Migrate demographic group for fair Graph Neural Networks.

Graph Neural networks (GNNs) have been applied in many scenarios due to the superior performance of graph learning. However, fairness is always ignored when designing GNNs. As a consequence, biased information in training data can easily affect vanilla GNNs, causing biased results toward particular demographic groups (divided by sensitive attributes, such as race and age). There have been efforts to address the fairness issue. However, existing fair techniques generally divide the demographic groups by raw sensitive attributes and assume that are fixed. The biased information correlated with raw sensitive attributes will run through the training process regardless of the implemented fair techniques. It is urgent to resolve this problem for training fair GNNs. To tackle this problem, we propose a brand new framework, FairMigration, which is able to migrate the demographic groups dynamically, instead of keeping that fixed with raw sensitive attributes. FairMigration is composed of two training stages. In the first stage, the GNNs are initially optimized by personalized self-supervised learning, and the demographic groups are adjusted dynamically. In the second stage, the new demographic groups are frozen and supervised learning is carried out under the constraints of new demographic groups and adversarial training. Extensive experiments reveal that FairMigration achieves a high trade-off between model performance and fairness.

TREM1/DAP12 based novel multiple chain CAR-T cells targeting DLL3 show robust anti-tumour efficacy for small cell lung cancer.

Small cell lung cancer (SCLC), recognized as the most aggressive subtype of lung cancer, presents an extremely poor prognosis. Currently, patients with small cell lung cancer face a significant dearth of effective alternative treatment options once they experience recurrence and progression after first-line therapy. Despite the promising efficacy of immunotherapy, particularly immune checkpoint inhibitors in non-small cell lung cancer (NSCLC) and various other tumours, its impact on significantly enhancing the prognosis of SCLC patients remains elusive. DLL3 has emerged as a compelling target for targeted therapy in SCLC due to its high expression on the membranes of SCLC and other neuroendocrine carcinoma cells, with minimal to no expression in normal cells. Our previous work led to the development of a novel multiple chain chimeric antigen receptor (CAR) leveraging the TREM1 receptor and DAP12, which efficiently activated T cells and conferred potent cell cytotoxicity. In this study, we have developed a DLL3-TREM1/DAP12 CAR-T (DLL3-DT CAR-T) therapy, demonstrating comparable anti-tumour efficacy against SCLC cells in vitro. In murine xenograft and patient-derived xenograft models, DLL3-DT CAR-T cells exhibited a more robust tumour eradication efficiency than second-generation DLL3-BBZ CAR-T cells. Furthermore, we observed elevated memory phenotypes, induced durable responses, and activation under antigen-presenting cells in DLL3-DT CAR-T cells. Collectively, these findings suggest that DLL3-DT CAR-T cells may offer a novel and potentially effective therapeutic strategy for treating DLL3-expressing SCLC and other solid tumours.

Synthesis of α,ω-End Functionalized Polydienes: Allylic-Bearing Heteroleptic Aluminums for Selective Alkylation and Transalkylation in Coordinative Chain Transfer Polymerization.

There are still challenges in the preparation of difunctional stereoregular polydienes, especially for the construction of initiating chain-end functionalization. Coordinative chain transfer polymerization (CCTP) provides a way to achieve the goal but usually requires sophisticated functionalized catalysts as well as expensive chain transfer agents (CTAs). In this work, heteroleptic aluminum with oligo(dienyl) substituents (oligo-Al agents) were readily prepared by living anionic polymerization (LAP) technique. The oligo-Al agents used in Nd-mediated CCTPs of dienes exhibit highly selective alkylation and transalkylation features. Kinetics and transfer efficiency studies using 1 H NMR, 13 C NMR, 1 H-13 C HSQC, and Dosy NMR analyses revealed that the resulting polydienes possess substituents at the initiating chain-end that have transferred from the oligo-Al agents. The functionalization efficiency of the initiating chain-end is up to 99 %, and the molar mass regulation efficiency of heteroleptic aluminum is higher than that of the traditional CTA Ali Bu2 H (0.608 vs. 0.410). Based on the experimental results and density functional theory (DFT) calculations, we propose a mechanism in which allylic-Al acts as an efficient alkylating moiety in catalyst preformation and also as an effective transfer agent in polymerization. Taking advantage of these features, di-functionalized polyisoprene, polybutadiene, and poly(isoprene-co-butadiene) can be facilely synthesized.

Boosting the Thermal Stability of α-Diimine Palladium Complexes in Norbornene Polymerization from Construction of Intraligand Hydrogen Bonding and Simultaneous Increasing Axial/Equatorial Bulkiness.

Increasing the thermostability of α-diimine late-transition-metal complexes and therefore rendering them more active at higher temperatures is of great importance, yet challenging for the olefin polymerization field. In the present research, a new family of α-diimine palladium complexes that can promote norbornene polymerization at high temperatures (up to 140 °C) is disclosed. Because of the conformational restriction caused by increasing the axial and equatorial bulkiness as well as the presence of intraligand H···F hydrogen bonds, N-aryl rotations can be efficiently restricted, therefore circumventing the deactivation of the active species at high temperatures. At 80-140 °C, these complexes can efficiently catalyze norbornene homopolymerizations, giving high catalytic activities up to 5.65 × 107 g of PNB per mole Ni per hour and polymers with high molecular weights up to 37.2 × 104 g/mol, which are highly superior to catalytic systems mediated by CF3-free complexes. Moreover, these complexes could also afford medium catalytic activities in the presence of polar 5-norbornene-2-carboxylic acid methyl ester (NB-COOCH3).

Correction: In-chain functionalized syndiotactic 1,2-polybutadiene by a Ziegler-Natta iron(iii) catalytic system.

[This corrects the article DOI: 10.1039/C9RA06499K.].

Synthesis and Properties of In-Situ Bulk High Impact Polystyrene Toughened by High cis-1,4 Polybutadiene.

A series of high impact polystyrenes (HIPS) were successfully prepared by in-situ bulk polymerization. Selective polymerization of butadiene (Bd) in styrene (St) was achieved by using a neodymium bis(2-ethylhexanol)phosphonate/diisobutyl aluminum hydride/diethylaluminum chloride (Nd(P507)3/Al(i-Bu)2H/AlEt2Cl) catalyst, affording a prepolymer with high cis-1,4 content of 96.6% and extremely low styrene content of 1.01%. The prepolymer solution was further subjected to the radical polymerization of styrene to produce HIPS. The impact strength of HIPS increased from 48.5 to 166.2 J/m, with an increase of rubber content from 5% to 15%, whereas the tensile strength at break decreased from 17 to 12.5 MPa. Moreover, the impact strength and the tensile strength at break of HIPS increased from 72.4 J/m to 120.6 J/m and 13.2 to 16 MPa, respectively, as the initiator concentration decreased from 0.05% to 0.01%. HIPS showed the highest impact strength of 84.8 J·m-1 and displayed well "salami" morphology when using a trifunctional 3,6,9-triethyl-3,6,9-trimethyl-1,4,7-triperoxonane initiator.

Synthesis of Propylene-co-Styrenic Monomer Copolymers via Arylation of Chlorinated PP and Their Compatibilization for PP/PS Blend.

A series of propylene-co-styrenic monomer copolymers were synthesized using the Friedel⁻Crafts alkylation reaction between chlorinated PP and substituted benzene, and the effects of these copolymers on a PP/PS (80/20) blend were investigated by using the impact test, morphology observation, thermo- and dynamic mechanical analysis, and rheology measurements. The results showed that the compatibilization efficiency varied as the variation of the substitute on the benzene ring of the styrenic monomer unit was incorporated in the PP chain in an order of methyl > ethyl > methoxyl. The copolymers bearing a crystalline isotactic polypropylene chain sequence and rubbery propylene-co-styrene-like unit chain segments may prepossess imaginable applications, giving an example for the synthesis and applications of PP-based copolymers, initiating a new way to broaden the polyolefin-based material family.

In-chain functionalized syndiotactic 1,2-polybutadiene by a Ziegler-Natta iron(iii) catalytic system.

Copolymerization of 1,3-butadiene with four 1-substituted 1,3-diene comonomers bearing amino and alkyoxy groups by a Ziegler-Natta iron(iii) catalytic system to access in-chain functionalized syndiotactic 1,2-polybutadiene is reported herein. The polar comonomer content can be easily regulated by varying the comonomer loadings or polymerization conditions, affording functionalized syndiotactic 1,2-polybutadiene with different amounts of functionalities. The incorporation of a polar comonomer showed little influence on the 1,2-content and stereoregularity of the resulting polymers, giving a 1,2-structure as high as ∼85% and an rrrr pentad of 81.0%. Significantly improved surface properties of the polymers was obtained after incorporation of polar comonomer, as revealed from the remarkably decreased water contact angles.

Ethylene Polymerization and Copolymerization with Polar Monomers Using Nickel Complexes Bearing Anilinobenzoic Acid Methyl Ester Ligand.

Neutral nickel complexes containing an anilinobenzoic acid methyl ester ligand are prepared and applied for the ethylene polymerization and copolymerization with polar monomers. The complex C2 containing isopropyl substituent on the aniline ligand conducts ethylene polymerization with high activity and good thermal stability. Most importantly, the catalyst promotes the copolymerization of ethylene and polar monomers with high activity (up to 277 kg·mol-1·h-1), affording ester-functionalized semicrystalline polyethylene with reasonable polar monomer content (up to 3.20 mol %).

Use of Vanadium Complexes Bearing Naphthalene-Bridged Nitrogen-Sulfonate Ligands as Catalysts for Copolymerization of Ethylene and Propylene.

Vanadium complexes bearing naphthalene-bridged nitrogen-sulfonate ligand ([ê²(N,O)-8-(PhN)-1-naphthalenesulfonato]VOCl (1a) and [ê²(N,O)-8-(PhN)-1-naphthalenesulfonato]VCl2 (1b)) were synthesized. Activated by ethylaluminium sesquichloride (EASC) and in the presence of ethyl trichloroacetate (ETCA) as reactivator, complexes 1a and 1b showed activities of up to 39.1 kg polymer (mol V)-1 h-1, affording the copolymers with high molecular weights (Mw up to 28 × 104) and narrow molecular weight distributions (Mw/Mn ~ 3.0) as well as high propylene incorporation of up to 49.4%. Compared to the traditional VOCl3 system, these complexes exhibited higher propylene incorporation ability and higher catalytic activities especially at high polymerization temperatures of 50 °C and above. Determined by DSC and 13C NMR, the copolymers obtained with 1a and 1b had more random structures than that with the VOCl3 system.

Iminopyridine-Based Cobalt(II) and Nickel(II) Complexes: Synthesis, Characterization, and Their Catalytic Behaviors for 1,3-Butadiene Polymerization.

A series of iminopyridine ligated Co(II) (1a⁻7a) and Ni(II) (1b⁻7b) complexes were synthesized. The structures of complexes 3a, 4a, 5a, 7a, 5b, and 6b were determined by X-ray crystallographic analyses. Complex 3a formed a chloro-bridged dimer, whereas 4a, 5a, and 7a, having a substituent (4a, 5a: CH3; 7a: Br) at the 6-position of pyridine, producing the solid structures with a single ligand coordinated to the central metal. The nickel atom in complex 5b features distorted trigonal-bipyramidal geometry with one THF molecule ligating to the metal center. All the complexes activated by ethylaluminum sesquichloride (EASC) were evaluated in 1,3-butadiene polymerization. The catalytic activity and selectivity were significantly influenced by the ligand structure and central metal. Comparing with the nickel complexes, the cobalt complexes exhibited higher catalytic activity and cis-1,4-selectivity. For both the cobalt and nickel complexes, the aldimine-based complexes showed higher catalyst activity than their ketimine counterparts.

[Cervical tracheal resection with primary anastomosis for benign tracheal stricture in adult].

OBJECTIVE: To introduce the outcomes of tracheal resection with primary end to end anastomosis for benign cervical tracheal stenosis, and to discuss the strategy for prevention of surgical complications. METHODS: A retrospective analysis was performed in 12 patients diagnosed as benign cervical tracheal stenosis from October 2009 to June 2012. Laryngo-tracheal endoscopic examination and computed tomography (CT) were used to assess the degree of stenosis, the grade of inflammation and edema of the subglottis and trachea, and the extent of stenosis and the remaining linear amount of normal airway. The Meyer and Cotton grading system was used to categorise the clinical severity of the stenoses. All patients underwent tracheal resection with primary end to end anastomosis. RESULTS: The length of cervical tracheal stenosis ranged from 2.3 to 4.1 cm. Grade II stenosis was present in three patients, Grade III stenosis was present in seven patients and grade IV stenosis in two patients. Successful extubation was achieved in all 12 cases. After surgery, temporary hoarseness occurred in 1 patient (8.3%); unilateral pulmonary atelectasis with pleural effusion occurred in 1 patient (8.3%); subcutaneous emphysema with infection occurred in 1 patient (8.3%); mild dysphagia occurred in 3 patients (25.0%); a slight deepening of the tone of voice occurred in 5 patients (41.7%), granulation tissue growth near the suture occurred in 3 patients (25.0%), and suture dehiscence did not occur in any patient. The follow-up period ranged from 6 months to 38 months, no patient developed restenosis. CONCLUSIONS: It presents a high success rate and good functional result of tracheal resection with primary end-to-end anastomosis. Therefore, it is an effective and reliable approach for the management of benign cervical tracheal stenosis. To avoid complications, the preoperative assessment, patients selection and postoperative management should be emphasized.

Synthesis of bis(N-arylcarboximidoylchloride)pyridine cobalt(II) complexes and their catalytic behavior for 1,3-butadiene polymerization.

A new family of bis(N-arylcarboximidoylchloride)pyridine cobalt(II) complexes with the general formula [2,6-(ArN=CCl)2C5H3N]CoCl2 (Ar = 2,4,6-Me3C6H2, 4a; 2,6-(i)Pr2C6H3, 4b; 2,6-Me2C6H3, 4c; C6H5, 4d; 4-Cl-2,6-Me2C6H2, 4e) and a typical Brookhart-Gibson-type reference complex [2,6-(2,4,6-Me3C6H2N=CMe)2C5H3N]CoCl2 (5a) were synthesized and characterized. Determined by X-ray crystallographic analysis, complexes 4a, 4c-e, and 5a adopted a trigonal bipyramidal configuration, and 4b adopted a distorted square pyramidal geometry. In combination with ethylaluminum sesquichloride (EASC), all the complexes were highly active towards 1,3-butadiene polymerization, affording polybutadiene with predominant cis-1,4 content (up to 96%). 4a with chlorine atoms at the imine groups exhibited higher catalytic activity than did 5a, indicating that the incorporation of chlorine atoms into the ligand improves the activity. The activity of the complexes in 1,3-butadiene polymerization was in the order of 4a > 4c ∼ 4e ∼ 4b > 4d, which is consistent with the trend of spatial opening degree around the metal center in the complexes as revealed by crystallographic data. Screening polymerization conditions proved that EASC was the most efficient among the cocatalysts examined.

Tumoral indoleamine 2,3-dioxygenase expression predicts poor outcome in laryngeal squamous cell carcinoma.

The development of laryngeal squamous cell carcinomas (LSCC) is strongly influenced by the host immune system. Indoleamine 2,3-dioxygenase (IDO) can promote and maintain an immunosuppressive microenvironment which can impede the efficacy of anticancer responses. The purpose of the current study is to investigate the prognostic value of intratumoral IDO expression in LSCC. The expression of IDO protein was retrospectively assessed by immunohistochemistry in 187 LSCC patients. The potential association of tumor IDO expression with clinical parameters and tumor-infiltrating lymphocytes (TILs) was analyzed separately. Survival curves were estimated by the Kaplan-Meier method, and differences between groups were determined by log-rank test. Multivariate logistic regression analysis was performed to determine the independent factors associated with survival. Based on the evaluation score, 90 carcinomas (48.1 %) were identified with high IDO expression and 97 carcinomas (51.9 %) showed low expression. Tumor IDO expression was not associated with clinical stage, presence of metastases, and other clinicopathological parameters. Also, high IDO expression was not correlated with tumor-infiltrating CD3(+) and CD8(+) TILs. Instead it was positively related with the density of FOXP3(+) Tregs. Furthermore, multivariate analysis identified a significant association of overall survival and disease-free survival with tumor IDO status. IDO high expression represents a significant negative prognostic factor in patients with LSCC. Current results provide further support for using IDO as an immunotherapeutic target in LSCC. The precise role of tumoral IDO in human LSCC remains to be elucidated in the future.

Endoscopic removal of esophageal impacted dentures.

OBJECTIVES: A retrospective study was conducted on 6 patients with esophageal impacted dentures removed via rigid esophagoscopy. METHODS: Six patients with esophageal impacted dentures were treated in our department, and the following technique was successfully performed. With the patients under general anesthesia, we inserted the endoscope to visualize the impacted dentures, fixed them with forceps, and then stuffed several cotton slivers soaked in saline solution into the esophagus around the dentures with another forceps. Then we extracted the dentures from the esophagus. RESULTS: All dentures were extracted through esophagoscopy, and there were no severe complications except for 1 case of esophageal hematoma. CONCLUSIONS: The dilation method using saline solution-soaked cotton slivers is relatively safe and effective in removing impacted dentures from the esophagus, avoiding open surgery and possible perforation.

Canal wall-down mastoidectomy with mastoid obliteration for pediatric cholesteatoma.

CONCLUSIONS: As cholesteatoma is widespread and erosive, it should be cleared away thoroughly, to keep a dry ear and conserve maximum hearing ability in children. Canal wall-down mastoidectomy with mastoid and epitympanum obliteration is a good choice for treatment of cholesteatoma in children. OBJECTIVE: To investigate canal wall-down mastoidectomy with mastoid and epitympanum obliteration for the treatment of cholesteatoma in children. PATIENTS AND METHODS: A retrospective analysis of all cases of pediatric middle ear cholesteatoma in children aged 5-12 years between 1999 and 2006 was conducted in Anhui Provincial Hospital. The follow-up information was completed. Forty-five patients (48 ears) were treated with canal wall-down mastoidectomy with mastoid and epitympanum obliteration and followed up for 2-5 years (mean 3.1 years). RESULTS: The recurrence rate and residual rate were 4.16% and 0%, respectively. All ears were dry within 8-10 weeks. Aural discharge was detected in two cases and controlled with antibiotic ear drops without complications. The dry ear rate was 95.8%. The air-bone gap closure had a mean of 17.2 +/- 2 dB. No obvious complication occurred after operations.

[Transoral endoscopic CO2 laser surgery for hypopharynx in experimental animals].

OBJECTIVE: To explore the substantial resection limits of CO2 laser surgery for hypopharynx and the course of wound healing in animals, for the purpose of evaluating the clinic usefulness of transoral CO2 laser surgery in the treatment of selected hypopharyngeal carcinomas. METHODS: Twenty-three dogs were randomly assigned to two groups. Group one (11 dogs) received left piriform sinus resection, group two (12 dogs) received the resection of posterior wall of the hypopharynx. Six dogs in group one were killed immediately or 4, 8, 12, 16, 20 d post-operatively. Seven dogs in group two were killed immediately or 7, 14, 21, 28, 35, 42 d post-operatively. The whole larynx and hypopharynx were taken out and the specimens were examined by naked eyes and under microscope. The other 5 dogs in each group were fed until the wound healed, the duration were observed. RESULTS: All the operations were successful and the results were satisfactory. In group one, the dogs could take food the day after operation; two dogs had slight cough during eating and recovered after five days. In group two, the dogs could take food the next day after operation, eight dogs had slight cough during eating and recovered after ten days. The excision dimension was satisfactory. In group one (resection of the lateral wall of piriform sinus), the size of raw surface was (7.5 +/- 0.8) cm2 (x +/- s) and the healing time was (18.4 +/- 1.5) d. In group two (resection of the posterior wall of the hypopharynx), the wound surface was (7.0 +/- 0.5) cm2 and the healing time was (39.8 +/- 1.9) d. The healing time in group two was significantly longer than that in group one (t = 19.535, P <0. 01). The post-operative healing process were observed, including cellulose membrane coverage, granulation filling and epithelization. CONCLUSIONS: Transoral CO2 laser was suitable for partial hypopharynx resection. Animals can recuperate well with little complications. Although the course of wound healing was delayed, wound surface can recover with good laryngeal and deglutition functions.

Synthesis and extremely high gas permeability of polyacetylenes containing polymethylated indan/tetrahydronaphthalene moieties.

Polymethylated poly(diphenylacetylene) derivatives, a new category of substituted polyacetylenes, were successfully synthesized, and proved to show extremely high gas permeability.

[Prevention of complications during paralaryngeal space neoplasms surgery].

OBJECTIVE: To explore the prevention of complications during the the paralaryngeal space (PPS) neoplasms surgery. METHOD: A retrospect study was carried out from 41 patients, suffering from paralaryngeal space neoplasms and recerving surgery from 1990 to 2002. The surgical procedures included oral approach in 6 cases, parotid approach in 6 cases, cervical approach in 25 cases, cervical approach with mandibular swing in 2 cases and lateral skull-base approach 2 in cases. Eight cases got the tracheodectomy during the operations. The tumor in 37 cases were resected throughly, except for 4 cases with partial resection. RESULT: The patients were followed up for 11 months to 6 years. The surgical complications consists of surgical cavity infections in 2 cases, a massive bleeding in 1 case with huge nerve sheath tumor and permanent nerves damage in 7 cases, including Horner's syndrome (2 cases) and nerves damage (5 cases), such as VII, IX, X and XI. Six cases relapsed: 1 case with benign tumor through oral approach and 5 cases with malignant neoplasms. CONCLUSION: Familiarity with PPS anatomy, preoperational evaluation in detail, proper surgery approach and perfect treatment during the operation are vital important to avoid the complications in PPS neoplasms.

[FCM detection and pathology observation of 5 mm cutting-edge of laryngocarcinoma].

OBJECTIVE: To explore the safety of 5 mm cutting-edges with the analysis of DNA contend and cell cycle and the pathology observation. METHOD: Twenty specimens of laryngocarcinoma and its cutting-edges were analyzed by flow cytometry, contrasting to 5 samples of normal larynx tissue, and their light-microscopy and electra-microscopy were discussed. RESULT: The DNA aneuploidy(AN) rate in the laryngocarcinoma, its cutting-edges and the normal tissue is respectively 60% (12/20), 15%(3/20) and 0. The rate of S phrase of the laryngocarcinoma and its cutting-edges is respectively 20.33 +/- 6.0 and 12.35 +/- 3.81, so the DI 1.78 +/- 0.82 and 1.07 +/- 0.04, PI 29.09 +/- 6.8 and 11.75 +/- 3.75, there are significant differences (P < 0.05). The light-microscopy showed 5 mm cutting-edges were infiltrated by carcinoma in the form of submucosa or extention of carcinoma in situ and the results was, to some extension, consistent with the findings of FCM. CONCLUSION: The safety of 5 mm cutting-edge varies depending on whether invading paraglottic space.