lead to an increase in the concentration of vacancy defects, which made our results different from those previously reported. The first principles calculation suggests that an increase in the selenium vacancy population is generally accompanied by a transition from a direct gap material to an indirect one. This opens up a new venue to engineer the optical, frictional and electronic properties of transition metal dichalcogenides using irradiation.