Phosphorus-containing polymers are of considerable interest as flame-retardants additives. We report investigations into the flame-retardant properties of a series of polyphosphinoboranes RR’PBH2n ...prepared by iron-catalyzed dehydrocoupling protocols. When cotton towel was impregnated with the polyphosphinoboranes and exposed to a flame, the presence of polyphosphinoborane was found to result in self-extinguishing of the flame leaving behind a charred material. In contrast, under analogous conditions, untreated cotton and cotton treated with polystyrene burnt and was completely consumed. Analysis of the char revealed the formation of phosphoric and boric acids, species commonly invoked for the action of related flame-retardant species. The use of P-disubstituted polyphosphinoboranes was found to slightly slow burning; however, the presence of halogenated groups in the side chain had little effect suggesting that it is the main chain that imparts any flame-retardant effect. Exposure of cotton treated with poly(phenylphosphinoborane) to water was not found to have any effect on flame-retardancy demonstrating the non-leachability of these polymers in aqueous media.
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•Polyphosphinoboranes were shown to function as flame retardant materials for cotton.•The polymers were prepared by catalytic dehydrocoupling and, in some cases, poly-polymerisation modification.•The polymers display self-extinguishing behaviour.•On impregnation into cotton, the polymers were non-leachable in water.
Polymers with a phosphorus-boron main chain have attracted interest as novel inorganic materials with potentially useful properties since the 1950s. Although examples have recently been shown to be ...accessible
via
several routes, the materials reported so far have been limited to P-mono(organosubstituted) materials, RHPBH
2
n
, containing P-H groups. Here we report a general route for the post-polymerisation modification of such polyphosphinoboranes giving access to a large range of previously unknown examples featuring P-disubstituted units. Insertion of alkenes, R′CH&z.dbd;CH
2
into the P-H bonds of poly(phenylphosphinoborane), PhHPBH
2
n
was facilitated by irradiation under UV light in the presence of the photoinitiator 2,2-dimethoxy-2-phenylacetophenone (DMPAP) and (2,2,6,6-tetramethylpiperidin-1-yl)oxyl (TEMPO) under benchtop conditions giving high molar mass, air-stable polymers PhR′PBH
2
n
with controlled functionalisation and tunable material properties. The mechanistic explanation for the favourable effect of the addition of TEMPO was also investigated and was proposed to be a consequence of reversible binding to radical species formed from the photolysis of DMPAP. This new methodology was also extended to the formation of crosslinked gels and to water-soluble bottlebrush copolymers showcasing applicability to form a wide range of polyphosphinoborane-based soft materials with tunable properties.
New, air-stable inorganic soft materials are accessible under mild conditions
via
TEMPO-mediated radical hydrophosphination of alkenes using polyphosphinoboranes.
Catalytic dehydropolymerization of halogen‐functionalized phosphine–boranes (4‐X‐C6H4)PH2⋅BH3 (1a: X = Br, 1b: X = I) with CpFe(CO)2(OTf) at 100 °C provides convenient access to ...halogen‐functionalized polyphosphinoboranes (4‐X‐C6H4)PH–BH2n (2a: X = Br, 2b: X = I). These polymers are useful precursors for post‐polymerization functionalization, which is demonstrated by Sonogashira coupling under mild conditions to yield the alkynyl‐functionalized polyphosphinoborane (4‐PhCC‐C6H4)PH–BH2n (3).
Halogen‐functionalized polyphosphinoboranes are obtained by iron‐catalyzed dehydropolymerization of phosphine‐boranes. These P‐B polymers are further functionalized by post‐polymerization Sonogashira coupling to provide polyphosphinoboranes featuring alkynyl groups in the side chain.
Polymers with a phosphorus-boron main chain have attracted interest as novel inorganic materials with potentially useful properties since the 1950s. Although examples have recently been shown to be ...accessible
several routes, the materials reported so far have been limited to P-mono(organosubstituted) materials, RHPBH
, containing P-H groups. Here we report a general route for the post-polymerisation modification of such polyphosphinoboranes giving access to a large range of previously unknown examples featuring P-disubstituted units. Insertion of alkenes, R'CHdouble bond, length as m-dashCH
into the P-H bonds of poly(phenylphosphinoborane), PhHPBH
was facilitated by irradiation under UV light in the presence of the photoinitiator 2,2-dimethoxy-2-phenylacetophenone (DMPAP) and (2,2,6,6-tetramethylpiperidin-1-yl)oxyl (TEMPO) under benchtop conditions giving high molar mass, air-stable polymers PhR'PBH
with controlled functionalisation and tunable material properties. The mechanistic explanation for the favourable effect of the addition of TEMPO was also investigated and was proposed to be a consequence of reversible binding to radical species formed from the photolysis of DMPAP. This new methodology was also extended to the formation of crosslinked gels and to water-soluble bottlebrush copolymers showcasing applicability to form a wide range of polyphosphinoborane-based soft materials with tunable properties.
Aims
To evaluate the efficacy and safety of ultra‐rapid lispro (URLi) versus lispro in a paediatric population with type 1 diabetes (T1D) in a Phase 3, treat‐to‐target study.
Materials and Methods
...After a 4‐week lead‐in to optimize basal insulin, participants were randomized to double‐blind URLi (n = 280) or lispro (n = 298) injected 0 to 2 minutes prior to meals (mealtime), or open‐label URLi (n = 138) injected up to 20 minutes after start of meals (postmeal). Participants remained on pre‐study basal insulin (degludec, detemir or glargine). The primary endpoint was glycated haemoglobin (HbA1c) change from baseline after 26 weeks (noninferiority margin 4.4 mmol/mol 0.4%).
Results
Both mealtime and postmeal URLi demonstrated noninferiority to lispro for HbA1c: estimated treatment difference (ETD) for mealtime URLi −0.23 mmol/mol (95% confidence interval CI −1.84, 1.39) and postmeal URLi −0.17 mmol/mol (95% CI −2.15, 1.81). Mealtime URLi reduced 1‐hour postprandial glucose (PPG) daily mean (P = 0.001) and premeal to 1 hour postmeal PPG excursion daily mean (P < 0.001) versus lispro. The rate and incidence of severe, nocturnal or documented hypoglycaemia (<3.0 mmol/L 54 mg/dL) were similar for all treatments. With mealtime URLi versus lispro, the rate of postdose hypoglycaemia (<3.0 mmol/L) was higher at ≤2 hours (P = 0.034). The incidence of treatment‐emergent adverse events was similar for all treatments. More participants reported an injection site reaction with mealtime URLi (7.9%) versus postmeal URLi (2.9%) and lispro (2.7%).
Conclusions
In children and adolescents with T1D, URLi demonstrated good glycaemic control, and noninferiority to lispro in HbA1c change for mealtime and postmeal URLi. When dosed at the beginning of meals, URLi reduced 1‐hour PPG and PPG excursions versus lispro.
Introduction
To assess time in range (TIR) (70–180 mg/dL) with postprandial glucose (PPG)-focused titration of ultra rapid lispro (URLi; Lyumjev®) in combination with insulin degludec in people with ...type 1 diabetes (T1D).
Methods
This phase 2, single-group, open-label, exploratory study was conducted in 31 participants with T1D on multiple daily injection therapy. Participants were treated with insulin degludec and Lispro for an 11-day lead-in and then URLi for a 46-day treatment period consisting of 35-day titration and 11-day endpoint maintenance period. Glucose targets for the titration period were PPG < 140 mg/dL or < 20% increase from premeal, fasting glucose 80–110 mg/dL, and overnight excursion ± 30 mg/dL or less. Participants used the InPen™ bolus calculator and Dexcom G6 continuous glucose monitoring (CGM).
Results
Primary endpoint mean TIR (70–180 mg/dL) with URLi during the maintenance period was 70.2%. TIR (70–180 mg/dL) and times below/above range were not significantly different with URLi (maintenance) versus lispro (lead-in). HbA1c decreased from 7.1% at screening to 6.8% at endpoint (least squares mean LSM change from baseline, − 0.36%;
P
< 0.001). Fructosamine and 1,5-anhydroglucitol improved (
P
< 0.001). Mean hourly glucose using CGM was reduced from 8:00
am
to 4:00
pm
with URLi. Overall highest PPG excursion across meals was significantly reduced at URLi endpoint compared with lispro lead-in (mean 56.5 vs 72.4 mg/dL;
P
< 0.001). Insulin-to-carbohydrate ratio (U/X g) was reduced (more insulin given) at breakfast at URLi endpoint vs lead-in (LSM 9.0 vs 9.7 g;
P
= 0.002) and numerically decreased at other meals. Total daily insulin dose (TDD) was higher at URLi endpoint compared with lispro lead-in (mean 50.2 vs 47.0 U;
P
= 0.046) with similar prandial/TDD ratio (mean 52.1% vs 51.2%). There were no severe hypoglycemia events during the study.
Conclusions
URLi in a basal-bolus regimen focusing on PPG targets demonstrated improved overall glycemic control and reduced PPG excursions without increased hypoglycemia in participants with T1D.
Trial Registration
ClinicalTrial.gov, NCT04585776.
Introduction
To evaluate time in range metrics and HbA1c in people with type 2 diabetes (T2D) treated with ultra rapid lispro (URLi) using continuous glucose monitoring (CGM) for the first time in ...this population.
Methods
This was a Phase 3b, 12-week, single-treatment study in adults with T2D on basal-bolus multiple daily injection (MDI) therapy using basal insulin glargine U-100 along with a rapid-acting insulin analog. Following a 4-week baseline period, 176 participants were newly treated with prandial URLi. Participants used unblinded CGM (Freestyle Libre). Primary endpoint was time in range (TIR) (70–180 mg/dl) during the daytime period at Week 12 compared to baseline with gated secondary endpoints of HbA1c change from baseline and 24-h TIR (70–180 mg/dl).
Results
Improved glycemic control was observed at Week 12 versus baseline including mean daytime TIR (change from baseline Δ 3.8%;
P
= 0.007), HbA1c (Δ − 0.44%;
P
< 0.001), and 24-h TIR (Δ 3.3%;
P
= 0.016) with no significant difference in time below range (TBR). After 12 weeks, there was a statistically significant decrease in postprandial glucose incremental area under curve, overall, across all meals, within 1 h (
P
= 0.005) or 2 h (
P
< 0.001) after the start of a meal. Basal, bolus, and total insulin dose were intensified with increased bolus/total dose ratio at Week 12 (50.7%) versus baseline (44.5%;
P
< 0.001). There were no severe hypoglycemia events during the treatment period.
Conclusions
In people with T2D, URLi in an MDI regimen was efficacious with improved glycemic control including TIR, HbA1c, and postprandial glucose without increased hypoglycemia/TBR.
Clinical Trial registration number
NCT04605991.
New, air-stable inorganic soft materials are accessible under mild conditions
via
TEMPO-mediated radical hydrophosphination of alkenes using polyphosphinoboranes.
Polymers with a phosphorus-boron ...main chain have attracted interest as novel inorganic materials with potentially useful properties since the 1950s. Although examples have recently been shown to be accessible
via
several routes, the materials reported so far have been limited to P-mono(organosubstituted) materials, RHPBH
2
n
, containing P–H groups. Here we report a general route for the post-polymerisation modification of such polyphosphinoboranes giving access to a large range of previously unknown examples featuring P-disubstituted units. Insertion of alkenes, R′CH
Created by potrace 1.16, written by Peter Selinger 2001-2019
CH
2
into the P–H bonds of poly(phenylphosphinoborane), PhHPBH
2
n
was facilitated by irradiation under UV light in the presence of the photoinitiator 2,2-dimethoxy-2-phenylacetophenone (DMPAP) and (2,2,6,6-tetramethylpiperidin-1-yl)oxyl (TEMPO) under benchtop conditions giving high molar mass, air-stable polymers PhR′PBH
2
n
with controlled functionalisation and tunable material properties. The mechanistic explanation for the favourable effect of the addition of TEMPO was also investigated and was proposed to be a consequence of reversible binding to radical species formed from the photolysis of DMPAP. This new methodology was also extended to the formation of crosslinked gels and to water-soluble bottlebrush copolymers showcasing applicability to form a wide range of polyphosphinoborane-based soft materials with tunable properties.
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