Photochemical Production of Methyl Halides with Guaiacol as the Precursor

Methyl halides are crucial trace greenhouse gases in the atmosphere,playing a significant role in global climate change and the atmospheric environment.This study investigated the photochemical production of methyl halides in an artificial seawater system using guaiacol as a precursor through laboratory simulation experiments.The influences of various environmental factors,including illumination time,radiation wavebands,illumination intensity,concentrations of guaiacol and halide ions(X^(-)),Fe^(3+),salinity,dissolved oxygen(DO),and pH value on the photochemical production of methyl halides were examined.We demonstrated that increased illumination intensity and duration promote the photochemical production of methyl halides,with a notable enhancement under UV-B radiation.Guaiacol and halide ions were identified as key precursors,and their high concentrations facilitated the formation of methyl halides.Additionally,different types of halide ions exhibited a competitive relationship in producing methyl halides.The study found that an increase in pH inhibited the photochemical formation of CH_(3)I due to the reaction between OH^(-)and·CH_(3).Dissolved oxygen was found to inhibit the photochemical formation of CH3I while promoting the formation of CH_(3)Cl.Conversely,an appropriate concentration of Fe^(3+)enhanced the photochemical production of methyl halides.Field observations indicated a high photochemical production of methyl halides in the natural waters near Qingdao’s coastal area,likely due to the high concentration of dissolved organic matter(DOM),which supports photochemical reactions.Furthermore,the photochemical production of methyl halides in natural seawater was significantly higher than in dark conditions,underscoring the importance of illumination in promoting these photochemical processes in seawater.

5-Fluorouracil dose escalation generated desensitized colorectal cancer cells with reduced expression of protein methyltransferases and no epithelial-to-mesenchymal transition potential

Background:Colorectal cancer(CRC)is one of the most frequently diagnosed cancers.In many cases,the poor prognosis of advanced CRC is associated with resistance to treatment with chemotherapeutic drugs such as 5-Fluorouracil(5-FU).The epithelial-to-mesenchymal transition(EMT)and dysregulation in protein methylation are two mechanisms associated with chemoresistance in many cancers.This study looked into the effect of 5-FU dose escalation on EMT and protein methylation in CRC.Materials and Methods:HCT-116,Caco-2,and DLD-1 CRC cell lines were exposed to dose escalation treatment of 5-FU.The motility and invasive potentials of the cells before and after treatment with 5-FU were investigated through wound healing and invasion assays.This was followed by aWestern blot which analyzed the protein expressions of the epithelial marker E-cadherin,mesenchymal marker vimentin,and the EMT transcription factor(EMTTF),the snail family transcriptional repressor 1(Snail)in the parental and desensitized cells.Western blotting was also conducted to study the protein expressions of the protein methyltransferases(PMTs),Euchromatic histone lysine methyltransferase 2(EHMT2/G9A),protein arginine methyltransferase(PRMT5),and SET domain containing 7/9(SETD7/9)along with the global lysine and arginine methylation profiles.Results:The dose escalation method generated 5-FU desensitized CRC cells with distinct morphological features and increased tolerance to high doses of 5-FU.The 5-FU desensitized cells experienced a decrease in migration and invasion when compared to the parental cells.This was reflected in the observed reduction in E-cadherin,vimentin,and Snail in the desensitized cell lines.Additionally,the protein expressions of EHMT2/G9A,PRMT5,and SETD7/9 also decreased in the desensitized cells and global protein lysine and arginine methylation became dysregulated with 5-FU treatment.Conclusion:This study showed that continuous,dose-escalation treatment of 5-FU in CRC cells generated 5-FU desensitized cancer cells that seemed to be less aggressive than parental cells.

Oxidative Methylation of Toluene with Methane over Basic Zeolite Catalysts Promoted with Alkali Metal Bromides and Alkali Metal Oxides

The catalytic effects for the oxidative methylation of toluene with methane over the basic zeolite catalysts prepared by promoting KY, KX, KM, KZSM-5 or KP with alkali-metal bromides and alkali-metal oxides have been investigated comparatively. The alkali-metal bromides promoted substrates are more effective than the alkali-metal oxides promoted systems. Moreover, the NaBr promoted systems are more active than KBr promoted systems. The most effective catalytic system (8wt%NaBr)/KZSM-5 gave a toluene conversion as high as 76.3% and a total C-8 selectivity of 76.4% (styrene/ethylbenzene=9.76) resulting in a total C-8 yield of 58.3%.

PREPARATION OF POLY(METHYL METHACRYLATE)/LAYERED DOUBLE HYDROXIDES NANOCOMPOSITES via in situ SOLUTION POLYMERIZATION

An exfoliated layered double hydroxides/poly（methyl methacrylate） （LDHs/PMMA） nanocomposite was prepared by in situ solution polymerization of methyl methacrylate （MMA） in the presence of 4-vinylbenzenesulfonate intercalated LDHs（MgAl-VBS LDHs）. MgAl-VBS LDHs was prepared by the ion exchange method, and the structure and composition of the MgAl-VBS LDHs were determined by X-ray diffraction （XRD）, infrared spectroscopy and elemental analysis. XRD and transmission electron microscopy （TEM） were employed to examine the structure of LDHs/PMMA nanocomposite. It was indicated that the LDHs layers were well exfoliated and dispersed in the PMMA matrix. The grafting of PMMA onto LDHs was confirmed by the extraction result and the weight fraction of grafted PMMA increased as the weight fraction of LDHs in the nanocomposites increased.

Reactive dividing wall column for hydrolysis of methyl acetate:Design and control

Reactive distillation and dividing wall column distillation are two kinds of effective separation technologies,and their integrated configuration,reactive dividing wall column(RDWC),presents attractive advantages.In this study,the rigorous simulation of RDWC for methyl acetate hydrolysis is performed,and sensitivity analysis is conducted to obtain the minimum reboiler duty.Then a comparison is made between the conventional process and RDWC process,and it shows that 20.1% energy savings can be achieved by RDWC process.In addition,the dynamic characteristic of RDWC is studied and an effective control strategy is proposed.The simple PI control scheme with three temperature loops can obtain reasonable control performance and maintain products at desired purities.It is proved that this RDWC process is an energy efficiency alternative with good controllability.

Studies on the esterifications of 9-(hydroxyimino)-4-methyl-8,9-dihydrofuro[2,3-h]chromen-2-one with acid chlorides under different conditions

The esterifications of 9-（hydroxyimino）-4-methyl-8,9-dihydrofuro[2,3-h]chromen-2-one （4） with acid chlorides afforded normal oxime-esters 3a-e in 35-78% yields in presence of excessive 4-dimethylaminopyridine as the acid scavenger, whereas the reactions gave unexpected 8-substituted products N-（8-chloro-4-methyl-2-oxo-2H-furo-[2,3-h]chromen-9-yl）amides （5a-c） and 4-methyl-2,9-dioxo-8,9-dihydro-2H-furo[2,3-h]chromen-8-ylcarboxyloates （6d-e） by using excessive acid chlorides. The structures of 10 new compounds were determined by 1H NMR, 13C NMR, MS and HRMS, and the possible mechanism for the formation of unexpected products 5a--c and 6d-e was also proposed.

Novel Distance-Related Matrix Index and QSPR Research for Thermodynamics of Methyl Halides

A novel topological index W F is defined by the matrices X,W and L as W F=XWL.The topological index WF based on the distance-related matrix of molecular graphs is used to code the structural environment of each atom-type in a molecular graph.Good QSPR models have been obtained for standard formation enthalpy of methyl halides.The result indicates that the idea of using multiple matrices to define the distance-related matrix topological index is valid.

Novel Synthesis of Benzotriazol-1-yl Methyl Selenides and Tellurides

Benzotriazol-1-yl methyl selenides and tellurides 4a-h can be simply synthesized by the reaction of 2a-b with 3 in good yields.

A Rapid and Convenient Procedure for the Permethylation of Polysaccharides

Butyllithium was directly added to the solution of polysaccharides in dimethyl sulfoxide. The methylsulfinyl carbanion, as a sugar alkoxide forming reagent, was generated from the solution. All the operations were performed as one-pot reactions. Five polysaccharides from different traditional Chinese medicines and three dextrans were methylated and satisfactory results have been achieved.

Study on the Total Synthesis of 3-Oxo-9β-Acetoxyilicic Acid─The Synthesis of 9β-Acetoxy-3(4),11(13)-Dien-5αH,7αH-12-Eudesmanoic Acid Methyl Ester

The synthesis of 99-acetoxy-3(4), 11(13)-dien-5αH 7αH-12-eudesmanoic acid methyl ester (2) was achieved from oxycarvone. The key step is the p-toluenesulfonhydrazide assisted reductiv rearrangement reaction

Polybutylacrylate/poly(methyl methacrylate) Core-Shell Elastic Particles as Epoxy Resin Toughener: Part I Design and Preparation

Polybutylacrylate (PBA)/poly(methyl methacrylate) (PMMA) core-shell elastic particles (CSEP), whose rubbery core diameter ranged from 0.08 μm to 1.38μm, were synthesized by using conventional emulsion polymerization, multi-step emulsion polymerization, and soapless polymerization. Allyl methacylate (ALMA) and ethylene glycol dimethacrylate (EGDMA) were selected as crosslinking reagents for core polymerization. Methacrylic acid (MAA) was used as functional co-monomer with methyl methacrylate as shell component. The content of vinyl groups in PBA rubbery core increased with the amount of crosslinking reagents. The core-shell ratio affected great on the morphology of the complex particles. Furthermore, the amounts of carboxyl on the surface of core-shell particles, copolymerized with acrylic acid, were determined by potentiometric titration. Results showed that methylacrylic acid was distributed mostly on the surface of particles.

DESIGN AND SYNTHESIS OF NOVEL CHIRAL IONIC LIQUIDS AND THEIR APPLICATION IN FREE RADICAL POLYMERIZATION OF METHYL METHACRYLATE

Two new chiral ionic liquids, 1 -((-)-menthoxycarbonylmethylene)-3-methylimidazolium hexafluorophosphateand 1-((-)-menthoxycarbonylmethylene)-3-hexadecylimidazolium hexafluorophosphate, were designed an d prepared. Theirchemical structures were characterized by ~1H-NMR. Reverse atom transfer radical polymerization of methyl methacrylate(MMA) in these two ionic liquids was carried out using AIBN/CuCl_2/bipy as the initiating system. The resultant well-definedpolymethyl methacrylate (PMMA) was employed as a macroinitiator to induce the atom transfer radical polymerization ofmenthyl methacrylate (MnMA) in chlorobenzene, which yielded a PMMA-b-PMnMA diblock copolymer with narrow polydispersity.

Deoxygenation of methyl laurate to hydrocarbons on silica-supported Ni-Mo phosphides: Effect of calcination temperatures of precursor

SiO2-supported Ni-Mo bimetallic phosphides were prepared by temperature-programmed reduction （TPR） method from the phosphate precur- sors calcined at different temperatures. Their properties were characterized by means of ultraviolet-visible diffuse reflectance spectroscopy （UV-Vis DRS）, H2 temperature-programmed reduction （H2-TPR）, X-ray diffraction （XRD）, transmission electron microscopy （TEM）, CO chemisorption, H2 and NH3 temperature-programmed desorptions （H2-TPD and NH3-TPD）. Their catalytic performances for the deoxygena- tion of methyl laurate were tested in a fixed-bed reactor. When the precursors were calcined at 400 and 500 ℃, respectively, NiMoP2 phase could be formed apart from Ni2P and MoP phases in the prepared C400 and C500 catalysts. However, when the precursors were calcined at 600, 700 and 800 ℃, respectively, only Ni2P and MoP phases could be detected in the prepared C600, C700 and C800 catalysts. Also, in C400, C500 and C600 catalysts, Mo atoms were found to be entered in the lattice of Ni2P phase, but the entering extent became less with the increase of calcination temperature. As the calcination temperature of the precursor increased, the interaction between Ni and Mo in the prepared catalysts decreased, and the phosphide crystallite size tended to increase, subsequently leading to the decrease in the surface metal site density and the acid amount. C600 catalyst showed the highest activity among the tested ones for the deoxygenation of methyl laurate. As the calcination temperature of the precursor increased, the selectivity to C12 hydrocarbons decreased while the selectivity to C11 hydrocarbons tended to increase. This can be mainly attributed to the decreased Ni-Mo interaction and the increased phosphide particle size. In sum, the structure and performance of Ni-Mo bimetallic phosphide catalyst can be tuned by the calcination temperature of precursor.

Electron Transfer Reaction Between Desoxyadenosine and Triplet 2-Methyl-1,4-naphthaquinone:A Laser Photolysis Study

Introduction Electron transfer oxidation of DNA by triplet artificial photonuclease reveals a bright prospect of its application in biology and medicine. Both molecular orbital calculation and laser experiments have indicated that the homo guanine sequence should be the final localization site of photoexcited hole via long range migration within DNA. However, the direct observation of the produced ion pairs of biomolecules especially the stabilized radical cation DNA or its components is hampered by the overwhelming transient absorption of protonated radical anion of photosensitizers, such as 2-methyl-1,4-naphthaguinonel （MQ）.

Studies of the Effects of Alkali Metal Oxides Promoter on the Oxidative Methylation of Toluene with Methane over KY Zeolite Catalysts

The toluene conversion, the selectivity to styrene and ethylbenzene( C8 selectivity) in the oxidative methylation of toluene with methane have been studied comparatively for the KY zeolite catalyst promoted with Li2O, Na2O, K2O, and Cs2O respectively. It was found that the effect of promoter decreased in the order: Cs2O>Na2O>Li2O>K2O.

Design and control of methyl acetate-methanol separation via heat-integrated pressure-swing distillation

Design and control of pressure-swing distillation(PSD) with different heat integration modes for the separation of methyl acetate/methanol azeotrope are explored using Aspen Plus and Aspen Dynamics. First, an optimum steady-state separation configuration conditions are obtained via taking the total annual cost(TAC) or total reboiler heat duty as the objective functions. The results show that about 27.68% and 25.40% saving in TAC can be achieved by the PSD with full and partial heat integration compared to PSD without heat integration. Second,temperature control tray locations are obtained according to the sensitivity criterion and singular value decomposition(SVD) analysis and the single-end control structure is effective based on the feed composition sensitivity analysis. Finally, the comparison of dynamic controllability is made among various control structures for PSD with partial and full heat integration. It is shown that both control structures of composition/temperature cascade and pressure-compensated temperature have a good dynamic response performance for PSD with heat integration facing feed flowrate and composition disturbances. However, PSD with full heat integration performs the poor controllability despite of a little bit of economy.

Differential DNA methylation analysis of SUMF2,ADAMTS5,and PXDN provides novel insights into colorectal cancer prognosis prediction in Taiwan

BACKGROUND Patients with colorectal cancer(CRC)undergo surgery,as well as perioperative chemoradiation or adjuvant chemotherapy primarily based on the tumor–node–metastasis(TNM)cancer staging system.However,treatment responses and prognostic outcomes of patients within the same stage vary markedly.The potential use of novel biomarkers can improve prognostication and shared decision making before implementation into certain therapies.AIM To investigate whether SUMF2,ADAMTS5,and PXDN methylation status could be associated with CRC prognosis.METHODS We conducted a Taiwan region cohort study involving 208 patients with CRC recruited from TriService General Hospital and applied the candidate gene approach to identify three genes involved in oncogenesis pathways.A methylation-specific polymerase chain reaction(MS-PCR)and Epi TYPER DNA methylation analysis were employed to detect methylation status and to quantify the methylation level of candidate genes in tumor tissue and adjacent normal tissue from participants.We evaluated SUMF2,ADAMTS5,and PXDN methylation as predictors of prognosis,including recurrence-free survival(RFS),progression-free survival(PFS),and overall survival(OS),using a Cox regression model and Kaplan–Meier analysis.RESULTS We revealed various outcomes related to methylation and prognosis.Significantly shorter PFS and OS were associated with the CpG_3+CpG_7 hypermethylation of SUMF2 from tumor tissue compared with CpG_3+CpG_7 hypomethylation[hazard ratio(HR)=2.24,95%confidence interval(CI)=1.03-4.85 for PFS,HR=2.56 and 95%CI=1.08-6.04 for OS].By contrast,a significantly longer RFS was associated with CpG_2 and CpG_13 hypermethylation of ADAMTS5 from normal tissue compared with CpG_2 and CpG_13 hypomethylation[HR(95%CI)=0.15(0.03-0.71)for CpG_2 and 0.20(0.04-0.97)for CpG_13].The relationship between the methylation status of PXDN and the prognosis of CRC did not reach statistical significance.CONCLUSION Our study found that CpG_3+CpG_7 hypermethylation of SUMF2 from tumor tissue was associated with significantly shorter PFS and OS compared with CpG_3+CpG_7 hypomethylation.CpG_2 and CpG_13 hypermethylation of ADAMTS5 from normal tissue was associated with a significantly longer RFS compared with CpG_2 and CpG_13 hypomethylation.These methylationrelated biomarkers which have implications for CRC prognosis prediction may aid physicians in clinical decision-making.

Tribenuron-Methyl Resistant Flixweed(Descurainia sophia)

Flixweed seeds were collected from suspected winter wheat fields and remote hillside in Shaanxi Province, China, their sensitivities to tribenuron-methyl were evaluated in the greenhouse. Results revealed that biotype S was susceptible to tribenuron, and its GRs0 was 0.23 g a.i. ha^-1, whereas biotypes R1, R2, R3, and R4 were resistant to the tribenuron, and their GR50 were 161.99, 79.70, 439.80, and 312.30, respectively. Biotypes R1 and R2 showed moderate resistance with resistant indices （RI） of 615.23 and 302.7, respectively. Whereas biotypes R3 and R4 showed high resistance to the herbicide with RI values as high as 1 670.34 and 1 186.10, respectively.