Zirconaaziridine-Mediated Ni-Catalyzed Diastereoselective C(sp2)-Glycosylation.

In the realm of organic synthesis, the catalytic and stereoselective formation of C-glycosidic bonds is a pivotal process, bridging carbohydrates with aglycones. However, the inherent chirality of the saccharide scaffold often has a substantial impact on the stereoinduction imposed by a chiral ligand. In this study, we have established an unprecedented zirconaaziridine-mediated asymmetric nickel catalysis, enabling the diastereoselective coupling of bench-stable glycosyl phosphates with a range of (hetero)aromatic and glycal iodides as feasible coupling electrophiles. Our developed method showcases a broad scope and a high tolerance for various functional groups. More importantly, precise stereocontrol toward both anomeric configurations of forming C(sp2)-glycosides can be realized by simply utilizing the popular chiral bioxazoline (biOx) ligands in this reductive Ni catalysis. Regarding the operating mechanism, both experimental and computational studies support the occurrence of a redox transmetalation process, leading to the formation of a transient, bimetallic Ni-Zr species that acts as a potent and efficient single-electron reductant in the catalytic process.

Proteus appendicitidis sp. nov., isolated from the appendiceal pus of an appendicitis patient in Yongzhou, China.

A Gram-negative, facultatively anaerobic, short rod-shaped bacterium, designated as strain HZ0627T, was isolated from the appendiceal pus of a patient with appendicitis in Yongzhou, Hunan, China. This strain was subjected to comprehensive phenotypic, phylogenetic, and genomic analyses using polyphasic taxonomic methods. Phylogenetic analysis of the 16S rRNA gene sequence revealed that this strain belonged to the genus Proteus and the family Morganellaceae, whereas that based on the rpoB gene sequence and phylogenomic analysis demonstrated that this strain was distinctly separated from other type strains of Proteus species. Moreover, whole-genome-based analyses, including in silico DNA-DNA hybridization (isDDH) and average nucleotide identity (ANI), revealed that strain HZ0627T had much lower isDDH rates (24.5-55.6%) and ANI (82.04-93.90%) than those of the thresholds (i.e., 70% and 95%, respectively) for species delineation, when compared to the type strains of other Proteus species. The cellular fatty acid profile of strain HZ0627T was dominated by C16:0 (34.5%), cyclo C17:0 (25.8%), C14:0 (12.6%), C16:1 iso I/14:0 3-OH (7.7%), C18:1ω7c/18:1ω6c (6.5%), and C16:1ω7c/16:1ω6c (4.9%), which clearly differentiated it from the documented type strains of Proteus species. In addition, several specific physiological traits, including optimal growth temperature, tolerance to sodium chloride, and carbon source utilization, differed from those of other Proteus species. Therefore, we propose the name Proteus appendicitidis sp. nov. for strain HZ0627T (= CCTCC AB 2022380T = KCTC 92986T), which represents the type strain of this novel Proteus species.

Detection of skin thickness and density in healthy Chinese people by using high-frequency ultrasound.

OBJECTIVES: Due to a recent development of high-frequency ultrasound (HFUS) systems, it is easier to realize high-resolution in vivo imaging of the biological tissues. The object of this study was to map the thickness and echo density of skin layers in healthy Chinese people and assess the influence of gender, age, and region on it. METHODS: A total of 189 volunteers (85 male, 104 female) with age range of 22-75-year old (mean age of 41.2-year old) were enrolled. The thickness and density of the epidermis and dermis layer were detected by high-frequency (22 or 75 MHz) ultrasonography at 13 different anatomical sites, including the forehead, cheeks, flexor and extensor forearms, flexor and extensor upper arms, inner and outer legs, inner and outer thighs, back, and abdomen. RESULTS: The thickness and density of epidermis/dermis between different anatomical sites were statistically significant (p < 0.05). The epidermis thickness of the face and trunk were less than that of the limbs, whereas the thicknesses of the dermis were on the contrary. The density of the epidermis/dermis of the face and trunk were less than that of the limbs. The thickness of dermis in most of the sites were higher in male than in female, and the density of epidermis and dermis in most of the sites were less in men than in women. The thicknesses/densities of dermis were lower in older age group in almost all sites, whereas only several sites reached statistical. The difference between the north and south regions showed the environment also influenced the thickness and density of the skin. CONCLUSION: HFUS provides a simple noninvasive method for evaluating the skin thickness and echo-density, which, reflecting intradermal structure, exhibit systematic regional variation. With the establishment of Chinese phenotypic database of skin thickness and density, it will be helpful for the skin disease assessment, skin surgery, and cosmetology technology.

Mechanochemical Degradation and Recycling of Synthetic Polymers.

The accumulation of plastic waste, due to lack of recycling, has led to serious environmental pollution. Although mechanical recycling can alleviate this issue, it inevitably reduces the molecular weight and weakens the mechanical properties of materials and is not suitable for mixed materials. Chemical recycling, on the other hand, breaks the polymer into monomers or small-molecule constituents, allowing for the preparation of materials of quality comparable to that of the virgin polymers and can be applied to mixed materials. Mechanochemical degradation and recycling leverages the advantages of mechanical techniques, such as scalability and efficient energy use, to achieve chemical recycling. We summarize recent progress in mechanochemical degradation and recycling of synthetic polymers, including both commercial polymers and those designed for more efficient mechanochemical degradation. We also point out the limitations of mechanochemical degradation and present our perspectives on how the challenges can be mitigated for a circular polymer economy.

Understanding the Structure-Polymerization Thermodynamics Relationships of Fused-Ring Cyclooctenes for Developing Chemically Recyclable Polymers.

Polymers that can be chemically recycled to their constituent monomers offer a promising solution to address the challenges in plastics sustainability through a circular use of materials. The design and development of monomers for next-generation chemically recyclable polymers require an understanding of the relationships between the structure of the monomers/polymers and the thermodynamics of polymerization/depolymerization. Here we investigate the structure-polymerization thermodynamics relationships of a series of cyclooctene monomers that contain an additional ring fused at the 5,6-positions, including trans-cyclobutane, trans-cyclopentane, and trans-five-membered cyclic acetals. The four- and five-membered rings trans-fused to cyclooctene reduce the ring strain energies of the monomer, and the enthalpy changes of polymerizations are found to be in the range of -2.1 to -3.3 kcal mol-1. Despite the narrow range of enthalpy changes, the ceiling temperatures at 1.0 M span from 330 to 680 °C, due to the low entropy changes, ranging from -2.7 to -5.0 cal mol-1 K-1. Importantly, geminal substituents on the trans-five-membered cyclic acetal fused cyclooctenes are found to reduce the ceiling temperature by ∼300 °C, although they are not directly attached to the cyclooctene. The remote gem-disubstituent effect demonstrated here can be leveraged to promote depolymerization of the corresponding polymers and to tune their thermomechanical properties.

Interactions on Proteins Arising from the Self-Assembly of a Polyelectrolyte Brush.

Surfaces grafted with polyelectrolyte chains for excellent performance in protein antifouling are highly desired in many applications, such as biomedical implants and devices. In general, the adsorbing/resisting behaviors of proteins can be mainly attributed to the electrostatic interactions that are associated with the charge properties of proteins and polyelectrolytes. By coarse-grained molecular dynamics simulations, we examined the self-assembled structures of polyanion and polyzwitterion brushes as well as the interactions on negatively and positively charged proteins. We found that in addition to charges, the structural polarization induced by self-assembly with a certain charge distribution shows significant influences on protein behavior. The large-scale dipole-dipole interactions between brushes and proteins can dominate the behavior of proteins on the brushes under certain circumstances. To ensure simulation accuracy, we compared two models and found a polar Martini model that explicitly treats electrostatic interactions as long-ranged ones, giving a more reasonable structural description compared with the normal Martini model that truncates electrostatic interactions.

The effects of nutritional support team intervention on postoperative immune function, nutritional statuses, inflammatory responses, clinical outcomes of elderly patients with gastric cancer.

BACKGROUND: To explore the effects of nutrition support team (NST) intervention on elderly patients with gastric cancer (GC). METHODS: The elderly GC patients (tumor stage I/II/III), admitted to our department from January 2015 to September 2021, were retrospectively analyzed and divided into NST group and traditional nutrition (TN) group according to nutritional management methods. The immune, inflammatory, nutrition-related indices, postoperative recovery and long-term prognosis of two groups were analyzed. RESULTS: A total of 258 elderly GC patients were included (NST group, n = 125; TN group, n = 133). After propensity score matching (PSM) in ratio of 1:1, 73 pairs of patients were matched. There were statistically significant differences in CD3 and CD4 level postoperative one month and IgG level postoperative one week between NST group and TN group (P < 0.05). There was no significant differences in serum CRP and IL-6 levels preoperative one day, postoperative one week and one month between two groups (P > 0.05). There were significant differences in body mass index (BMI) between the two groups postoperative one month (P < 0.05). The rate of infectious complications in TN group was significantly higher than that in NST group (P < 0.05). There was no statistically significant differences in 3-year relapse-free survival (RFS) or 3-year overall survival (OS) between NST group and TN group (P > 0.05). CONCLUSIONS: Compared with TN management, NST intervention might be benefit to the immune function recovery and nutritional status, but there was no evidence that NST could improve the prognosis of elderly GC patients.

Long non-coding RNA MCF2L-AS1 promotes the aggressiveness of colorectal cancer by sponging miR-874-3p and thereby up-regulating CCNE1.

BACKGROUND: Long non-coding RNAs (lncRNAs) have drawn growing attention because of the role which they play in various diseases, including colorectal cancer (CRC). However, the potential functions of lncRNA MCF2L antisense RNA 1 (MCF2L-AS1) in tumors remained largely unclear. The present study aimed to explore the clinical significance and the biological effects of lncRNA MCF2L antisense RNA 1 (MCF2L-AS1) in CRC. METHODS: Reverse transcriptase-polymerase chain reaction was performed to determine the expression of MCF2L-AS1 in CRC. The clinical significance of MCF2L-AS1 in CRC patients was analyzed statistically. In vitro experiments were performed to determine the effects of MCF2L-AS1 on the cellular progression of CRC cells. Bioinformatic assays, luciferase reporter assays and RNA-pulldown assays were performed to predict for potential microRNAs that can interact with MCF2L-AS1 and mRNAs that can interact with miR-874-3p. RESULTS: We identified a novel CRC-related lncRNA, MCF2L-AS1, which is distinctly highly expressed in CRC. Its diagnostic value for CRC patients was also demonstrated. Clinical assays revealed that high MCF2L-AS1 expression is associated with advanced stages, positive metastasis and the poor prognosis of CRC patients. Multivariate assays confirmed that MCF2L-AS1 expression is an independent poor prognostic factor for both 5-year overall survival and 5-year disease-free survival of CRC patients. Functionally, we confirmed that knockdown of MCF2L-AS1 distinctly suppresses the proliferation, migration and invasion of CRC cells and also promotes apoptosis. Mechanistic investigation showed that MCF2L-AS1 functions as an endogenous sponge for miR-874-3p to increase the expression of CCNE1. CONCLUSIONS: Our findings identified a novel CRC-related lncRNA, MCF2L-AS1, which may be used as a potential diagnostic and prognostic biomarker for CRC patients. In addition, the newly identified MCF2L-AS1/miR-874-3p/CCNE1 axis can modulate the initiation and progression of CRC.

Effect of single-incision laparoscopic distal gastrectomy guided by ERAS and the influence on immune function.

BACKGROUND: To evaluate the immune function of gastric cancer patients after single-incision laparoscopic distal gastrectomy (SIDG) or multiport laparoscopic distal gastrectomy (MLDG) guided by enhanced recovery after surgery (ERAS). METHODS: A retrospective cohort study was performed on 120 patients who underwent laparoscopic distal gastrectomy for gastric cancer. The patients were divided into two groups according to operation method: group A (MLDG) and group B (SIDG), both guided by ERAS concept. The indicators reflecting immune function and inflammation, such as CD3+, CD4+, CD8+ and NK cell count, CD4+/CD8+ cell ratios, IgA, IgM and IgG levels, C-reactive protein (CRP), total lymphocyte count (TLC) and neutrophil-to-lymphocyte ratio (NLR) were tested 3 days and 7 days after surgery. RESULTS: The skin incision length of patients in group B was significantly shorter than that in group A, but the operation time was significantly longer in group B than that in group A (P < 0.05). There were no significant differences in preoperative CD3+, CD4+, CD8+, natural killer (NK) cells, CD4+/CD8+, IgA, IgM and IgG levels between two groups (P < 0.05). Three days after surgery, the immune function indices were decreased in both groups, but with no significant difference between two groups (P > 0.05). On the 7th day after surgery, the immune indexes of both groups recovered somewhat, approaching the preoperative level (P > 0.05). Inflammation indexes increased 3 days after surgery and decreased 7 days after surgery in both groups, among them the CRP level in group A was higher than that in group B (P < 0.05). The 3-year survival rate were 96.7% in group A and 91.7% in group B, respectively, with no statistically significant difference. CONCLUSION: Compared with MLDG guided by ERAS, SIDG under the guidance of the ERAS concept has better cosmetic effect and similar effect on immune function of gastric cancer patients.

A novel large deletion in the APC gene associated with Gardner syndrome in a Chinese family.

INTRODUCTION: Gardner syndrome is a hereditary disease characterized by familial adenomatous polyposis (FAP), accompanied by soft tissue tumors. MATERIAL AND METHODS: a Chinese FAP family was enrolled and followed-up for three years. RESULTS: a novel large germline fragment deletion (EX10_16DEL) of the adenomatous polyposis coli (APC) gene was identified by multiplex ligation-dependent probe amplification (MLPA). An unexpected abdominal tumor grew two years after a subtotal colectomy of the proband. The immunohistochemistry study of the abdominal tumor showed SMA(focal+), calponin(+), ß-catenin(nucleus+) and CD34(focal+), CD117(-), which was consistent with a desmoid tumor. CONCLUSION: when a FAP related desmoid tumor appears, the possibility of Gardner syndrome should be considered. This is the first largest deletion of the APC gene in the Chinese population associated with Gardner syndrome.

A Polymer with "Locked" Degradability: Superior Backbone Stability and Accessible Degradability Enabled by Mechanophore Installation.

Though numerous applications require degradable polymers, there are surprisingly few polymer systems that combine superior stability and controllable degradability. Particularly, the degradability of a conventional degradable polymer is typically enabled by cleavable groups on the backbone, which can be attacked by stimuli in ambient conditions, causing undesirable material deterioration. Here we report a general strategy to overcome this issue: "locking" the degradability during handling and use of the polymers and "unlocking" it when degradation is needed. This strategy is demonstrated with a cyclobutane-fused lactone (CBL) polymer. The cyclobutane keeps polymer backbone intact under conditions that hydrolyze the lactone and allows the ester group to be recovered when undesirable hydrolysis occurs. When backbone degradation is needed, the degradability can be unlocked by mechanochemical activation that converts the polyCBL into a linear polyester. The rare combination of two intrinsically conflicting properties, i.e., backbone stability and accessible degradability, can make this polymer a potential option for new sustainable materials.

Conditional survival and recurrence of remnant gastric cancer after surgical resection: A multi-institutional study.

The present study was designed to evaluate the dynamic survival and recurrence of remnant gastric cancer (RGC) after radical resection and to provide a reference for the development of personalized follow-up strategies. A total of 298 patients were analyzed for their 3-year conditional overall survival (COS3), 3-year conditional disease-specific survival (CDSS3), corresponding recurrence and pattern changes, and associated risk factors. The 5-year overall survival (OS) and the 5-year disease-specific survival (DSS) of the entire cohort were 41.2% and 45.8%, respectively. The COS3 and CDDS3 of RGC patients who survived for 5 years were 84.0% and 89.8%, respectively. The conditional survival in patients with unfavorable prognostic characteristics showed greater growth over time than in those with favorable prognostic characteristics (eg, COS3, ≥T3: 46.4%-83.0%, Δ36.6% vs ≤T2: 82.4%-85.7%, Δ3.3%; P < 0.001). Most recurrences (93.5%) occurred in the first 3 years after surgery. The American Joint Committee on Cancer (AJCC) stage was the only factor that affected recurrence. Time-dependent Cox regression showed that for both OS and DSS, after 4 years of survival, the common prognostic factors that were initially judged lost their ability to predict survival (P > 0.05). Time-dependent logistic regression analysis showed that the AJCC stage independently affected recurrence within 2 years after surgery (P < 0.05). A postoperative follow-up model was developed for RGC patients. In conclusion, patients with RGC usually have a high likelihood of death or recurrence within 3 years after radical surgery. We developed a postoperative follow-up model for RGC patients of different stages, which may affect the design of future clinical trials.

Failure of enhanced recovery after surgery in laparoscopic colorectal surgery: a systematic review.

PURPOSE: Enhanced recovery after surgery programs has been applied extensively in laparoscopic colorectal surgery. However, several studies have found that some patients fail from ERAS programs. It is important to identify these patients so that remedial action can be taken in a timely manner. The aim of this study was to perform a systematic review of ERAS failure and related risk factors following laparoscopic colorectal surgery. METHODS: A literature search of the PubMed, EMBASE, OVID, and Cochrane databases was performed. The search strategy involved terms related to ERAS, failure, and colorectal surgery. The main outcomes were definitions of ERAS failure and related risk factors. RESULTS: Seven studies including 1463 patients were analyzed. The definition of ERAS failure was mostly associated with a prolonged postoperative length-of-stay (poLOS). Twenty-four kinds of identified risk factors were divided into three parts, the operative part, the pathophysiological part, and the ERAS elements, of which operative factors including more intraoperative blood loss and longer operative duration were the most frequently identified. CONCLUSIONS: ERAS failure was mostly related to a prolonged poLOS, and operative factors were the most frequently identified risk factors for ERAS failure following laparoscopic colorectal surgery. These findings will help physicians to take remedial action in a timely manner. Nonetheless, high-quality randomized controlled trials following a standardized framework for evaluating ERAS programs are needed in the future.

The factors related to failure of Enhanced Recovery after Surgery (ERAS) in colon cancer surgery.

PURPOSE: Enhanced Recovery after Surgery has been proven effective for patients with gastrointestinal cancer. But radical enhanced recovery could also lead to adverse clinical outcomes. Compared with reports on the estimation of successful implementation of enhanced recovery, studies on risk factors of enhanced recovery failure are still lacking. METHODS: A retrospective analysis was carried out on 102 patients in ERAS who underwent elective colon cancer surgery. This study included 102 patients with colon cancer between 2015 and 2019, defining enhanced recovery failure as postoperative length of stay over 10 days, stay in ICU over 24 h after surgery, reoperation, death, or unplanned readmission within 30 days after surgery. Univariate and multivariate analyses were performed to explore potential risk factors of failure. RESULTS: Aged ≥ 75, open operation, number of drainage tube over 1, re-urethral catheterization, and Clavien-Dindo grade over 2 were associated with ERAS failure, according to univariate analysis. Multivariate analysis showed that age ≥ 75 [OR 7.231; P = 0.009]; open operation (OR 3.599; P = 0.021); and number of drainage tube over 1 (OR 3.202; P = 0.020) were independent risk factors for ERAS failure. CONCLUSIONS: We found age ≥ 75, open operation, and number of drainage tube over 1 are independent risk factors associated with ERAS failure after colon cancer surgery.

Epidemiological and clinical comparisons of paediatric and adult sporotrichosis in Jilin Province, China.

Sporotrichosis is endemic in Jilin Province of Northeast China. While paediatric cases make a substantial contribution to the epidemiological profile of sporotrichosis, the differences in the epidemiology and clinical manifestations of sporotrichosis between paediatric and adult patients remain unclear. We retrospectively reviewed the clinical records of 2968 cases of sporotrichosis (2113 adult patients aged ≥ 15 years and 855 paediatric patients aged < 15 years) over a nine-year period (01/01/2010-31/12/2018-). All the patients were diagnosed with sporotrichosis based on fungal culture of material from a skin lesion. In paediatric patients, the male:female ratio was 1.3:1, the incidence of sporotrichosis in the cold seasons was high (79.0%), most lesions occurred in the facial region (92.2%), and there was a preponderance of fixed cutaneous sporotrichosis (86.8%). In adult patients, the male:female ratio was 1:2.4, the incidence of sporotrichosis in the cold seasons was 66.0%, most lesions affected the extremities (48.6%) and the face (44.9%), and fixed cutaneous sporotrichosis was common (69.3%). The results indicate there were significant differences in the distribution of paediatric and adult sporotrichosis patients by sex, season with the highest occurrence of sporotrichosis, lesion sites and clinical types. Our results suggest that the epidemiology and clinical manifestations between paediatric and adult patients were different, and the route of infection of sporotrichosis in children may differ from that of adults in Jilin Province.

Graphene-Like Covalent Organic Framework with a Wide Band Gap Synthesized On Surface via Stepwise Reactions.

Developing graphene-like two-dimensional materials naturally possessing a band gap has sparked enormous interest. Thanks to the inherent wide band gap and high mobility in the 2D plane, covalent organic frameworks containing triazine rings (t-COFs) hold great promise in this regard, whilst the synthesis of single-layer t-COFs remains highly challenging. Herein, we present the fabrication of a well-defined graphene-like t-COF on Au(111). Instead of single/multiple-step single-type reactions commonly applied for on-surface synthesis, distinct stepwise on-surface reactions, including alkynyl cyclotrimerization, C-O bond cleavage, and C-H bond activation, are triggered on demand, leading to product evolution in a controlled step-by-step manner. Aside from the precise control in sophisticated on-surface synthesis, this work proposes a single-atomic-layer organic semiconductor with a wide band gap of 3.41 eV.

A novel splicing mutation of PTCH1 in a Chinese family with nevoid basal cell carcinoma syndrome.

Nevoid basal cell carcinoma syndrome (NBCCS) is a rare autosomal dominant disease characterized by the development of multiple jaw keratocysts and basal cell carcinomas (BCC) and accompanied by diverse phenotypes. The establishment of diagnosis lies on the identification of a heterozygous germline pathogenic variant in the patched homolog 1 gene (PTCH1). PTCH1 has alternative splicing and selective initial coding exon, leading to three types of encoding proteins (PTCHL, PTCHM and PTCHS). The expression of each protein in NBCCS remains ambiguous, especially the importance of the first two exons in translation. Here, we report a Chinese NBCCS family of a novel PTCH1 heterozygous mutation (IVS 2, c.394+1G>T, g.10652G>T) identified by genomic sequencing and reverse-transcription-PCR as aberrant splicing. To the best of our knowledge, this is the first report of NBCCS with a splicing site mutation in intron 2 resulting in exon 2 skipping. Our finding suggests that exon 2 plays an important role in the development of NBCCS and further speculates that the role of longer isoforms PTCHL and PTCHM is crucial in NBCCS, while that of short isoform PTCHS might be dispensable.

Characteristics of Polybrominated Diphenyl Ethers Released from Thermal Treatment and Open Burning of E-Waste.

Primitive processing of e-waste potentially releases abundant organic contaminants to the environment, but the magnitudes and mechanisms remain to be adequately addressed. We conducted thermal treatment and open burning of typical e-wastes, that is, plastics and printed circuit boards. Emission factors of the sum of 39 polybrominated diphenyl ethers (∑39PBDE) were 817-1.60 × 105 ng g-1 in thermal treatment and nondetected-9.14 × 104 ng g-1, in open burning. Airborne particles (87%) were the main carriers of PBDEs, followed by residual ashes (13%) and gaseous constituents (0.3%), in thermal treatment, while they were 30%, 43% and 27% in open burning. The output-input mass ratios of ∑39PBDE were 0.12-3.76 in thermal treatment and 0-0.16 in open burning. All PBDEs were largely affiliated with fine particles, with geometric mean diameters at 0.61-0.83 µm in thermal degradation and 0.57-1.16 µm in open burning from plastic casings, and 0.44-0.56 and nondetected- 0.55 µm, from printed circuit boards. Evaporation and reabsorption may be the main emission mechanisms for lightly brominated BDEs, but heavily brominated BDEs tend to affiliate with particles from heating or combustion. The different size distributions of particulate PBDEs in emission sources and adjacent air implicated a noteworthy redisposition process during atmospheric dispersal.