Review on Metal-Acid Tandem Catalysis for Hydrogenative Rearrangement of Furfurals to C_(5) Cyclic Compounds

Hydrogenative rearrangement of biomas s-derived furfurals(furfural and 5-hydroxymethyl furfural) to C_(5) cyclic compounds(such as cyclopentanones and cyclopentanols) offers an expedient reaction route for acquiring O-containing value-added chemicals thereby replacing the traditional petroleum-based approaches.The scope for developing efficient bifunctional catalysts and establishing mild reaction conditions for upgrading furfurals to cyclic compounds has stimulated immense deliberation in recent years.Extensive efforts have been made toward developing catalysts for multiple tandem conversions,including those with various metals and supports.In this scientific review,we aim to summarize the research progress on the synergistic effect of the metal-acid sites,including simple metal-supported acidic supports,adjacent metal acid sites-supported catalysts,and in situ H_(2)-modified bifunctional catalysts.Distinctively,the catalytic performance,catalytic mechanism,and future challenges for the hydrogenative rearrangement are elaborated in detail.The methods highlighted in this review promote the development of C_(5) cyclic compound synthesis and provide insights to regulate bifunctional catalysis for other applications.

Clonal immunoglobulin heavy chain and T-cell receptor γ gene rearrangements in primary gastric lymphoma

AIM:To study the diagnostic value of immunoglobulin heavy chain(IgH)and T-cell receptorγ (TCR-γ)gene monoclonal rearrangements in primary gastric lymphoma(PGL).METHODS:A total of 48 patients with suspected PGL at our hospital were prospectively enrolled in this study from January 2009 to December 2011.The patients were divided into three groups(a PGL group,a gastric linitis plastica group,and a benign gastric ulcer group)based on the pathological results(gastric mucosal specimens obtained by endoscopy or surgery)and follow-up.Endoscopic ultrasonography(EUS)and EUSguided biopsy were performed in all the patients.The tissue specimens were used for histopathological examination and for IgH and TCR-γ gene rearrangement polymerase chain reaction analyses.RESULTS:EUS and EUS-guided biopsy were successfully performed in all 48 patients.In the PGL group(n=21),monoclonal IgH gene rearrangements were detected in 14(66.7%)patients.A positive result for each set of primers was found in 12(57.1%),8(38.1%),and 4(19.0%)cases using FR1/JH,FR2/JH,and FR3/JH primers,respectively.Overall,12(75%)patients with mucosal-associated lymphoid tissue lymphoma(n=16)and 2(40%)patients with diffuse large B-cell lymphoma(n=5)were positive for monoclonal IgH gene rearrangements.No patients in the gastric linitis plastica group(n=17)and only one(10%)patient in the benign gastric ulcer group(n=10)were positive for a monoclonal IgH gene rearrangement.No TCRgene monoclonal rearrangements were detected.The sensitivity of monoclonal IgH gene rearrangements was 66.7%for a PGL diagnosis,and the specificity was96.4%.In the PGL group,8(100%)patients with stage IIE PGL(n=8)and 6(46.1%)patients with stage IE PGL(n=13)were positive for monoclonal IgH gene rearrangements.CONCLUSION:IgH gene rearrangements may be associated with PGL staging and may be useful for the diagnosis of PGL and for differentiating between PGL and gastric linitis plastica.

Endoscopic appearance of AIDS-related gastrointestinal lymphoma with c-MYC rearrangements: Case report and literature review

Acquired immune deficiency syndrome (AIDS)-related lymphoma (ARL) remains the main cause of AIDS-related deaths in the highly active anti-retroviral therapy (HAART) era. Recently, rearrangement of MYC is associated with poor prognosis in patients with diffuse large B-cell lymphoma. Here, we report a rare case of gastrointestinal (GI)-ARL with MYC rearrangements and coinfected with Epstein-Barr virus (EBV) infection presenting with various endoscopic findings. A 38-yearold homosexual man who presented with anemia and was diagnosed with an human immunodeficiency virus infection for the first time. GI endoscopy revealed multiple dish-like lesions, ulcerations, bloody spots, nodular masses with active bleeding in the stomach, erythematous flat lesions in the duodenum, and multiple nodular masses in the colon and rectum. Magnified endoscopy with narrow band imaging showed a honeycomb-like pattern without irregular microvessels in the dish-like lesions of the stomach. Biopsy specimens from the stomach, duodenum, colon, and rectum revealed diffuse large B-cell lymphoma concomitant with EBV infection that was detected by high tissue EBV-polymerase chain reaction levels and Epstein-Barr virus small RNAs in situ hybridization. Fluorescence in situ hybridization analysis revealed a fusion between the immunoglobulin heavy chain (IgH) and c-MYC genes, but not between the IgH and BCL2 loci. After 1-mo of treatment with HAART and R-CHOP, endoscopic appearance improved remarkably, and the histological features of the biopsy specimens revealed no evidence of lymphoma. However, he died from multiple organ failure on the 139 th day after diagnosis. The cause of his poor outcome may be related to MYC rearrangement. The GI tract involvement in ARL is rarely reported, and its endoscopic findings are various and may be different from those in non-AIDS GI lymphoma; thus, we also conducted a literature review of GI-ARL cases.

Rearrangement on surface structures by boride to enhanced cycle stability for LiNi0.80Co0.15Al0.05O2 cathode in lithium ion batteries

The side reaction between the active material and liquid-electrolyte cause structural damage and particle pulverization is one of the important factors leading to the capacity decay of LiNi0.80Co0.15Al0.05O2(NCA)materials in Li ion batteries(LIBs).Surface modification is an effective strategy for NCA cathodes,which could alleviate the degradation associated with surface processes.Herein,a surface structure rearrangement of NCA cathode secondary particles was reported by in-situ forming a solid electrolyte LiBO2.The LiBO2 is beneficial for alleviating the stress during charge/discharge process,thereby slowing down the rate of cracks formation in the secondary particles,which facilitates the Li+de-intercalation as well as prevents penetration of the liquid-electrolyte into the interior of the particles.As a result,the surface structure rearrangement NCA(RS-NCA)delivers a high discharge capacity of 202.5 m Ah g^-1 at 0.1 C,and exhibits excellent cycle stability with discharge capacity retaining 148 m Ah g^-1 after 200 cycles at 2 C.This surface structure rearrangement approach provides a new viewpoint in designing high-performance high-voltage LIBs.

Bcl-1 Rearrangement and Cyclin D1 Protein Expression in Multiple Myeloma Precursor Cells

The rearrangement of Bcl-1 gene (Bcl-1/IgH rearrangement) and expression of cyclin D1 in multiple myeloma (MM) precursor cells were studied and the role of cyclin D1 in the pathogenesis of MM was investigated. The BCL-1 rearrangement and cyclin D1 protein expression in 15 cases of MM were detected. By using hemi-nested polymerase chain reaction (PCR) the genomic DNA from fresh peripheral blood and bone marrow was amplified and the expression of cyclin D1 in the smears was detected by using immunohistochemical method. Ten volunteer with normal bone marrow served as control group. The results showed Bcl-1 rearrangement was detectable in 3/15 (20 %) MM patients and cyclin D, expression in 4/15 (27 % ) MM patients. BeLl-1 rearrangement and cyclin D1 protein expression were also detected in MM precursor cells. No overexpression of cyclin D1 or the rearrangement of the BeL-1 gene was found in the 10 volunteers. It was concluded that Bel-1 rearrangement and cyclin D1 protein overexpression were detected in MM precursor cells, speculating that overexpression of cyclin D1 protein may play an initial (critical) role in the pathogenesis of MM.

Clinicopathologic characteristics and therapeutic responses of Chinese patients with non-small cell lung cancer who harbor an anaplastic lymphoma kinase rearrangement

Introduction: The rearrangement of the anaplastic lymphoma kinase(ALK) gene accounts for approximately 1%–6% of lung adenocarcinoma cases and deines a molecular subgroup of tumors characterized by clinical sensitivity to ALK inhibitors such as crizotinib. This study aimed to identify the relationship between ALK rearrangement and the clinico?pathologic characteristics of non?small cell lung cancer(NSCLC) and to analyze the therapeutic responses of crizotinib and conventional chemotherapy to ALK rearrangement in NSCLC patients.Methods: A total of 487 lung cancer patients who underwent testing for ALK rearrangement in our department were included in this study. ALK rearrangement was examined by using fluorescence in situ hybridization(FISH) assay.Results: Among the 487 patients, 44(9.0%) were diagnosed with ALK rearrangement by using FISH assay. In 123 patients with adenocarcinoma who were non?smokers and of a young age(≤58 years old), the frequency of ALK rearrangement was 20.3%(25/123). Short overall survival(OS) was associated with non?adenocarcinoma tumor type(P = 0.006), poorly diferentiated tumors(P al growth factor rece= 0.001), advanced?stage tumors(P < 0.001), smoking history(P ptor(EGFR)(P = 0.008), and wild?type epidermrter time to cancer p= 0.008). Moreover, patients with poorly diferentiated and advanced?stage tumors had a shorogression compared with those with well diferentiated(P = 0.023) and early?stage tumors(P = 0.001), respectively.Conclusions: ALK?rearranged NSCLC tends to occur in younger individuals who are either non?smokers or light smokers with adenocarcinoma. Patients with ALK rearrangement might beneit from ALK inhibitor therapy.

REARRANGEMENT AND EXPRESSION OF T CELL RECEPTOR β GENE IN HUMAN HEMOPOIETIC CELL LINES AND PRIMARY CELLS FROM ACUTE LYMPHOCYTIC LEUKEMIAS

Using Southern blot, Northern blot and Quick blot methods, we examined the rearrangement and expression of TCR βgene in four early differentiation stage cell lines from human hemopoietic system, namely HL-60, Jurkat, Daudi and Raji cells as well as lymphocytes from 17 acute lymphocytic leukemia （ALL） patients. The results showed. Ⅰ) Rearrangement of TCR βgene was seen in Jurkat cells. A germline pattern was observed in HL-60, Daudi and Raji cells. 2) Eight of 9 patients with T-ALL had cells with rearranged TCR βgene. But two of 3 patients with B-ALL and three of 5 patients with nonT, nonB-ALL also had cells with rearranged TCR βgene. 3) A 1.3 kb full-length transcript and a 1.0 kb truncated transcript were detected in Jurkat cells by probing with 32P-TCR βcDNA. But some leukemic B cells also expressed an incompleted transcript. 4) TCR βmRNA was detected in six of 8 patients with T-ALL, four of 5 patients with nonT, nonB-ALL and one of 3 patients with B-ALL. But the level of expression was quite differ ent. The dual-rearrangement and the abnormal expression may give us a new clue for researching leukemogenesis.

The Effective Catalyst (Cobalt Salt/Lewis Acid) for Beckmann Rearrangement of Cycloalkanone Oximes to Lactams under Mild Conditions

The Beckmann rearrangement of cyclohexanone oxime was achieved by the combined use of cobalt salt and Lewis acids co-catalysts (each 10 mol%). Various combinations of cobalt salts and Lewis acids gave lactams in a satisfactory yield under mild conditions. This method makes it possible to reduce undesirable byproducts.

Research Progress in Refining Process for Production of Caprolactam by Beckman Rearrangement Reaction

Caprolactam, which is mainly produced via the Beckmann rearrangement reaction, is an important chemical material. The strict specifications of caprolactam products make the refining process of caprolactam extremely important. According to the different rearrangement process, the refining process of caprolactam is also different. The main refining sequence of liquid phase rearrangement products includes extraction, ion exchange, hydrogenation, and distillation. The refining process of gas phase rearrangement products is conducted mainly through distillation, crystallization, and hydrogenation. In this paper, the research progress of caprolactam refining technology will be summarized according to different rearrangement reaction processes, which will provide a reference for the selection of appropriate caprolactam refining process.

Theoretical Study on the Transition State of N-nitropyrazoles Rearrangement Reaction

Theoretical studies on the rearrangement reactions of nitropyrazoles have been investigated. In order to gain a better understanding of the intermediate process of rearrangement reactions, the transition states of the rearrangement reactions were obtained by TS method at the B3 LYP/6-311 G(d, p) level of theory. The natural bond orbital charge, electrostatic potential and frontier molecular orbital of the molecules in the process of rearrangement were analyzed, and the solvent effect was also discussed. The rearrangement of nitropyrazoles involves two transition states and one intermediate, and the nitro group and hydrogen atom are two transfer groups for rearrangement reactions. The migration of these two groups leads to the change of charge distribution and molecular structure. The structural changes of the molecules in different solvents are not significant, but the dipole moment of the molecule has obvious change.

Iron (III) Chloride Catalyzed Claisen Rearrangement Reaction of Allyloxyarenes under Microwave Conditions

The Claisen rearrangement is a [3,3]-sigmatropic rearrangement which is an important method for new C-C bond formation in organic synthesis. This reaction is a typical thermal reaction that requires a high temperature and long reaction time. In this paper, the acceleration effects of the iron (III) chloride (FeCl3) catalyst and microwave irradiation during the Claisen rearrangement reaction of allyloxyarene derivatives are reported. The FeCl3 catalyst was able to initiate the reaction at low temperature and induced the subsequent cyclization reaction. The moderation of excellent yields was obtained in a short reaction time. The formation of complex ferric-arenes under microwave irradiation conditions to efficiently absorb the microwaves was expected and confirmed.

CHEMISTRY OF DENUDATINE.Ⅳ.AN UNUSUAL REARRANGEMENT BY CONTRACTION OF RING C IN DENUDATINE AND DIACETYLDENUDATINE

An unusual rearrangement by contraction of the ring C in denudatine 1 and di-acetyldenudatine 2 is presented.

THE RELATIONSHIP BETWEEN NON-HODGKIN'S LYMPHOMA AND THE GENE REARRANGEMENT

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STRUCTURAL REARRANGEMENT AND PROPERTIES OF QUENCHED TITANATE GLASSES REHEATED AT T_g

The structural rearrangement of quenchedtitanate glasses reheated at T_g. was investigated by ESR andIR spectroscopies. From the ESR observations it is suggestedthat the structure was readjtsted and became more compactafer the heat-treatment. A removal of residual vacancies isrelated to the diffusion of oxygen ions. The combination ofmore oxygen with titanium ions to form titanium-oxygenpolyhedra and the transformation of boron-oxygen groups areconfirmed from IR spectra. Some physical properties are improved after heating.

CHEMISTRY OF DENUDATINE. I. A NOVEL REARRANGEMENT OF DENUDATINE

Treatment of denudatine 1 with 10% HCl soln. at 45-50℃ for 3 days leads to a pair of epimers 4A and 4B, Structures of 4A and 4B have been elucidated on the basis of chemical and spectral methods.

T-CELL RECEPTOR GENE REARRANGEMENT ANALYSIS IN THE PRIMARY CUTANEOUS T-CELL LYMPHOMA

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COPE REARRANGEMENT INVOLVING CARBON—CARBON BOND CLEAVAGE

A new type of Cope rearrangement involving carbon-carbon bond cleavage (or de-tbutylation) was found during the heating of 4-allyl-4-methyl-2, 6-di-t-butylsemiquinone,

CHEMISTRY OF DENUDATINE Ⅲ. REARRANGEMENT OF DENUDATINE

Treatment of denudatine 1 with 10％ HCl soln. at 30-40℃ for 1 day leads to another rearrangement product 3 along with a pair of epimers 2A and 2B. Upon adding a little EtOH in the reaction solution, only a pair of epimers 4A and 4B were obtained along with the unchanged starting material.

THE REARRANGEMENT OF 1,7β-DIMETHYL-7α-HYDROXY-8aα-CARBOXYMETHYL-9β-CARBOMETHOXY-4bα, 5, 6, 7, 8, 8a-HEXAttYDROFLUORENE LACTONE INDUCED BY DIBAL-H

1,7β- Dimethyl-7α- hydroxy-8aα-carboxymethyl-9β-carbomethoxy-4bα, 5, 6, 7, 8, 8α-hexahydrofluorene lactone(2) is converted to 8, 12-epoxyallogibberic acid methyl ester(4) by the action of diisobutyl aluminum hydride (DIBAL-H) with a novel rearrangement reaction.

STUDY ON THE REARRANGEMENT REACTION OF 5－AMINO－1－AMINOCARBONYL－1，2，AND ITS ANALOGUES

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