Microbial Transformation of Taxoids and Synthesis of Taxoids ith an Oxetane Ring

Microbial trdrisformation of taxoids was inveStigared: taxoid 2 was transformed into 1β and 14β hydroxylated derivahves 3 and 4, unnatural taxoid 6 was transformed into 1β-hydroxy derivative 7 and 11(15-1) abeotaxane 8. Taxoids with an oxetane ring, 11-13 were synthesized from 1 via chemical reachons.

Synthesis of 1,1,3,3,5,5-hexamethyl-1,5-bis[(3-ethyl-3-methoxyoxetane)propyl]trisiloxane and Research on Its UV-curing Performance

A compound,3-ethyl-3-hydroxymethyloxetane(EHO),was synthesized with diethyl carbonate and trihydroxypropane as raw materials,3-ethyl-3-allylmethoxy oxetane(EAMO)was synthesized with EHO and allyl bromide,and 1,1,3,3,5,5-hexamethyl-1,5-bis[(3-ethyl-3-methoxyoxetane)propyl]trisiloxane(HMBEMOPTS)was synthesized with EAMO and 1,1,3,3,5,5-hexamethyltrisiloxane(HMTS).HMBEMOPTS is a novel UV-curable oligomer.The test of photo-DSC shows the photosensitivity of HMBEMOPTS is better than the ordinary oxetane,3-ethyl-3-[(3-ethyloxetan-3-yl)methoxymethyl]oxetane.HMBEMOPTS was mixed with bisphenol A type epoxy resin E-51 to prepare a cationic UV-curable system,and triarylsulfonium hexafluoroantimonate(UV-6976)was used as a cationic photoinitiator.The mechanical tests of coating films prove that when the mass fraction of HMBEMOPTS is 50%,the mechanical properties of the curing system are the best.The impact strength of the UV-curable films is measured to be 40 kg·cm and the flexibility is 2 mm;the tensile strength and flexural strength of the prepared specimens are 20.74 MPa and 13.43 MPa,respectively.The experimental results show that HMBEMOPTS can effectively improve photosensitivity and flexibility of the photosensitive resin.

Construction of the Oxetane Ring from 5α-Acyloxy-Δ^(4(20))-taxoids

-An oxetane ring can be constructed from 5 α-acyloxy-Δ4(20) -taxoids with osmylation as the first step in the usual manner. The innovation reported here is the use of an intramolecularly available acyl group for the protection of 20-OH by an unexpected 5-to 20-migration under slightly basic conditions.

Directing the Metabolism of Drugs Away from CYP450: The Use of Oxetane Rings

Treatment of health problems that accompany aging often includes pharmacotherapy. It is thus common for older adults—and, increasingly, younger adults—to be on multiple medications, either prescription or over-the-counter (OTC). With the consumption of multiple medications, drug-drug interactions (DDIs) are a concern. The site of drug-drug interactions is often at the level of drug metabolism. If a drug inhibits (or enhances) the metabolism of another, the blood level (therapeutic effect) can be decreased below the required level, or adverse effects can increase. Because most currently used drugs are metabolized via cytochrome P450-catalyzed pathways, drug discovers seek drugs that are metabolized by alternate pathways. Medicinal chemists have come upon a strategy—the incorporation of oxetane rings in the drug structure—that increases the likelihood that a drug will not be metabolized via CYP450. The same modification gives other desirable physical properties to the molecule. Although there are no guarantees that there will be fewer DDIs or an absence of other unexpected problems, the strategy could pave the way for new drugs that are safer and easier to use with concomitant medications.

Synthesis, UV-curing Behavior and Surface Properties of New Fluorine-containing Aromatic Oxetane Monomers

In this paper, we combined high-end cationic UV-curable material with fluorinated chain obtaining a series of new fluorine-containing aromatic oxetane monomers via a mild nucleophilic substitution reaction. The structures and properties of monomers were characterized using ~1 H-NMR, ^（19） F-NMR, dynamic viscosity tests and differential scanning calorimetry（DSC）. It was determined that all of the fluorinated monomers obtained had much lower viscosity and higher thermostability after the introduction of hexafluorobenzene. Then, UV-curable coatings were prepared using four fluorine-containing aromatic oxetane monomers（FOX1-4）; the UV-curing kinetics, with three kinds of initiators, and properties of the cured films were evaluated using real-time Fourier transform infrared（FTIR） spectroscopy, water and diiodomethane contact angle tests, surface energy calculations and scanning electron microscopy（SEM）. The FTIR spectroscopy results showed that the coatings possessed excellent conversion rate（〉 99% with liquid initiator PAG-201 in 150 s）, and as the fluorine content increased, the monomers exhibited decreased mobility with the increasing viscosity and worse solubility with fluorinated monomers, resulting in a lower conversion rate. Moreover, the coatings possessed favorable hydrophobic and oleophobic properties and low surface energies owing to the fluoride chains floating to the membrane-air interface, which was also confirmed by discrete concave structures in SEM images. These new kinds of monomers can replace traditional fluorinated cationic monomers applied to the fingerprint resistant, fouling resistant, scratch resistant and anti-aging coatings, adhesives or printing ink materials.

A facile approach for the construction of the oxetane ring from 5α-acyloxy-Δ^(4(20)) - taxoids

An oxetane ring can be constructed from 5α-acyloxy-Δ4(20)-taxoids. Hie facile intramolecular acyl migration from 5- to 20-position under slightly basic conditions enabled the construction of the oxetane ring in a convenient short cut, whereas the acyl migration from 2- to 20-position left the 2-hydroxyl accessible to a later benzoylation. An unexpected five-mem-bered 4-O, 20- O sulfite ring was formed in the attempted construction of the oxetane ring with 5α-triflate as a leaving group. After the construction of the oxetane ring, treatment with strong base LiHMDS and acetyl chloride gave the expected 4-O-acetate while treatment with acetic anhydride and DMAP gave a 4-O-acetoacetate.

Synthesis of novel D-seco-taxoids derived from 1-deoxybaccatinⅥ

New D-seco-taxoids were synthesized from 1-deoxybaccatinⅥand their structures were confirmed by 1H NMR,13C NMR, ESIMS and X-ray crystallography.The key step of the synthesis involved the opening of the oxetane ring under acid and basic conditions in order to obtain new multidrug resistance（MDR） reversal agents and new synthetic precursors of paclitaxel analogues.

Crystal Studies and Antitumor Activities of Novel D-seco-taxoids Derived from 1-Deoxybaccatin Ⅵ

Two novel taxoids were synthesized from 1-deoxybaccatin Ⅵ and their crystal structures were determined by X-ray crystallographic techniques. The influences of oxetane ring on molecular conformations and bioactivity were investigated. The result shows that the oxetane ring plays an important role in the conformation and bioactivity of the diterpenoid core. In the structure of compound 3, the six-membered A ring exhibits the 1,4-di-planar conformation, the eightmembered B ring adopts a boat-chair conformation, and the six-membered C ring exhibits a slightly distorted half-chair conformation. However, in D-seco-taxoid 4, the six-membered C ring exhibits a boat conformation with the release of ring strain for the D-ring opening.

Effects of Nano-Aluminium on The Combustion of A PolyNIMMO-Based Propellant

Propellants containing micro-aluminium particles have been shown to produce faster burn rates than conventional gun propellants.However,they are also more abrasive than conventional propellants.Nano-material propellants have been reported to give similar benefits to micron-material propellants but without the disadvantage of increased abrasion.Tests were conducted to compare the burn rates,ignitability and wear rates of a propellant loaded with 0% aluminium,15% micro-aluminium and 15%nano-aluminium.Closed vessel tests showed a burn rate increase of 39% in the range 30-250 MPa,and 70% at low pressure(50-100MPa)for the nano-aluminium propellant compared with the baseline propellant.The micro-aluminium propellant showed only a 10%increase in the burn rate compared with the standard propellant.The ignition delay for the nano-aluminium propellant was slightly shorter than that of the baseline propellant.Substantially increased wear rates were measured for the micro-aluminium propellant.The nano-aluminium propellant showed reduced wear rates compared with the micro-aluminium propellant but these were still substantially greater than those for the baseline propellant.