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Thianthrene 양이온 라디칼과 Benzyl alcohol의 반응에 대한 새로운 메카니즘
문형민 전남대학교 교육대학원 2009 국내석사
상온과 acetonitrile 용매 내에서 thianthrene cation radical perchlorate (Th^(+.)ClO₄^(-))는 Benzylalcohol (23)과 반응하였다. 이 반응의 주요 생성물은 Benzyl carbocation으로부터 N-benzylacetamide (24)와 Thianthrene(Th), Thianthrene Oxide(ThO)였다. Benzyl carbocation은 Thianthrene cation radical과 Benzyl alcohol이 반응해서 형성된 착물(27)의 SN1반응에 의해서 ThO를 잃고 생성되었다. 이 Benzyl carbocation이 acetonitrile 용매와 반응하여 Ritter-type 중간체를 거쳐서 N-benzylacetamide가 형성된다. 치환된 Benzyl alcohol의 경우 안정화된 Benzyl carbocation의 생성으로 많은 양의 N-benzyl acetamide와 Dibenzyl ether의 생성이 이루어짐이 이미 연구되었지만, 치환되지 않은 Benzyl alcohol의 경우 N-benzyl acetamide의 생성이 어렵다는 지금까지의 보고와는 달리, 우리의 연구에서는 N-benzyl acetamide를 얻을 수 있었으며, Dibenzyl ether는 생성되지 않았다. 반응에서 2 moles의 Thianthrene cation radical(Th^(+.))은 환원된 Thianthrene(Th)과 산화되어 Thianthrene oxide(ThO)가 되었다. 이는 원래 Th 와 ThO가 같은 양이 형성되어야 하나 부생성물이 미량 생성되어 ThO의 양이 상대적으로 더 적게 형성됨을 알 수 있었다. Thianthrene cation radical perchlorate (Th^(+.)ClO₄^(-)) reacted readily with Benzyl alcohol(23) in an acetonitrile solution at room temperature. Benzyl alcohol (23) was converted into N-benzylacetamide, which arose from hydration, during workup, of a Ritter-type intermediate from reaction of benzyl cation with solvent acetonitrile. While Th^(+.) was converted quantitatively into thianthrene (Th) and Thianthrene oxide (ThO), the oxygen atom of ThO came from the benzyl alcohol.
폴리에스테르 織物의 Benzyl alcohol과 Sodium hydroxide 混合水溶液에 依한 減量加工에 關한 硏究
polyester georgette fabric was floated in various conditions of sodium hydroxide solution and sodium hydroxide/benzyl alcohol mixture solution. The effects of benzyalcohol addition in sodium hydroxide solution were measured as the weight loss, improvement of handle and changes of breaking strength and elongation of fabric. The results were expressed as follows ; The tendency of weight loss in the NaOH solution was accelerated by the addition of small amount of benzyl alcohol (1-2%). By the addition of small amount of benzylalcohol, it was possible to lower the treating temperature and to reduce the NaOH concentration in alkali treatment of polyester fabric. The fabric treated in NaOH/benayl alcohol mixture solution showed lower weight loss and higher breaking strength and elongation than that in NaOH solution, when the same handle improvement was concerned.
톨루엔 대사산물 중 뇨중 벤질알콜의 분석방법의 관한 연구
연구배경 ; 산업현장에서의 톨루앤 노출형태는 톨루엔을 생산하는 정유화학근로자, 톨루엔을 원료 또는 용제로 사용하는 화학공장이나 실험실에 근무하는 근로자, 염료 및 도료생산자는 톨루엔에 노출될 위험성이 크다. 톨루엔의 대사산물중 마뇨산은 여러 가지 벤조산함유 음식뿐아니라 여러종류의 음료섭취에도 영향을 받아서 정확한 측정이 힘든 반면 벤질알콜은 이러한 영향을 받지않는 대사산물로써 만성적인 폭로에 사용할 수 있는 대사산물이다. 연구방법 : 본 연구에서는 톨루엔의 대사산물 중에서 요중 Bezyl alcohol에 대한 분석방법을 가스크로마토그래피(Gas Chromatography.GC)의 불꽃 이온화 검출기(Flame lonzation Detector, FID)와 질량분석검출기(Mass Selective Detector.MSD)를 이용하여 , 신속 정확하게 정량할 수 있는 분석법을 개발하고자 하었다. 각 분석방법의 검토조건으로 선택성(Specificity), 직선성(Linearity), 검출한계(limit of detection, LOD), 및 정량한계(limit of quantification, LOQ), 회수율(Recovery), 정밀성(Precision) 및 정확성(Accuracy)에 대하여 정토하였다. 결과 ; GC-FID와 GC-MSD를 이용하여 Benzyl alcohol을 분석한 결과를 비교해보면, 우선 선택성은 GC-FID의 머무름 시간이 7.085분에 나타났으며, GC-MS법을 사용한 SlM모드에서 얻어진 머무름 시간은 6.87분으로 다른 방해물질의 간섭을 받지 않고 분리되었다. 두 방법 간의 직선성은 각 농도별 범위에서 GC-FID는 r^(2)=0.994, GC-MS는 r^(2)=0.999로 나타나 두 분석방법 모두 직선성 0.99 이상의 값을 보였다. GC-FID법의 LOD가 7.2㎍ BeOH, LOQ가 24㎍ BeOH/L를 나타내었고, GC-MS법이 LOD 0.8㎍ BeOH/L이었고, LOQ 2.6㎍ BeOH/L 이었다. 회수율은 각각 93%, 97%를 나타내었고, 정밀도(CV,%)는 3.83%, 1.73%이고 정확도는±16.5%, ±9.12%로 나타났다. 결론 ; Benzyl alcohol의 분석방법을 비교해 보았을 때 GC-MS법이 GC-FID보다 약 10배 정도의 낮은 검출한계(LOD)꼭 정량한계(LOQ)가 나타났는데, 이는 SIM모드 방법이 특정 이온만 정출할 수 있어 선택성이 좋고, 높은 검출 감도를 보였다. 따라서 FID 와 MSD방법이 둘 다 벤질알콜을 검출하는데 좋은결과를 보일수있는 검사방법이라고 생각이 들며 즘 더 많은 조건을 고려한다면 향후 툴루엔 근로자의 건강관리에 많은 도움이 될 수 있을것이라 생각한다 Background: Hippuric acid that toluene metabolites is influenced by some food, any other drink containing that bonzoic acid. it is not abailabe to detect accuracy for exposure. on the other hand, benzyl alcohol is not infuenced by these condition that is use to dectect chronic toluene exposure. Material & Method: Analytic methods using Gas chromatography(GC) - Flame lonization Detector (FID) and GC-Mass Selective Detector(MSD) to measure benzyl alcohol in urine as a metabolite of toluene were compared in terms of the specificity, linearity, limit of detection(LOD), limit of quantification(LOQ), recovery rates, precision and accuracy. Results: Specificity in GC-FID was retention time 7.085 minutes and 6.87 minutes for GC-MS in terms of retention time. For Linearity, GC-FID was r^(2)=0.994, GC-MS was r^(2)=0.999 which means it has lineanty. For GC-FID, LOD was 7.2㎍ BeOH/L, LOQ was 24㎍ BeOH/L. For GC-MS, LOD was 0.8㎍ BeOH/L and LOQ was 2.6㎍ BeOH/L. The recovery rate was 93%, 97% each other. And coefficients of variation (as an index of precision) were 3.83% for GC-FID, 1.73% for GC-MS. Accuracy were ±16.5%, ±9.12%. Conclusion: GC-MS showed 10 times lower LOD and LOQ than GC-FID. This results can be explained that the SIM mode used in GC-MS can detect a specific ion.
Non-aqueous sol-gel routes are elegant approaches for the synthesis of nanomaterials such as metal oxide nanocrystals and ordered organic-inorganic hybrid materials. These routes involving the reaction of metal oxide precursors in organic solvents (e.g. benzyl alcohol) at moderate temperature and pressure, offer advantages such as high crystallinity of the as synthesized oxides, high purity, high reproducibility and the ability to control the crystal growth without the need of additional ligands. Moreover, non-aqueous sol-gel is particularly suitable for one-pot synthesis of multi-metal and doped oxide materials. Microwave synthesis has recently shown several important advantages compared to traditional heating for the synthesis of inorganic nanomaterials by soft chemistry. In particular, the “benzyl alcohol route” greatly benefits from microwave heating by decreasing the reaction time to just a few minutes for nanoparticle formation, suppressing side reactions and improving the yield. In this thesis, a one-pot non-aqueous synthesis of crystalline SnO2- and Fe3O4-based graphene heterostructures in just few minutes for Li-ion battery applications is introduced. Here, the combined properties of the microwave heating and the “benzyl alcohol route” allow to selectively grow metal oxide nanoparticles at the surface of graphene oxide, which is reduced during synthesis. The as-fabricated nanostructures show good lithium intercalation-deintercalation performances at high rate and good cycling stability compared to the separate nano-building blocks. 본 연구에서는 리튬 이온 전지의 음극제로 사용하기 위해 마이크로웨이브를 열원으로 하여 비가수성 졸-겔 반응을 통한 산화 주석, 자철석과 리튬 이온 이차 전지의 전극으로서 이상적인 성질을 가지고 있다고 알려져 있는 그라핀-금속 산화물(산화주석, 자철석)혼합체를 원팟으로 합성하였다. 여기서 마이크로웨이브 가열과 ‘벤질 알코올’ 경로의 특성이 결합되어 그라핀 옥사이드 표면 위에서 금속 산화물이 선택적으로 형성될 수 있었다. 그리고 리튬 이온 이차 전지의 음극으로서 성능 시험을 통하여 단순히 금속 산화물만 있을 경우보다 향상된 주기 성질과 높은 전류 속도에서도 안정적으로 용량을 유지하는 것을 확인하였다.
Adawi, Hayat Ismail Princeton University ProQuest Dissertations & Thes 2023 해외박사(DDOD)
소속기관이 구독 중이 아닌 경우 오후 4시부터 익일 오전 9시까지 원문보기가 가능합니다.
The industrial ubiquity of crystalline Bronsted acid zeolite catalysts incentivizes their adaptation for emerging conversions, including for upgrading biomass-derived platform molecules to fuels and chemicals conventionally produced from nonrenewable petroleum. The aluminosilicate backbones of zeolites form periodic architectures with micropores of molecular diameters (dpore < 1 nm). Micropores can sieve molecules and reduce activation energies through van der Waals stabilization of confined moieties, but they can also inhibit diffusion of desired bulky species. Expanded zeolite applications necessitate structure-function studies of modified hierarchical zeolites containing auxiliary mesopores (dpore = 2-50 nm) capable of increasing catalytic efficiency by enhancing diffusion of bulky molecules.This dissertation investigated impacts of mesopores on reaction, diffusion, and deactivation in hierarchical zeolites by probing competing parallel reactions with kinetically relevant differences in effective diffusivities (De): alkylation of 1,3,5-trimethylbenzene (TMB) by benzyl alcohol (BA) to 1,3,5-trimethyl-2-benzylbenzene (TM2B), or self-etherification of BA to dibenzyl ether (DBE). These probes exclusively interrogated how steric differences (predicted from calculated confinement energies for adsorbed molecules using periodic density-functional theory) impacted observed activity, by precluding complicating interactions between zeolites' hydrophilic silanol defects and heavily oxygenated biomass. Proton-normalized reaction rates were measured for (hierarchical) zeolites synthesized from MFI, MOR, and BEA parent architectures of different crystal sizes, using post-synthetic demetallation treatments under ambient or autogenous pressures.Extracted rate constants demonstrated prevailing kinetic control for hierarchical zeolites that increased De,TMB relative to microporous zeolites with crystal radii (R) below thresholds that otherwise overinflated the relevant diffusion timescale (De,TMB/R2 ). Subsequent thermogravimetric analyses of spent catalysts revealed that graphitic coke formed from undesired polyalkylation of products preferentially deposited in micropores and dampened activity by irreversibly blocking protons. Subsequently extracted deactivation rate constants (kD) scaled logarithmically with coke accumulation. In contrast, BA, TMB, TM2B, DBE unbiasedly saturated all pores without inducing kinetically relevant deactivation. Hierarchical zeolites accommodated more coke than microporous parents at equivalent BA conversions while delaying onsets of measurable kD. These findings extend to many zeolite- and zeotype-catalyzed reactions, including ketone reduction on tin-type BEA explored in this dissertation. Ultimately, careful kinetics analysis complemented thorough catalyst characterization to inform future selection and design of heterogeneous catalysts.