Enzyme-Inspired Coordination Polymers for Selective Oxidization of C(sp3)-H Bonds via Multiphoton Excitation.

Nature's blueprint provides the fundamental principles for expanding the use of abundant metals in catalysis; however, mimicking both the structure and function of copper enzymes simultaneously in one artificial system for selective C-H bond oxidation faces marked challenges. Herein, we report a new approach to the assembly of artificial monooxygenases utilizing a binuclear Cu2S2Cl2 cluster to duplicate the identical structure and catalysis of the CuA enzyme. The designed monooxygenase Cu-Cl-bpyc facilitates well-defined redox potential that initially activated O2via photoinduced electron transfer, and generated an active chlorine radical via a ligand-to-metal charge transfer (LMCT) process from the consecutive excitation of the in situ formed copper(II) center. The chlorine radical abstracts a hydrogen atom selectively from C(sp3)-H bonds to generate the radical intermediate; meanwhile, the O2•- species interacted with the mimic to form mixed-valence species, giving the desired oxidization products with inherent product selectivity of copper monooxygenases and recovering the catalyst directly. This enzymatic protocol exhibits excellent recyclability, good functional group tolerance, and broad substrate scope, including some biological and pharmacologically relevant targets. Mechanistic studies indicate that the C-H bond cleavage was the rate-determining step and the cuprous interactions were essential to stabilize the active oxygen species. The well-defined structural characters and the fine-modified catalytic properties open a new avenue to develop robust artificial enzymes with uniform and precise active sites and high catalytic performances.

[Treatment of open fracture of lower limb in high altitude area].

OBJECTIVE: To explore the treatment methods and experience of open fracture of lower limb in high altitude area. METHODS: From January 2016 to January 2021, 62 patients with open fractures of lower limbs were treated by staged surgery with the concept of injury control orthopedics, emphasizing wound treatment and combining various fracture fixation methods. There were 51 males and 11 females, ranging in age from 14 to 59 years old, with a mean of (37.2±12.3) years old; and the course of disease ranged from 7 to 59 days, with a mean of (23.7±15.5) days. According to Gustilo Anderson classification, there were 14 cases of typeⅠ, 24 cases of typeⅡ, 14 cases of typeⅢA, 8 cases of typeⅢB and 2 cases of typeⅢC. The fracture repair and wound healing were observed, and the clinical efficacy was evaluated by Johner-Wruhs evaluation standard. RESULTS: Fifty-five patients were followed up, and the duration ranged from 4 to 36 months, with a mean of (14.7±8.5) months, and 7 cases were lost to follow-up. According to Johner-Wruhs evaluation criteria, 33 cases got an excellent result, 16 good, 4 poor and 2 bad. The wound healing was poor in 2 cases, partial necrosis of Achilles tendon in 1 case, nonunion of fracture in 1 case and delayed healing of fracture in 2 cases. CONCLUSION: It is an effective method to treat the open fracture of lower extremity in high altitude area to pay attention to the management of soft tissue injury, the management of wound moisturizing, staged operation of fracture and full protection of blood supply at the fracture end. Paying attention to the treatment of soft tissue injury and the management of wound moisturizing, staged operation of fracture and full protection of blood supply at the fracture end are effective methods for the treatment of open fracture of lower limbs in high altitude areas.

Direct Peritoneal Resuscitation with Pyruvate Protects the Spinal Cord and Induces Autophagy via Regulating PHD2 in a Rat Model of Spinal Cord Ischemia-Reperfusion Injury.

Direct peritoneal resuscitation with pyruvate (Pyr-PDS) has emerged as an interesting candidate to alleviate injury in diverse organs, while the potential mechanism has yet to be fully elucidated. To explore the effect of autophagy in the spinal cord ischemia-reperfusion (SCIR) injury and the underlying mechanism, we established a model of SCIR in vivo and in vitro. In vivo, male SD rats underwent aortic occlusion for 60 min and then followed by intraperitoneally infused with 20 mL of pyruvate or normal saline for 30 min, and the spinal cords were removed for analysis after 48 h of reperfusion. The functional and morphological results showed that Pyr-PDS alleviated SCIR injury; meanwhile, the expression of autophagy-related genes and transmission electron microscopy displayed autophagy was activated by SCIR injury, and Pyr-PDS treatment could further upregulate the degree of autophagy which plays a protective part in the SCIR injury, while there is no significant difference after treatment with saline. In addition, SCIR injury inhibited expression of PHD2, which results to activate its downstream HIF-1α/BNIP3 pathway to promote autophagy. In the Pyr-PDS, the results revealed PHD2 was further inhibited compared to the SCIR group, which could further activate the HIF-1α/BNIP3 signaling pathway. Additionally, oxygen-glucose deprivation and reoxygenation were applied to SH-SY5Y cells to mimic anoxic conditions in vitro, and the expression of autophagy-related genes, PHD2, and its downstream HIF-1α/BNIP3 pathway showed the same trend as the results in vivo. Besides, IOX2, a specific inhibitor of PHD2 was also treated to SH-SY5Y cells during reoxygenation, in which the result is as same as the pyruvate group. Then, we observed the expression of autophagy-related genes and the HIF-1α signal pathway in the process of reoxygenation; the results showed that as the reoxygenation goes, the expression of the HIF-1α signal pathway and degree of autophagy came to decrease gradually, while treated with pyruvate could maintain autophagy high and stable through keeping PHD2 at a lower level during reoxygenation, and the latter was observed downregulated during reoxygenation process from 0 to 24 hours in a time-effect way. The above results indicated that direct peritoneal resuscitation with pyruvate showed effective protection to ischemia-reperfusion of the spinal cord through activating autophagy via acting on PHD2 and its downstream HIF-1α/BNIP3 pathway.

Pyruvate Protects Against Intestinal Injury by Inhibiting the JAK/STAT Signaling Pathway in Rats With Hemorrhagic Shock.

BACKGROUND: This study aimed to investigate the role of Janus kinase/signal transducers and activators of transcription (JAK/STAT) signaling pathway in protection by peritoneal resuscitation (PR) using pyruvate-peritoneal dialysis solution (PY-PDS) against intestinal injury from hemorrhagic shock (HS) in rats. MATERIALS AND METHODS: Sixty-four rats were assigned to eight groups: group SHAM; group intravenous resuscitation (VR); groups NS, LA, and PY in which the rats were subjected to HS and PR with normal saline (NS), lactate-peritoneal dialysis solution (LA-PDS), and PY-PDS, respectively, combined with VR; and groups DMSO, RPM, and AG490 in which the rats were subjected to HS and VR with pretreatment of dimethyl sulfoxide (DMSO), rapamycin (RPM), and tyrphostin B42 (AG490). RESULTS: At 2 h after HS and resuscitation, the levels of diamine oxidase, 15-F2t-isoprostane, thromboxane B2, and endothelin-1, in the blood and the intestinal mucosal apoptotic index and caspase-3 were lower in groups PY, RPM, and AG490 than in groups VR, NS, LA, and DMSO. Group PY showed lower levels of malondialdehyde and myeloperoxidase and a higher level of superoxide dismutase than groups VR, NS, and LA. Phosphorylated JAK2 and phosphorylated STAT3 levels were lower in groups PY, RPM, AG490, and LA than in groups VR, NS, and DMSO. CONCLUSIONS: The protection mechanism of PR with PY-PDS combined with VR was related to the inhibition of the JAK/STAT signaling pathway during HS and resuscitation. The process might include suppression of oxidative stress, reduction of neutrophil infiltration, regulation of microcirculation, and inhibition of apoptosis.

Palladium Supported on Calcium Decorated Carbon Nanotube Hybrids for Chemoselective Hydrogenation of Cinnamaldehyde.

The chemoselective hydrogenation of cinnamaldehyde (CAL) to the corresponding hydrocinamaldehyde (HCAL) is a type of important reactions in fine chemistry, which is critically dependent on the rational design the chemical structure of active metal. In this work, calcium promoted palladium on CNT hybrid (Ca-Pd@CNT) with monolithic structure was synthesized through one-pot alginate gel process. The catalytic performance results showed that moderate Ca promotion catalyst (Ca-Pd@CNTHCl-2h) present a superior CAL hydrogenation activity with CAL conversion of 99.9% and HCAL selectivity of 86.4% even at the lager Pd nanoparticle size (c.a. 5 nm). The characterization results show that the electron transfer between the additive Ca promoter and Pd nanoparticles (NPs) could modify the electron structure of Pd species and induce the formation of the partial positively charged Pdδ+ species on the Pd NPs surface in the Ca-Pd@CNTHCl-2h catalyst resulting to the satisfactory catalytic performance. Furthermore, the one-pot gel synthesis methodology for microscopic carbon supported catalyst could also endows its great potential industry application in heterogeneous catalysis with easily handling during the transportation and reaction, and attributed to reducing the overall pressure drop across in the fix-bed reactor.