Publications by authors named "Dongbing Zhao"

69 Publications

Personalized analysis of minimal residual cancer cells in peritoneal lavage fluid predicts peritoneal dissemination of gastric cancer.

J Hematol Oncol 2021 Oct 12;14(1):164. Epub 2021 Oct 12.

State Key Laboratory of Molecular Oncology, National Cancer Center/National Clinical Research Center for Cancer/Cancer Hospital, Chinese Academy of Medical Sciences and Peking Union Medical College, Panjiayuan nanli 17, Chaoyang District, Beijing, 100021, China.

Peritoneal dissemination (PD) is a major type of gastric cancer (GC) recurrence and leads to rapid death. Current approaches cannot precisely determine which patients are at high risk of PD to provide early intervention. In this study, we developed a technology to detect minimal residual cancer cells in peritoneal lavage fluid (PLF) samples with a personalized assay profiling tumor-specific mutations. In a prospective cohort of 104 GC patients, the technology detected all the cases that developed PD with 100% sensitivity and 85% specificity. The minimal residual cancer cells in PLF were associated with a significantly increased risk of PD (HR = 145.13; 95% CI 20.20-18,435.79; p < 0.001), which was the strongest independent predictor over pathologic diagnosis and cytological diagnosis. In pathologically high-risk (pT4) patients, the PLF mutation profiling model exhibited a greater specificity of 91% and a positive predictive value of 88% while retaining a sensitivity of 100%. This approach may help in the postsurgical management of GC patients by detecting PD far before metastatic lesions grow to a significant size detectable by conventional methods such as MRI and CT scanning.
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http://dx.doi.org/10.1186/s13045-021-01175-2DOI Listing
October 2021

Nickel(0)-Catalyzed Asymmetric Ring Expansion Toward Enantioenriched Silicon-Stereogenic Benzosiloles.

Angew Chem Int Ed Engl 2021 Sep 29. Epub 2021 Sep 29.

Nankai University, College of Chemistry, CHINA.

The development of a straightforward strategy to obtain enantioenriched silicon-stereogenic benzosiloles remains a challenging yet appealing synthesis venture due to their potential future application in chiral electronic and optoelectronic devices. In this context, all of the existing methods rely on Rh-catalyzed systems and are somewhat limited in scope. Herein, we disclose the first Ni(0)-catalyzed ring expansion process that enables the preparation of benzosiloles possessing tetraorganosilicon stereocenters in excellent yields and enantioselectivities. The presented catalysis strategy is further applied to the asymmetric synthesis of silicon-stereogenic bis-silicon-bridged π-extended systems. Preliminary studies reveal that such compounds exhibit pronounced fluorescence emission, Cotton effects and circularly polarized luminescence (CPL) activity.
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http://dx.doi.org/10.1002/anie.202111025DOI Listing
September 2021

A ring expansion strategy towards diverse azaheterocycles.

Nat Chem 2021 Oct 19;13(10):1006-1016. Epub 2021 Jul 19.

State Key Laboratory and Institute of Elemento-Organic Chemistry, College of Chemistry, Nankai University, Tianjin, China.

The development of innovative strategies for the synthesis of N-heterocyclic compounds is an important topic in organic synthesis. Ring expansion methods to form large N-heterocycles often involve the cycloaddition of strained aza rings with π bonds. However, in some cases such strategies suffer from some limitations owing to the difficulties in controlling the regioselectivity and the accessibility of specific π-bond synthons. Here, we report the development of a general ring expansion strategy that involves a formal cross-dimerization between three-membered aza heterocycles and three- and four-membered-ring ketones through synergistic bimetallic catalysis. These formal cross-dimerizations of two different strained rings are efficient and scalable, and provide a straightforward and broadly applicable means of assembling diverse N-heterocycles, such as 3-benzazepinones, dihydropyridinones and uracils, which are versatile units in numerous drugs and biologically active compounds. Preliminary mechanistic studies revealed that the C-C bond of strained ring ketones is first cleaved by the Pd species during the reaction.
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http://dx.doi.org/10.1038/s41557-021-00746-7DOI Listing
October 2021

Regional and racial disparity in proximal gastric cancer survival outcomes 1996-2016: Results from SEER and China National Cancer Center database.

Cancer Med 2021 07 9;10(14):4923-4938. Epub 2021 Jun 9.

Department of Pancreatic and Gastric Surgical Oncology, National Cancer Center/National Clinical Research Center for Cancer/Cancer Hospital, Chinese Academy of Medical Sciences and Peking Union Medical College, Beijing, China.

Background: Given the growing incidence and aggressive biological behavior of proximal gastric cancer (PGC) as reported, it is important to understand which regional or racial populations are at poor prognosis so that interventions can be treated appropriately. We sought to explore regional treatment differences as well as racial genes influence survival outcomes in China and the US patients with PGC.

Methods: PGC patients defined as tumors with the epicenter located in cardia (C16.0) or fundus (C16.1) from 1996 to 2016 were identified from the Surveillance Epidemiology and End Results (SEER) in the United States as well as data from a high-volume National Cancer Center Database in China. Overall survival (OS) curves were plotted for different regional or racial groups, respectively, using the Kaplan-Meier method and compared statistically using the log-rank test. Differentially expressed genes (DEGs) analysis was performed using TCGA database.

Results: Finally, the cohort consistent of 40973 PGC patients who enrolled in SEER database (n = 36305) or China National Cancer Center (n = 4668), and divided into 4 racial groups: Chinese (n = 5179), Black (n = 2429), White (n = 31185), and Others (n = 2096). After controlling for confounding variables, racial factors were independently associated with poor survival included Black ethnicity (HR = 1.376, 95% CI: 1.066-1.7760, p = 0.014) and White ethnicity (HR = 1.262, 95% CI: 1.005-1.583, p = 0.045) when compared to Chinese ethnicity in total PGC patients. Even in the same region for only US group, Chinese PGC patients also showed better prognosis.

Conclusions: In conclusion, we demonstrated the different survival outcomes of PGC patients in different regions or races from two high-volume database SEER and China National Cancer Center database. These survival differences are likely influenced by a number of factors (e.g., access to screening, quality of gastrectomy, neo/adjuvant therapy, and biological genes itself). More importantly, a better understanding of these disparities could lead to interventions that may help to abolish these disparities.
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http://dx.doi.org/10.1002/cam4.4033DOI Listing
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC8290239PMC
July 2021

Exceeding 30 ELNs is strongly recommended for pT3-4N0 patients with gastric cancer: A multicenter study of survival, recurrence, and prediction model.

Cancer Sci 2021 Aug 2;112(8):3266-3277. Epub 2021 Jul 2.

National Cancer Center/National Clinical Research Center for Cancer/Cancer Hospital, Chinese Academy of Medical Sciences and Peking Union Medical College, Beijing, China.

The argument concerning the exact minimum number of examined lymph nodes (ELNs) has continued for a long time among various regions, and no consensus has been reached for stratified pathological T stages for data to date. Data from 4607 pN0 patients with gastric cancer were analyzed. Kaplan-Meier analysis showed the similar overall survival (OS) outcomes among the 3 groups (ELNs ≤ 15, 16 ≤ ELNs ≤ 29 and ELNs ≥ 30, P = .171). However, the ELNs ≥ 30 group had a better disease-free survival (DFS) outcome compared with the others (all P < .05). An increased ELN group (ELNs ≥ 30) showed an improved OS only for pT3 patients (hazard ratio [HR] = 0.397, 95% confidence interval (CI): 0.182-0.866, P = .020), while an improved DFS for pT3 patients (HR = 0.362, 95%CI: 0.152-0.860, P = .021) and pT4 patients (HR = 0.484, 95%CI: 0.277-0.844, P = .011) in the multivariate analysis. A well discriminated and calibrated nomogram was constructed to predict the probability of the OS and DFS, with the C-index for OS and DFS prediction of 0.782 (95%CI: 0.735 to 0.829) and 0.738 (95%CI: 0.685 to 0.791), respectively. This study provides new and useful insights into the impact of ELN count on reducing stage migration and postoperative recurrence of pN0 patients with gastric cancer in 2000-2017. In conclusion, a larger number of ELNs is suggested for surgeons to prolong the prognosis of pN0 gastric cancer, especially for pT3 patients.
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http://dx.doi.org/10.1111/cas.15003DOI Listing
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC8353901PMC
August 2021

Modular Synthesis of Pentagonal and Hexagonal Ring-Fused NBN-Phenalenes Leading to an Excited-State Aromatization-Induced Structural Planarization Molecular Library.

J Am Chem Soc 2021 04 7;143(15):5903-5916. Epub 2021 Apr 7.

State Key Laboratory and Institute of Elemento-Organic Chemistry, College of Chemistry, Nankai University, Tianjin 300071, People's Republic of China.

Although polycyclic aromatic hydrocarbons (PAHs) with a nitrogen-boron-nitrogen (NBN) moiety have recently attracted tremendous interest due to their intriguing electronic and optoelectronic properties, all of the NBN-fused π-systems reported to date are called NBN-dibenzophenalenes and were synthesized by electrophilic aromatic substitution. The synthesis of NBN-phenalenes remains challenging, and transition-metal catalysis has never been utilized to construct NBN-embedded π-scaffolds. Herein, a palladium-catalyzed cyclization/bicyclization strategy was developed for the synthesis of diverse pentagonal and hexagonal ring-fused NBN-phenalenes and half-NBN-phenalenes. All of the NBN-embedded π-scaffolds presented in our paper are fluorescent in both solution and the solid state. Further investigations showed that the five-membered NBN rings exhibit the properties of traditional luminogens, while those with a six-membered NBN ring generally undergo photoinduced structural planarization (PISP) and exhibit different colors and quantum yields of fluorescence with different concentrations in solution. Time-resolved spectroscopy and TD-DFT calculations revealed that excited-state aromatization is the driving force for PISP in hexagonal ring-fused NBN-π systems, leading to the formation of excimers. Notably, the scope of PISP compounds is still quite limited, and PISP has never been observed in NBN-π systems before. These hexagonal ring-fused NBN-π systems constitute a novel PISP molecular library and appear to be a new class of aggregation-induced excimer emission (AIEE) materials. Finally, the AIEE behavior of these six-membered NBN rings was applied to the detection of nitro explosives, achieving excellent sensitivity. In general, this work provides a new viewpoint for synthesizing NBN-fused π-systems and understanding the excited-state motion of luminogens.
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http://dx.doi.org/10.1021/jacs.1c01339DOI Listing
April 2021

Development and validation of a novel competing risk model for predicting survival of esophagogastric junction adenocarcinoma: a SEER population-based study and external validation.

BMC Gastroenterol 2021 Jan 26;21(1):38. Epub 2021 Jan 26.

Department of Pancreatic and Gastric Surgical Oncology, National Cancer Center/National Clinical Research Center for Cancer/Cancer Hospital, Chinese Academy of Medical Sciences and Peking Union Medical College, No. 17 PanjiayuanNanli, Chaoyang District, Beijing, 100021, China.

Background: Adenocarcinoma in Esophagogastric Junction (AEG) is a severe gastrointestinal malignancy with a unique clinicopathological feature. Hence, we aimed to develop a competing risk nomogram for predicting survival for AEG patients and compared it with new 8th traditional tumor-node-metastasis (TNM) staging system.

Methods: Based on data from the Surveillance, Epidemiology, and End Results (SEER) database of AEG patients between 2004 and 2010, we used univariate and multivariate analysis to filter clinical factors and then built a competing risk nomogram to predict AEG cause-specific survival. We then measured the clinical accuracy by comparing them to the 8th TNM stage with a Receiver Operating Characteristic (ROC) curve, Brier score, and Decision Curve Analysis (DCA). External validation was performed in 273 patients from China National Cancer Center.

Results: A total of 1755 patients were included in this study. The nomogram was based on five variables: Number of examined lymph nodes, grade, invasion, metastatic LNs, and age. The results of the nomogram was greater than traditional TNM staging with ROC curve (1-year AUC: 0.747 vs. 0.641, 3-year AUC: 0.761 vs. 0.679, 5-year AUC: 0.759 vs. 0.682, 7-year AUC: 0.749 vs. 0.673, P < 0.001), Brier score (3-year: 0.198 vs. 0.217, P = 0.012; 5-year: 0.198 vs. 0.216, P = 0.008; 7-year: 0.199 vs. 0.215, P = 0.014) and DCA. In external validation, the nomogram also showed better diagnostic value than traditional TNM staging and great prediction accuracy.

Conclusion: We developed and validated a novel nomogram and risk stratification system integrating clinicopathological characteristics for AEG patients. The model showed superior prediction ability for AEG patients than traditional TNM classification.
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http://dx.doi.org/10.1186/s12876-021-01618-7DOI Listing
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC7836166PMC
January 2021

Bis-silylation of internal alkynes enabled by Ni(0) catalysis.

Nat Commun 2021 Jan 4;12(1):68. Epub 2021 Jan 4.

State Key Laboratory and Institute of Elemento-Organic Chemistry, College of Chemistry, Nankai University, 300071, Tianjin, China.

1,2-Bis-silyl alkenes have exciting synthetic potential for programmable sequential synthesis via manipulation of the two vicinal silyl groups. Transition metal-catalyzed bis-silylation of alkynes with disilanes is the most straightforward strategy to access such useful building blocks. However, this process has some limitations: (1) symmetric disilanes are frequently employed in most of the reactions to assemble two identical silyl groups, which makes chemoselective differentiation for stepwise downstream transformations difficult; (2) the main catalysts are low-valent platinum group transition metal complexes, which are expensive; and (3) internal alkynes remain challenging substrates with low inherent reactivity. Thus, the development of abundant metal-catalyzed bis-silylation of internal alkynes with unsymmetrical disilanes is of significance. Herein, we solve most of the aforementioned limitations in bis-silylation of unsaturated bonds by developing a strongly coordinating disilane reagent and a Ni(0) catalytic system. Importantly, we sufficiently realize the stepwise recognition of the two silyl groups, making this synthetic protocol of wide potential utility.
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http://dx.doi.org/10.1038/s41467-020-20392-wDOI Listing
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC7782505PMC
January 2021

The Effect of Neoadjuvant Therapies for Patients with Locally Advanced Gastric Cancer: A Propensity Score Matching Study.

J Cancer 2021 1;12(2):379-386. Epub 2021 Jan 1.

Department of Pancreatic and Gastric Surgical Oncology, National Cancer Center/ National Clinical Research for Cancer/Cancer Hospital, Chinese Academy of Medical Sciences and Peking Union Medical College, Beijing 100021, China.

The aim of this study was to evaluate the effect of neoadjuvant therapies (NAT) on patients with locally advanced gastric cancer (LAGC). This study retrospectively analyzed LAGC patients treated at the China National Cancer Center between October 2006 and December 2018. All patients included were divided into two groups, NAT followed by surgery (NAT-Surgery) and adjuvant chemotherapy following surgery (Surgery-ACT). Subgroup analysis compared between patients underwent either neoadjuvant chemotherapy (nCT) or neoadjuvant chemoradiation (nCRT) was conducted. Propensity score matching (PSM) was implemented to reduce selection bias. In total, 2779 patients were included in this study (494 of NAT-Surgery group and 2285 of Surgery-ACT group). After PSM, the patients in NAT-Surgery group had a significantly longer overall survival (OS) than patients in Surgery-ACT group (<0.001). Subgroup analysis revealed that grade 3 or 4 adverse events were more frequently observed in nCRT group during neoadjuvant treatment (52.0% in nCRT group vs. 34.0% in nCT group, =0.010). Pathological complete response (pCR) being achieved in 17.0% after nCRT versus 4.0% after nCT (<0.001). Patients of the nCRT group obtained better disease-free survival (DFS, =0.024) and local-recurrence-free survival (LRFS, =0.014) than patients in nCT group, while there was no significant difference in OS between the two groups. In conclusion, NAT improved survival outcomes among LAGC patients over surgery followed by adjuvant chemotherapy. In comparison with nCT, nCRT resulted in higher pCR rate, better DFS and LRFS, without significantly affecting OS.
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http://dx.doi.org/10.7150/jca.46847DOI Listing
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC7738980PMC
January 2021

Silicon and oxygen synergistic effects for the discovery of new high-performance nonfullerene acceptors.

Nat Commun 2020 Nov 16;11(1):5814. Epub 2020 Nov 16.

State Key Laboratory and Institute of Elemento-Organic Chemistry, College of Chemistry, Nankai University, Tianjin, 300071, China.

In organic electronics, an aromatic fused ring is a basic unit that provides π-electrons to construct semiconductors and governs the device performance. The main challenge in developing new π-skeletons for tuning the material properties is the limitation of the available chemical approach. Herein, we successfully synthesize two pentacyclic siloxy-bridged π-conjugated isomers to investigate the synergistic effects of Si and O atoms on the geometric and electronic influence of π-units in organic electronics. Notably, the synthesis routes for both isomers possess several advantages over the previous approaches for delivering conventional aromatic fused-rings, such as environmentally benign tin-free synthesis and few synthetic steps. To explore their potential application as photovoltaic materials, two isomeric acceptor-donor-acceptor type acceptors based on these two isomers were developed, showing a decent device efficiency of 10%, which indicates the great potential of this SiO-bridged ladder-type unit for the development of new high-performance semiconductor materials.
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http://dx.doi.org/10.1038/s41467-020-19605-zDOI Listing
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC7669892PMC
November 2020

Clinical Outcomes of Proximal Gastrectomy versus Total Gastrectomy for Proximal Gastric Cancer: A Systematic Review and Meta-Analysis.

Dig Surg 2021 5;38(1):1-13. Epub 2020 Nov 5.

National Cancer Center/National Clinical Research Center for Cancer/Cancer Hospital, Chinese Academy of Medical Sciences and Peking Union Medical College, Beijing, China,

Introduction: The extent of optimal gastric resection for proximal gastric cancer (PGC) continues to remain controversial, and a final consensus is yet to be met. The current study aimed to compare the perioperative outcomes, postoperative complications, and overall survival (OS) of proximal gastrectomy (PG) versus total gastrectomy (TG) in the treatment of PGC through a meta-analysis.

Methods: We systematically searched PubMed, Embase, The Cochrane Library, and Web of Science for articles published in English since database establishment to October 2019. Evaluated endpoints were perioperative outcomes, postoperative complications, and long-term survival outcomes.

Results: A total of 2,896 patients in 25 full-text articles were included, of which one was a prospective randomized study, one was a clinical phase III trial, and the rest were retrospective comparative studies. The PG group showed a higher incidence of anastomotic stenosis (OR = 2.21 [95% CI: 1.08-4.50]; p = 0.03) and reflux symptoms (OR = 3.33 [95% CI: 1.85-5.99]; p < 0.001) when compared with the TG group, while no difference was found in PG patients with double-tract reconstruction (DTR). The retrieved lymph nodes were clearly more in the TG group (WMD = -10.46 [95% CI: -12.76 to -8.17]; p < 0.001). The PG group was associated with a better 5-year OS relative to TG with 11 included studies (OR = 1.35 [95% CI: 1.03-1.77]; p = 0.03). After stratification for early gastric cancer and PG with DTR groups, however, there was no significant difference between the 2 groups (OR = 1.35 [95% CI: 0.59-2.45]; p = 0.62).

Conclusion: In conclusion, PG was associated with a visible improved long-term survival outcome for all irrespective of tumor stage, while a similar 5-year OS for only early gastric cancer patients between the 2 groups. Future randomized clinical trials of esophagojejunostomy techniques, such as DTR following PG, are expected to prevent postoperative complications and assist surgeons in the choice of surgical approach for PGC patients.
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http://dx.doi.org/10.1159/000506104DOI Listing
October 2021

Open vs. laparoscopic surgery for locally advanced gastric cancer after neoadjuvant therapy: Short-term and long-term survival outcomes.

Oncol Lett 2020 Jul 14;20(1):861-867. Epub 2020 May 14.

Department of Pancreatic and Gastric Surgical Oncology, National Cancer Center/National Clinical Research Center for Cancer/Cancer Hospital, Chinese Academy of Medical Sciences and Peking Union Medical College, Beijing 100021, P.R. China.

The aim of the present study was to compare the short-term and long-term survival outcomes of laparoscopic gastrectomy vs. open gastrectomy in treating locally advanced gastric cancer (LAGC) after neoadjuvant therapy. This study retrospectively reviewed the medical records of 270 patients with LAGC, who underwent laparoscopic (n=49) or conventional open (n=221) surgery following neoadjuvant therapy between January 2007 and December 2016 in China National Cancer Center. Postoperative parameters and survival outcomes including overall survival and disease-free survival were analyzed. Patients who underwent laparoscopic gastrectomy (LP) had significantly shorter postoperative stay and a decreased number of metastatic lymph nodes harvested compared to those who underwent open surgery. The 75% disease-free survival (DFS) time in the laparoscopic surgery group (25.7 months) was higher compared with the open surgery group (15.6 months). However, no significant difference was observed in 5-year overall survival and DFS between the two groups. In conclusion, LG provides non-inferior short- and long-term survival outcomes compared with open surgery, suggesting a laparoscopic approach may be justified for patients with LAGC receiving neoadjuvant therapy. More randomized controlled trials are required to investigate the positive effects of LG for LAGC following neoadjuvant therapy.
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http://dx.doi.org/10.3892/ol.2020.11626DOI Listing
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC7285756PMC
July 2020

Ring Expansion to 6-, 7-, and 8-Membered Benzosilacycles through Strain-Release Silicon-Based Cross-Coupling.

Angew Chem Int Ed Engl 2020 05 20;59(22):8481-8485. Epub 2020 Mar 20.

State Key Laboratory and Institute of Elemento-Organic Chemistry, College of Chemistry, Nankai University, 94 Weijin Road, Tianjin, 300071, China.

The synthesis of silacycles is highly appealing due to their important applications in organic synthesis, medicinal chemistry, and materials chemistry. However, sila-tetralins and sila-benzosuberanes are surprisingly under-represented due to a lack of general methods to access these compounds. We successfully developed a Pd-catalyzed strain-release silicon-based cross-coupling as an unprecedented ring-expansion method, which constitutes a general route for preparing diverse sila-tetralins and sila-benzosuberanes.
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http://dx.doi.org/10.1002/anie.202001539DOI Listing
May 2020

Divergent Synthesis of Vinyl-, Benzyl-, and Borylsilanes: Aryl to Alkyl 1,5-Palladium Migration/Coupling Sequences.

Angew Chem Int Ed Engl 2020 04 25;59(16):6555-6560. Epub 2020 Feb 25.

State Key Laboratory and Institute of Elemento-Organic Chemistry, College of Chemistry, Nankai University, 94 Weijin Road, Tianjin, 300071, China.

Organosilicon compounds have been extensively utilized both in industry and academia. Studies on the syntheses of diverse organosilanes is highly appealing. Through-space metal/hydrogen shifts allow functionalization of C-H bonds at a remote site, which are otherwise difficult to achieve. However, until now, an aryl to alkyl 1,5-palladium migration process seems to have not been presented. Reported herein is the remote olefination, arylation, and borylation of a methyl group on silicon to access diverse vinyl-, benzyl-, and borylsilanes, constituting a unique C(sp )-H transformation based on a 1,5-palladium migration process.
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http://dx.doi.org/10.1002/anie.201914740DOI Listing
April 2020

Proton Insertion Chemistry of a Zinc-Organic Battery.

Angew Chem Int Ed Engl 2020 Mar 3;59(12):4920-4924. Epub 2020 Feb 3.

Key Laboratory of Advanced Energy Materials Chemistry (Ministry of Education), Renewable Energy Conversion and Storage Center, College of Chemistry, Nankai University, Tianjin, 300071, P. R. China.

Proton storage in rechargeable aqueous zinc-ion batteries (ZIBs) is attracting extensive attention owing to the fast kinetics of H insertion/extraction. However, it has not been achieved in organic materials-based ZIBs with a mild electrolyte. Now, aqueous ZIBs based on diquinoxalino [2,3-a:2',3'-c] phenazine (HATN) in a mild electrolyte are developed. Electrochemical and structural analysis confirm for the first time that such Zn-HATN batteries experience a H uptake/removal behavior with highly reversible structural evolution of HATN. The H uptake/removal endows the Zn-HATN batteries with enhanced electrochemical performance. Proton insertion chemistry will broaden the horizons of aqueous Zn-organic batteries and open up new opportunities to construct high-performance ZIBs.
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http://dx.doi.org/10.1002/anie.201916529DOI Listing
March 2020

Three-component vicinal-diarylation of alkenes direct transmetalation of arylboronic acids.

Chem Sci 2019 Sep 3;10(34):7952-7957. Epub 2019 Jul 3.

State Key Laboratory and Institute of Elemento-Organic Chemistry , College of Chemistry , Nankai University , 94 Weijin Road , Tianjin 300071 , China . Email: ; Email:

Herein, we report three-component vicinal-diarylation of non-conjugated alkenes initiated by transmetalation of arylboronic acids, which provides complementary access to β,γ-diaryl carbonyl compounds. We have also screened a large number of chiral ligands for developing an enantioselective version of this reaction and obtained the preliminary results (up to 79 : 21 e.r.). Notably, the methodology developed herein represents the first three component -vicinal-dicarbofunctionalization of non-conjugated alkenes involving palladium catalysis.
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http://dx.doi.org/10.1039/c9sc02182eDOI Listing
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC6836572PMC
September 2019

Long-term Results of Conversion Therapy for Initially Unresectable Gastric Cancer: Analysis of 122 Patients at the National Cancer Center in China.

J Cancer 2019 15;10(24):5975-5985. Epub 2019 Oct 15.

Department of Pancreatic and Gastric Surgical Oncology, National Cancer Center/National Clinical Research Center for Cancer/Cancer Hospital, Chinese Academy of Medical Sciences and Peking Union Medical College, Beijing 100021, China.

To assess the long-term survival and prognostic factors of conversion therapy in patients with initially unresectable gastric cancer. We conducted a retrospective study of clinicopathological and survival data of 122 consecutive patients who were diagnosed with initially unresectable gastric cancer and underwent the conversion surgery after systemic chemotherapy at the China National Cancer Center between May 2006 and May 2017. For all the 122 patients, the 3- and 5-year overall survival (OS) rates from the date of chemotherapy initiation were 61.0% and 52.0%, respectively, with a median OS of 63.6 months. During follow-up, the recurrence was observed in 49 (40.1%) patients who underwent conversion surgery. According to the multivariate COX regression analysis, receipt of postoperative adjuvant chemotherapy (POAC) was the only significant independent predictor of a favorable OS (HR 0.40; 95% CI 0.18-0.85, =0.017). Log-rank analysis showed that POAC group experienced a survival advantage in terms of PFS when compared with observation group (HR 0.53, 95%CI 0.31-0.92, =0.009). Conversion therapy may provide long-term survival for patients with initially unresectable gastric cancer. Postoperative adjuvant chemotherapy might be recommended for patients who underwent conversion therapy.
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http://dx.doi.org/10.7150/jca.35527DOI Listing
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC6856572PMC
October 2019

Nickel-catalyzed intermolecular oxidative Heck arylation driven by transfer hydrogenation.

Nat Commun 2019 11 5;10(1):5025. Epub 2019 Nov 5.

State Key Laboratory and Institute of Elemento-Organic Chemistry, College of Chemistry, Nankai University, Tianjin, 300071, China.

The conventional oxidative Heck reaction between aryl boronic acids and alkenes typically involved the Pd/Pd/Pd catalytic cycle incorporating an external oxidant and often suffered C=C bond isomerization for internal alkyl-substituted alkenes via chain-walking. Herein, we demonstrate that the regioselectivity (γ-selectivity vs. δ-selectivity) and pathway selectivity (hydroarylation vs. oxidative Heck coupling) of a directed Ni-catalyzed alkene arylation can be controlled by judicious tuning of the coordination environment around the nickel catalyst via optimization of an appropriate phosphine ligand and directing group. In this way, the Ni(0)-catalyzed oxidative Heck arylation that relies on transfer hydrogenation of an acceptor olefin is developed with excellent E/Z selectivity and regioselectivity. Mechanistic investigations suggest that the addition of the acceptor is crucial for lowering the energy for carbometalation and for enabling catalytic turnover.
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http://dx.doi.org/10.1038/s41467-019-12949-1DOI Listing
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC6831602PMC
November 2019

Plasmon-Enhanced Deuteration under Visible-Light Irradiation.

ACS Nano 2019 Sep 9;13(9):10754-10760. Epub 2019 Sep 9.

Key Lab of Advanced Energy Materials Chemistry (Ministry of Education), Renewable Energy Conversion and Storage Center, College of Chemistry , Nankai University , Weijin Road 94 , Tianjin 300071 , China.

Deuteration has found important applications in synthetic chemistry especially for pharmaceutical developments. However, conventional deuteration methods using transition-metal catalysts or strong bases generally involve harsh reaction conditions, expensive deuterium source, insufficient efficiency, and poor selectivity. Herein, we report an efficient visible-light-driven dehalogenative deuteration of organic halides using plasmonic Au/CdS as photocatalyst and DO as deuterium donor. Electron transfer from Au to CdS, which has been confirmed by surface-enhanced Raman spectroscopy, plays a decisive role for the plasmon-mediated dehalogenation. The deuteration is revealed to proceed a radical pathway in which substrates are first activated by the photoinduced electron transfer to generate aryl radicals, and the radicals are further trapped by DO to give deuterated products. Under visible-light irradiation, excellent deuteration efficiency is achieved with high functional group tolerance and a wide range of substrates at room temperature. Compared with bare CdS, the photocatalytic activity increases ∼18 times after the loading of plasmonic Au nanoparticles. This work sheds light on the interfacial charge transfer between plasmonic metals and semiconductors as an important criterion for rational design of visible-light photocatalysts.
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http://dx.doi.org/10.1021/acsnano.9b05523DOI Listing
September 2019

Effects of Neoadjuvant Chemotherapy Toxicity and Postoperative Complications on Short-term and Long-term Outcomes After Curative Resection of Gastric Cancer.

J Gastrointest Surg 2020 06 28;24(6):1278-1289. Epub 2019 May 28.

National Cancer Center/National Clinical Research Center for Cancer/Cancer Hospital, Chinese Academy of Medical Sciences and Peking Union Medical College, Beijing, 100021, China.

Background: Whether neoadjuvant chemotherapy (NAC) increased the risk of postoperative morbidities for patients with locally advanced gastric cancer (GC) is unknown. Whether neoadjuvant chemotherapy toxicity (NCT) and postoperative complications (POCs) correlate with short-term and long-term outcomes also remains unclear. We aimed to evaluate the role of NAC on the development of POCs, as well as the impact of NCT and POCs on postoperative and oncologic outcomes in curatively resected GC treated with NAC.

Methods: This study retrospectively reviewed 230 patients who underwent curative gastrectomy for locally advanced GC (clinically T3/4 or N+) after NAC between 2006 and 2016. Five hundred patients undergoing upfront and curative surgery were selected as a control group. After matching, the incidence of POCs was compared between two groups. In the NAC group, clinicopathological characteristics of patients who experienced POCs were compared to those who did not. Logistic and Cox multivariate regression analyses were used to examine factors associated with POCs, disease-free survival (DFS), and overall survival (OS).

Results: Following matching, 230 and 230 patients treated with surgery plus NAC and upfront surgery remained, respectively. The incidence of POCs was 28.7% and 24.3%, respectively (p = 0.290). In the NAC group, NCT (OR [odds ratio] 22.968, 95% CI [confidence interval] 2.948-> 99, p = 0.003) and operation time (OR 1.006, 95% CI 1.001-1.011, p = 0.021) were independent predictive factors of POCs. NCT did not affect oncologic outcomes. The Cox regression model demonstrated that POCs were independently associated with worse DFS (HR [hazard ratio] 2.128, 95% CI 1.240-3.653, p = 0.006) but not OS for patients treated with NAC.

Conclusions: The administration of NAC is not associated with an elevated risk of POCs. For patients treated with NAC, NCT is an independent predictor of POCs, but does not affect oncologic outcomes. POCs is independently associated with worse DFS but not OS. NAC should be considered a safe approach in patients who have locally advanced GC. Strategies to minimize chemotherapy toxicity and postoperative morbidities associated with NAC are warranted.
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http://dx.doi.org/10.1007/s11605-019-04257-2DOI Listing
June 2020

Development and validation of a nomogram to individually predict survival of young patients with nonmetastatic gastric cancer: A retrospective cohort study.

Saudi J Gastroenterol 2019 Jul-Aug;25(4):236-244

Department of Pancreatic and Gastric Surgery, National Cancer Centre/National Clinical Research Center for Cancer/Cancer Hospital, Chinese Academy of Medical Sciences and Peking Union Medical College, Beijing, China.

Background/aims: Evidence regarding gastric cancer (GC) patients <40 years old is limited. The aim of the study was to identify risk factors affecting overall survival (OS) of young patients with nonmetastatic GC and to establish a nomogram for prognostic prediction using data from the Surveillance, Epidemiology and End Results (SEER) database. Furthermore, this study sought to externally validate this nomogram in an independent patient cohort.

Patients And Methods: In this retrospective cohort study, the records of patients aged <40 years with nonmetastatic GC (n = 559), from the SEER database, between 2006 and 2015, were examined. The nomogram was established based on the Cox proportional hazards regression model using the SEER dataset. Patients with nonmetastatic GC (n = 201) in our department between 2009 and 2015 were selected as an external validation set. Discrimination and calibration were performed in both cohorts.

Results: The multivariate Cox model identified race, tumor subsites, tumor size, depth of invasion, lymph node metastasis, number of examined lymph nodes, and surgery as independent covariates associated with OS. The nomogram exhibited superior discriminative power than the eighth tumor, node, metastasis (TNM) staging system in both the training set [Harrell's concordance index (C index): 0.762 vs. 0.635,P < 0.001] and validation set (C index: 0.805 vs. 0.712,P= 0.176). Calibration of the nomogram was good in both cohorts.

Conclusions: We developed a nomogram predicting 3- and 5-year OS rates in young patients with nonmetastatic GC. Both the training set and validation set showed good discrimination and calibration, suggesting good clinical applicability.
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http://dx.doi.org/10.4103/sjg.SJG_378_18DOI Listing
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC6714466PMC
April 2020

Rhodium(iii) vs. cobalt(iii): a mechanistically distinct three-component C-H bond addition cascade using a Cp*Rh catalyst.

Chem Commun (Camb) 2019 Jan;55(5):695-698

State Key Laboratory and Institute of Elemento-Organic Chemistry, College of Chemistry, Nankai University, Tianjin, 300071, China.

Three-component C-H bond additions across two different coupling partners remain underdeveloped. Herein, we report the first three-component RhIII-catalyzed C-H bond additions to a wide range of dienes and aldehydes. Our method constitutes a complementary access with Ellman's CoIII-catalytic system to homoallylic alcohols.
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http://dx.doi.org/10.1039/c8cc08792jDOI Listing
January 2019

Nickel(0)-catalyzed linear-selective hydroarylation of unactivated alkenes and styrenes with aryl boronic acids.

Chem Sci 2018 Sep 18;9(33):6839-6843. Epub 2018 Jul 18.

State Key Laboratory and Institute of Elemento-Organic Chemistry , College of Chemistry , Nankai University , 94 Weijin Road , Tianjin 300071 , China . Email:

Herein, we describe the first linear-selective hydroarylation reaction of unactivated alkenes and styrenes with aryl boronic acids, which was achieved by introducing a directing group on the alkenes. This efficient, scalable reaction serves as a method for modular assembly of structurally diverse alkyl arenes, including γ-aryl butyric acid derivatives, which are widely utilized as chemical building blocks for the synthesis of various drugs and other biologically active compounds.
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http://dx.doi.org/10.1039/c8sc02101eDOI Listing
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC6115005PMC
September 2018

A prospective phase I study of hypo-fractionated neoadjuvant radiotherapy for locally advanced gastric cancer.

BMC Cancer 2018 Aug 8;18(1):803. Epub 2018 Aug 8.

Department of Radiation Oncology, Chinese National Cancer Center/Cancer Hospital, Chinese Academy of Medical Sciences, 17 Panjiayuannanli, Chaoyang District, Beijing, 100021, China.

Background: Previous studies have reported that neoadjuvant chemoradiotherapy can downstage the advanced gastric cancer. However, no studies are available on the application of hypo-radiotherapy to neoadjuvant radiotherapy. This study sought to assess the maximum tolerated dose (MTD) and dose-limited toxicity (DLT) of hypo-fractionated chemoradiotherapy for local advanced gastric cancer.

Method: Patients with cT3-4 and/or lymph node-positive locally advanced gastric cancer or Siewert II/III esophagogastric junction adenocarcinoma were enrolled. Preoperative chemoradiation was followed by 3 cycles of oxaliplatin + S-1 neoadjuvant chemotherapy with an interval duration of 3-4 weeks. D2 resection was performed 2-4 weeks after neoadjuvant therapy. Three cycles of adjuvant chemotherapy were planned after surgery. Intensity-modulated radiotherapy (IMRT) was used. The radiotherapy dose level was defined using three levels, namely, 40.0 Gy/2.5 Gy, 41.6 Gy/2.6 Gy, 43.2 Gy/2.7 Gy delivered concurrently with S-1 at 80 mg/m.

Results: From May 2016 to Dec 2016, nine patients with a median age of 63 years were enrolled in this study. The most common grade I-III adverse events were leukopenia (88.9%), nausea (88.9%), vomiting (77.8%) and weight loss (66.7%). Grade III adverse events consisted of vomiting and weight loss.

Conclusion: The MTD of hypo-fractionated radiotherapy for locally advanced gastric cancer was 40.0 Gy/2.5 Gy, and the DLTs were vomiting and weight loss.

Trial Registration: Clinicaltrials.gov ID: NCT03427684 (Retrospectively registered on February 9, 2018).
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http://dx.doi.org/10.1186/s12885-018-4707-9DOI Listing
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC6083620PMC
August 2018

Intermolecular σ-Bond Cross-Exchange Reaction between Cyclopropenones and (Benzo)silacyclobutanes: Straightforward Access towards Sila(benzo)cycloheptenones.

Angew Chem Int Ed Engl 2018 05 25;57(21):6329-6332. Epub 2018 Apr 25.

State Key Laboratory and Institute of Elemento-Organic Chemistry, College of Chemistry, Nankai University, 94 Weijin Road, Tianjin, 300071, China.

Described herein is the first intermolecular σ-bond exchange reaction between the C-C bond of cyclopropenones and C-Si bond of (benzo)silacyclobutanes and it proceeds smoothly by treatment with either 1 mol % of a palladium or 2 mol % of a nickel catalyst. This reaction constitutes an unprecedented route for the synthesis of various sila(benzo)suberones. And it is also the first example of a σ-bond exchange reaction involving cyclopropenones.
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http://dx.doi.org/10.1002/anie.201803156DOI Listing
May 2018

Prognostic factors associated with locally advanced gastric cancer patients treated with neoadjuvant chemotherapy followed by surgical resection.

Oncotarget 2017 Sep 6;8(43):75186-75194. Epub 2017 Sep 6.

National Cancer Center/Cancer Hospital, Chinese Academy of Medical Sciences & Peking Union Medical College, Beijing, China.

In this retrospective study, we analyzed prognostic factors associated with survival outcomes in 73 locally advanced gastric cancer patients treated with neoadjuvant chemotherapy (NAC) followed by surgical resection. Median disease-free survival (DFS) for 64 patients that received R0 resection was 685 days, whereas median overall survival (OS) for 73 patients was 930 days. Multivariate analysis demonstrated that post-treatment nodal stages (P = 0.002), nervous invasion (P = 0.0492) and serum CA199 levels (P = 0.0398) were independent prognostic factors for DFS. Nodal stages (P = 0.0007), presence of nervous invasion (P = 0.0259) and non-radical resection (P = 0.0165) were independent prognostic factors for OS. These results indicate that post-treatment nodal stages, neural invasion and serum CA199 levels are all associated with poor DFS. Moreover, post-treatment nodal stage, resection type and neural invasion status are independent prognostic factors for OS.
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http://dx.doi.org/10.18632/oncotarget.20660DOI Listing
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC5650411PMC
September 2017

Effects of alcohol drinking and smoking on pancreatic ductal adenocarcinoma mortality: A retrospective cohort study consisting of 1783 patients.

Sci Rep 2017 08 29;7(1):9572. Epub 2017 Aug 29.

Department of Pancreatic and Gastric Surgery, National Cancer Center/Cancer Hospital, Chinese Academy of Medical Sciences and Peking Union Medical College, Beijing, 100021, China.

The effects of alcohol drinking and smoking on pancreatic ductal adenocarcinoma (PDAC) mortality are contradictory. Individuals who were diagnosed as PDAC and hospitalized at the China National Cancer Center between January 1999 and January 2016 were identified and included in the study. Ultimately, 1783 consecutive patients were included in the study. Patients were categorized as never, ex-drinkers/smokers or current drinkers/smokers. Hazard ratios (HRs) of all-cause mortality and 95% confidence intervals (CIs) were estimated using Cox proportional hazards models. Compared with never drinkers, the HRs were 1.25 for ever drinkers, 1.24 for current drinkers, and 1.33 for ex-drinkers (trend P = 0.031). Heavy drinking and smoking period of 30 or more years were positive prognostic factors for PDAC. For different smoking and alcohol drinking status, only subjects who are both current smokers and current drinkers (HR, 1.45; 95% CI, 1.03-2.05) were associated with reduced survival after PDAC compared to those who were never smokers and never drinkers. Patients who are alcohol drinkers and long-term smokers before diagnosis have a significantly higher risk of PDAC mortality. Compared to those who neither smoker nor drink, only patients who both smokers and drinkers were associated with reduced survival from PDAC.
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http://dx.doi.org/10.1038/s41598-017-08794-1DOI Listing
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC5574975PMC
August 2017

Pancreatic neuroendocrine cancer with liver metastases and multiple peritoneal metastases: report of one case.

Transl Gastroenterol Hepatol 2016 23;1:65. Epub 2016 Aug 23.

Department of Abdominal Surgery, Cancer Institute & Hospital, Peking Union Medical College & Chinese Academy of Medical Sciences, Beijing 100021, China.

Pancreatic neuroendocrine tumor (pNET) is a rare pancreatic tumor, with its incidence showing a rising trend in recent years. Most of its distant metastases are found in the liver. This article describes a 59-year-old male patient with pNET with liver metastasis and multiple abdominal metastases, focusing on the management of this tumor in its advanced stage.
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http://dx.doi.org/10.21037/tgh.2016.07.05DOI Listing
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC5244620PMC
August 2016

A rare case of retroperitoneal paraganglioma-case report and literature review.

Transl Gastroenterol Hepatol 2016 18;1:58. Epub 2016 Jul 18.

Department of Abdominal Surgery, Cancer Institute & Hospital, Chinese Academy of Medical Science and Peking Union Medical College, Beijing 100021, China.

Paraganglioma is a rarely type of neuroendocrine neoplasm with the ability of neuropeptide and catecholamine secretion. Hypertension and sympathetic hyperactivity was the most common clinical presentation. And it is still a challenge to determine the biological behavior pathologically. Here, we reported a case of paraganglioma originated from retroperitoneal with the classical clinical presentation. Radical resection was performed successfully and malignant tendency was revealed in pathology. Meanwhile, literature review was conducted in order to figure out the diagnosis and prognosis.
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http://dx.doi.org/10.21037/tgh.2016.06.01DOI Listing
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC5244753PMC
July 2016

Breast cancer in young women of Chinese Han population: A retrospective study of patients under 25 years.

Pathol Res Pract 2016 Nov 3;212(11):1015-1020. Epub 2016 Sep 3.

Abdominal Surgical Oncology Department, National Cancer Center/Cancer Hospital, Chinese Academy of Medical Sciences and Peking Union Medical College, Beijing 100021, China. Electronic address:

Background: Breast cancer has aggressive clinical and pathological features in younger women and is characterized by poorer prognosis than in older women. However, data on women <25 years are limited.

Objective: The aim of the present study was to evaluate the different pathological characteristics and prognostic factors in Chinese women with breast cancer <25 years at the time of diagnosis.

Methods: This retrospective study included 94 patients (aged <25) of Chinese Han population with operable breast cancer at the National Cancer Center/Cancer Hospital, Chinese Academy of Medical Sciences between January 1, 2000 and September 30, 2015. Univariate and multivariate Cox regression analysis were performed. The median follow-up duration was 64 months (range, 11-200 months).

Results: The HER2-positive and triple-negative groups had a higher T (P=0.002) and N stage than the luminal A group (P=0.014). The 5-year overall survival (OS) was 90.4%, and the disease-free survival (DFS) was 74.5%. The 5-year DFS varied among the four groups were 94.1 vs. 76.9 vs. 45.5 vs. 66.7%, respectively; P=0.009. Multivariate analysis showed that only estrogen receptor (ER) status was a significant predictor of OS and DFS [Hazard ratio (HR)=5.3, 95% confidence interval (CI)=1.11-25.27, P=0.036; HR=2.712, 95%CI=1.27-5.80, P=0.01).

Conclusion: HER2-positive and triple-negative breast cancer are more likely to have poor prognosis in patients<25years. Hence, ER status may be identified as an independent prognostic factor for predicting young women with breast cancer.
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http://dx.doi.org/10.1016/j.prp.2016.08.010DOI Listing
November 2016
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