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SummaryThe composition of the copolymers of 1,3-dioxolane with 1,3-dioxepane was investigated using FT-IR and DSC. The first method produce accurate values for the overall composition, the later allows discriminating between the copolymer and the mixture of homopolymers.

Coordinated anionic ring-opening polymerization of ɛ-caprolactone in the presence of alcohols enables functional oligocaprolactones to be obtained easily in a single step. As observed by NMR and Maldi Tof mass spectroscopy, the functionalization of the oligomers, as well as the molecular weight distribution, depend strongly on the chemical structure of the alcohol. Hydroxy telechelic polymers can also be used as transfer agents. Finally, it was found that the chemical nature of the alcohol has a great influence on the kinetics, which suggests a coordination of this moiety on the Lewis site, during all the reaction. Copyright © 2004 Society of Chemical Industry

Summary: Photocationic polymerization for three cyclic acetals, namely 1,3-dioxolane, 1,3-dioxepane and 1,3,6-trioxocane, respectively, has been studied. Several cationic photo-initiators (diaryliodonium or triarylsulfonium salts, and one arene-metal complex) have been used. Differential scanning photo-calorimetry (DPC) has been employed to record the dependence conversion versus time. DPC thermogrames, in turn, have been utilized to calculate the propagation reaction constants as well as the corresponding activation energies. The values for the propagation constants at 30°C are 1.6·102 L/mol·s for 1,3-dioxolane, using a diaryliodonium salt as photoinitiator, 1.6·103 L/mol·s for 1,3-dioxepane and 6.1·103 L/mol·s for 1,3,6-trioxocane, respectively, in the presence of a triarylsulfonium salt as photoinitiator. The activation energies are in the range of 9.6÷19.6 kcal/mole.

Summary: A BF3 complex has been grafted onto silica and used as initiator to polymerize 1,3-dioxolane and 1,3-dioxepane. Grafting the active centers leads to a decrease of the reaction rate. The molecular weight increases steadily, parallel to the monomer conversion and the polydispersity is rapidly stabilized at a low value. MALDI-TOF mass spectrometry analysis shows that most of the polymer chains are initiated by a proton and lost a CH2O unit. An exchange process between polymer chains bound to the silica and those remaining in the reactional medium was proposed. Finally, a semi-continuous process was investigated by adding continuously dioxolane during a 100 hours period.

Functionalised polycaprolactones have been obtained by anionic coordinated ring‐opening polymerisation with Al(OiPr)3as the initiator in the presence of monosaccharides as transfer agents. 1H and 13C NMR spectroscopy, as well as MALDI‐TOF mass spectrometry clearly show the functionalisation of the polycaprolactone chains. Protected monosaccharides bearing primary hydroxyl groups are suited best to get well‐controlled polymer chains. Polycaprolactones functionalised with galactopyranose end groups have been used for the preparation of nanoparticles according to the emulsification‐diffusion procedure. Nanospheres and nanocapsules with diameters around 0.50 μm could be obtained.

34 consecutive patients with PIF or Rel-AML treated with dose-intense EC between 10/2004-12/2011 were evaluated. All patients received initial induction therapy with daunorubicin 45–90mg/m2 IV bolus d1–3 and cytarabine 100mg/m2 CI d1–7, and consolidation with HIDAC for 1–3 courses if CR was achieved. Treatment: 27 patients (79%) received etoposide 3gm/m2 by continuous infusion over 48–72hours followed by cyclophosphamide 50mg/kg iv infusion daily for 3 or 4 days. The remaining 7 patients received reduced etoposide 1.8–2.4gm/m2. The decision to use a given dose of EC was left to the discretion of the treating physician. Chi-Square, Fischers Exact Test and Cox regression analysis were bused for statistical analysis.Patient demographics can be seen in Table 1. Most patients had rel-AML (62%), previous exposure to high or intermediate-dose cytarabine (75%), were < 60 years old (70%), had intermediate or unfavorable cytogenetics (92%), and received at least 1 salvage regimen (in addition to induction and consolidation) prior to dose-intense EC (65%). Patient outcomes are seen in Table 2. Overall, CR was achieved in 32% of patients. Median duration of CR after DI-EC treatment was 5 months. Figure 1 shows overall survival curve. No significant difference in response was found for patient's age >60years (p<0.3085), gender (p<0.1345), exposure to high or intermediate dose cytarabine (p<0.4254), the number of salvage regimens received prior to EP (p<0.1672), or etoposide dose intensity (p<0.5172). Rel-AML patients had significantly higher CR rates compared to PIF (p<0.0145). Subset analysis shows unfavorable karyotype (Figure 2) to be associated with a poorer response (p<0.0223). Grade 3–4 GI toxicity was observed in 19(59%) patients, which was not associated with etoposide dose level (p<0.99) Microbiologically confirmed infections occurred in 26(76%) patients but was not associated with etoposide dose. Treatment related mortality was observed in 6(18%) patients.Dose intense EP therapy was moderately effective in achieving CR, especially in heavily pre-treated rel-AML patients. The regimen was successful as a temporizing treatment prior to allogeneic HSCT. Infection rates are high and warrant close surveillance and early aggressive antibiotic therapy.No relevant conflicts of interest to declare.

Medical records were used to identify newly diagnosed patients with AML who received daunorubicin 90mg/m2(Dau-90) or idarubicin 12mg/m2(Ida-12) between 1/2007 and 6/2012. Patients with APL were excluded. MDS patients who evolved to AML were included. AML was diagnosed by WHO criteria. Patients received daunorubin 90mg/m2 IV bolus or idarubicin 12mg/m2 IV bolus on days 1–3. Cytarabine 100mg/m2 by continuous infusion was given concomitantly on day 1–7 to both groups. All patients underwent marrow biopsy on day 14 after initiation of therapy. If residual disease was found, patients were considered treatment failure. Patients without residual disease were re-biopsied around the time of WBC recovery to assess CR. CR rates are reported after a single induction course.28 Ida-12 and 37 Dau-90 patients were identified. Table 1 shows patient demographics and outcomes. There was no significant baseline difference between the 2 study arms for gender, age, weight, maximum WBC prior to therapy, cytogenetic risk group, percent of patients with FLT-3 ITD or NPM mutations, or combined risk factors. A non-significant trend was observed in the percent of marrow blasts prior to therapy and in the number of patients>60years(but not for age >55) within the Ida-12 study arm. Overall CR was similar between the Ida-12 and Dau- 90 treatment groups(p<0.1072) Subset analysis shows CR rates were significantly higher in Ida-12 treated patients who had an unfavorable karyotype(p<0.0359) or unfavorable combined cytogenetic risk(0.0388) or for age > 55 years(p<.0063). Overall morbidity and mortality was similar between groups.Ida-12 appears to be as effective as Dau-90 for achieving CR after a single induction course. Thus, Thus, substitution of Ida-12 for Dau-90 during times of drug shortages appears acceptable. Ida-12 may potentially be superior for patients >55 years or for those with unfavorable cytogenetics. These results warrant validation from a randomized clinical trial.No relevant conflicts of interest to declare.

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Abstract 4314