1D Cu(I)-based chiral organic-inorganic hybrid material with second harmonic generation and circular polarized luminescence.

In recent years, organic-inorganic hybrid materials have demonstrated exceptional performance in nonlinear optics, attracting widespread attention. However, there are relatively few examples of coordination compounds synthesized with Cu as the metal center that exhibit excellent nonlinear optical properties. In this study, we successfully synthesized a pair of enantiomers named R/S-Cu2I2 by reacting chiral ligands with CuI. The crystal structure reveals a one-dimensional copper-iodide chain structure built by Cu2I2 clusters, and its ordered arrangement in space provides not only a strong second harmonic generation (SHG) signal (1.24 × KDP) but also a large birefringence (0.15@1064 nm). Under excitation at 395 nm, the crystals exhibit red fluorescence peaked at 675 nm. The CD spectra of R/S-Cu2I2 show a distinct mirror-symmetric Cotton effect, and their CPL signals are corresponding and opposite in the emission range, with a maximum glum of approximately ±2.5 × 10-3. Theoretical calculations using density functional theory were also carried out to enhance our understanding of the correlation between their structures and optical properties.

Effect of Postoperative Prolonged sedation with Dexmedetomidine after successful reperfusion with Endovascular Thrombectomy on long-term prognosis in patients with acute ischemic stroke (PPDET): study protocol for a randomized controlled trial.

BACKGROUND: Endovascular thrombectomy (EVT) is a standard treatment for acute ischemic stroke (AIS) with large vessel occlusion. Hypertension and increased blood pressure variability within the first 24 h after successful reperfusion are related to a higher risk of symptomatic intracerebral hemorrhage and higher mortality. AIS patients might suffer from ischemia-reperfusion injury following reperfusion, especially within 24 h. Dexmedetomidine (DEX), a sedative commonly used in EVT, can stabilize hemodynamics by inhibiting the sympathetic nervous system and alleviate ischemia-reperfusion injury through anti-inflammatory and antioxidative properties. Postoperative prolonged sedation for 24 h with DEX might be a potential pharmacological approach to improve long-term prognosis after EVT. METHODS: This single-center, open-label, prospective, randomized controlled trial will include 368 patients. The ethics committee has approved the protocol. After successful reperfusion (modified thrombolysis in cerebral infarction scores 2b-3, indicating reperfusion of at least 50% of the affected vascular territory), participants are randomly assigned to the intervention or control group. In the intervention group, participants will receive 0.1~1.0 µg/kg/h DEX for 24 h. In the control group, participants will receive an equal dose of saline for 24 h. The primary outcome is the functional outcome at 90 days, measured with the categorical scale of the modified Rankin Scale, ranging from 0 (no symptoms) to 6 (death). The secondary outcome includes (1) the changes in stroke severity between admission and 24 h and 7 days after EVT, measured by the National Institute of Health Stroke Scale (ranging from 0 to 42, with higher scores indicating greater severity); (2) the changes in ischemic penumbra volume/infarct volume between admission and 7 days after EVT, measured by neuroimaging scan; (3) the length of ICU/hospital stay; and (4) adverse events and the all-cause mortality rate at 90 days. DISCUSSION: This randomized clinical trial is expected to verify the hypothesis that postoperative prolonged sedation with DEX after successful reperfusion may promote the long-term prognosis of patients with AIS and may reduce the related socio-economic burden. TRIAL REGISTRATION: ClinicalTrials.gov NCT04916197. Prospectively registered on 7 June 2021.

Enriched environment ameliorates fear memory impairments induced by sleep deprivation via inhibiting PIEZO1/calpain/autophagy signaling pathway in the basal forebrain.

AIMS: To verify the hypothesis that an enriched environment (EE) alleviates sleep deprivation-induced fear memory impairment by modulating the basal forebrain (BF) PIEZO1/calpain/autophagy pathway. METHODS: Eight-week-old male mice were housed in a closed, isolated environment (CE) or an EE, before 6-h total sleep deprivation. Changes in fear memory after sleep deprivation were observed using an inhibitory avoidance test. Alterations in BF PIEZO1/calpain/autophagy signaling were detected. The PIEZO1 agonist Yoda1 or inhibitor GsMTx4, the calpain inhibitor PD151746, and the autophagy inducer rapamycin or inhibitor 3-MA were injected into the bilateral BF to investigate the pathways involved in the memory-maintaining role of EE in sleep-deprived mice. RESULTS: Mice housed in EE performed better than CE mice in short- and long-term fear memory tests after sleep deprivation. Sleep deprivation resulted in increased PIEZO1 expression, full-length tropomyosin receptor kinase B (TrkB-FL) degradation, and autophagy, as reflected by increased LC3 II/I ratio, enhanced p62 degradation, increased TFEB expression and nuclear translocation, and decreased TFEB phosphorylation. These molecular changes were partially reversed by EE treatment. Microinjection of Yoda1 or rapamycin into the bilateral basal forebrain induced excessive autophagy and eliminated the cognition-protective effects of EE. Bilateral basal forebrain microinjection of GsMTx4, PD151746, or 3-MA mimicked the cognitive protective and autophagy inhibitory effects of EE in sleep-deprived mice. CONCLUSIONS: EE combats sleep deprivation-induced fear memory impairments by inhibiting the BF PIEZO1/calpain/autophagy pathway.

Chiral Luminescent Sensor Eu-BTB@d-Carnitine Applied in the Highly Effective Ratiometric Sensing of Curing Drugs and Biomarkers for Diabetes and Hypertension.

Chiral drugs are of great significance in drug development and life science because one pair of enantiomers has a different combination mode with target biological active sites, leading to a vast difference in physical activity. Metal-organic framework (MOF)-based chiral hybrid materials with specific chiral sites have excellent applications in the highly effective sensing of drug enantiomers. Sitagliptin and clonidine are effective curing drugs for controlling diabetes and hypertension, while insulin and norepinephrine are the biomarkers of these two diseases. Excessive use of sitagliptin and clonidine can cause side effects such as stomach pain, nausea, and headaches. Herein, through post-synthetic strategy, MOF-based chiral hybrid material Eu-BTB@d-carnitine (H3BTB = 1,3,5-benzenetrisbenzoic acid) was synthesized. Eu-BTB@d-carnitine has dual emission peaks at 417 and 616 nm when excited at 330 nm. Eu-BTB@d-carnitine can be applied in luminescent recognition toward sitagliptin and clonidine with high sensitivity and low detection limit (for sitagliptin detection, Ksv is 7.43 × 106 [M-1]; for clonidine detection, Ksv is 9.09 × 106 [M-1]; limit of detection (LOD) for sitagliptin is 10.21 nM, and LOD of clonidine is 8.34 nM). In addition, Eu-BTB@d-carnitine can further realize highly sensitive detection of insulin in human fluids with a high Ksv (2.08 × 106 [M-1]) and a low LOD (15.48 nM). On the other hand, norepinephrine also can be successfully discriminated by the hybrid luminescent platform of Eu-BTB@d-carnitine and clonidine with a high Ksv value of 4.79 × 106 [M-1] and a low LOD of 8.37 nM. As a result, the chiral hybrid material Eu-BTB@d-carnitine can be successfully applied in the highly effective ratiometric sensing of curing drugs and biomarkers for diabetes and hypertension.

Solvothermal preparation of luminescent zinc(II) and cadmium(II) coordination complexes based on the new bi-functional building block and photo-luminescent sensing for Cu2+, Al3+ and L-lysine.

In industry, over usage of Cu2+ and Al3+ will lead to toxic wastewater, which further to give serious pollution for the environment. On the other hand, L-lysine can enhance serotonin release in the amygdala, with subsequent changes in psychobehavioral responses to stress. Therefore it is the urgent problem to design a method for detecting the amount of Cu2+, Al3+, and L-lysine. In this work, through the solvothermal synthesis method, two new coordination complexes based on the new bifunctional building block 4'-(1H-1,2,4-triazole-1-yl)- [1,1'-biphenyl]-4-carboxylic acid (HL) have been synthesized, namely, [Zn(L)2·4H2O] (complex 1) and [Cd(L)2·4H2O] (complex 2). X-ray single-crystal diffractometer was used to analyze its structure, powder X-ray diffraction (PXRD) patterns confirmed that 1 and 2 powder's purity and 1 can keep stable during the detection process of Cu2+, Al3+, and L-lysine, respectively. Elemental analysis, thermogravimetric analysis, infrared analysis, ultraviolet analysis and fluorescent spectrum have been used to characterize these complexes. The photo-luminescent test showed that 1 can accurately recognize Al3+ and Cu2+ among various cations. On the other hand, 1 can distinguish L-lysine among amino acid molecules. Therefore, 1 can be utilized as a multifunctional fluorescent probe for Al3+(Ksv = 1.5570 × 104 [M]-1), Cu2+(Ksv = 1.4948 × 104 [M]-1) and L-lysine (Ksv = 4.9118 × 104 [M]-1) with low detection limits (17.5 µM, 18.2 µM, 5.6 µM) respectively.

Dual-emission CdTe quantum dot@ZIF-365 ratiometric fluorescent sensor and application for highly sensitive detection of l-histidine and Cu2.

l-histidine acts as a semi-essential amino acid, which is medically used in the treatment of gastric ulcer, anemia, allergies. However, the overuse of l-histidine will result in terrible damage to heart disease, slow growth of animals and water pollution in the environment. In addition, Cu2+ pollution is common environmental pollution in the industry. It has the characteristics of high accumulation, migration, and persistence. Given this, through the post-synthesis strategy, CdTe quantum dots (QDs) were the first time to introduce into zeolitic imidazolate framework-ZIF-365 to synthesis dual-emission hybrid material CdTe@ZIF-365 with high quantum yield. TEM mappings and N2 absorption tests are applied to confirm the combination mode between CdTe quantum dots and ZIF-365. It should be noted that CdTe@ZIF-365 can be successfully utilized as a bi-functional ratiometric sensor for highly sensitive discrimination of l-histidine and Cu2+. Firstly, CdTe@ZIF-365 is applied to a fluorescent ratiometric sensor for Cu2+ with high sensitivity (the Ksv value is 2.7417✕107 [M-1]) and selectivity in the mixed cation ions' solution. On the other hand, CdTe@ZIF-365 also behaved as the first example for an excellent ratiometric fluorescent senor for l-histidine with high sensitivity (the Ksv value is 6.0507✕108 [M-1]) and selectivity in the mixed amino acids' solutions.

Solvothermal and Ultrasonic Preparation of Two Unique Cluster-Based Lu and Y Coordination Materials: Metal-Organic Framework-Based Ratiometric Fluorescent Biosensor for an Ornidazole and Ronidazole and Sensing Platform for a Biomarker of Amoeba Liver Abscess.

Through powerful solvothermal and facile ultrasonic synthetic strategies, two unique cluster-based lanthanide Lu and Y nanoporous metal organic frameworks (MOFs) have been successfully prepared, namely, {[Lu2(L)2]·2DMF·H2O}n (Lu-MOF) and [Y(L)(DMF)0.75]n (Y-MOF) (H3L = terphenyl-3,4'',5-tricarboxylic acid). In addition, both the morphologies and nanosizes of Lu-MOF and Y-MOF materials also have been deliberately tuned by adjustable ultrasonic conditions including irradiation time (40, 60, and 80 min) and power (70 w, 100 w). Currently, it is noted that the abuse of antibiotics such as ornidazole and ronidazole leads to great damage to human health, and therefore the development of highly effective and facile detection methods for ornidazole and ronidazole is quite important. Herein, to improve the fluorescent sensing sensitivity of antibiotics, Eu3+ and Tb3+ have been introduced into Lu-MOF (under a solvothermal preparation method) to fabricate a dual-emission hybrid material Eu3+/Tb3+@Lu-MOF through a postsynthesis strategy, which can be successfully applied as a self-calibrated ratiometric fluorescent sensor for ornidazole and ronidazole with high selectivity and sensitivity (the Ksv value for ornidazole is 1.0854 × 106 [M-1], and the Ksv value for ronidazole is 1.0595 × 107 [M-1]) and low detection limit values (2.85 nM for ornidazole and 26.7 nM for ronidazole). On the other hand, amoeba liver abscess (ALA) will easily lead to irregular fever, night sweats, and other tortured symptoms; C-reactive protein autoantibody (CRP Ab) is the important biomarker for the detection of ALA. Given this, Y-MOF (under the solvothermal preparation method) also has been successfully designed to combine FAM-labeled NH-ssDNA to construct the scarcely reported excellent hybrid FAM-labeled NH-ssDNA/Y-MOF sensing platform for the highly effective discrimination of CRP Ab with excellent sensitivity and selectivity in real samples such as human serum solution.

Supermicrosurgery in fingertip defects-split tibial flap of the second toe to reconstruct multiple fingertip defects: A case report.

BACKGROUND: Injuries to multiple fingertips pose a significant treatment dilemma. Numerous reconstructive options exist, all with the ultimate goal of restoring function and sensibility to the injured fingertips. CASE SUMMARY: A 24-year-old male suffered injury to multiple fingertips of the right hand, resulting in exposed distal phalanges of the middle, ring, and small fingers. The amputated distal stumps were not possible for replantation. Free flap coverage was selected in order to achieve better functional outcome. The fingertip defects were covered by performing a right second toe split tibial flap using local anesthesia at the harvest site and brachial plexus nerve block for the right upper extremity. At 6-month follow-up, all three of the reconstructed fingertips had some preserved nail growth, Semmes-Weinstein Monofilaments testing was equal to the contralateral side and the Static Two-Point Discrimination were comparable to the contralateral side. CONCLUSION: This report provides a novel reconstructive option for the management of multiple fingertip injuries and demonstrates the utility of supermicrosurgery in management of these injuries.