title: The relationship between home and early childhood setting in supporting early literacy

authors: McLachlan, Claire

abstract: This review examines the relationship between language and literacy experience in the home environment and their implications for literacy in early childhood settings. Building on early sociocultural research into how children develop language and literacy within the home environments, recent research on how home environments support children's developing language and literacy knowledge and skills are explored, along with the research on the importance of 'serve and return' interactions between caregivers and young children for maximum brain development and language acquisition. The review also examines research on the use of multimodal literacies in home environments, along with the contribution of family literacy models to understanding how families support children's development. The implications of this body of research are examined in relation to what it means for early childhood teachers to support literacy learning and development in diverse learners and create a reciprocal learning environment for literacy.

text: The relationship between home and early childhood setting in supporting early literacy This review examines the relationship between language and literacy experience in the home environment and their implications for literacy in early childhood settings. Building on early sociocultural research into how children develop language and literacy within the home environments, recent research on how home environments support children's developing language and literacy knowledge and skills are explored, along with the research on the importance of 'serve and return' interactions between caregivers and young children for maximum brain development and language acquisition. The review also examines research on the use of multimodal literacies in home environments, along with the contribution of family literacy models to understanding how families support children's development. The implications of this body of research are examined in relation to what it means for early childhood teachers to support literacy learning and development in diverse learners and create a reciprocal learning environment for literacy.

year: 2025

title: ESIMS targeted synthesis of novel {Pt2S2} derivatives

authors: Fortney-Zirker, Ryland

subjects: Inorganic Chemistry

abstract: Electrospray ionisation mass spectrometry (ESIMS) was used to investigate ring-
opening reactions of several epoxides with the nucleophilic dinuclear PtII
complexes
[Pt2(μ-E)2(PPh3)4] (E = S, 1a; Se, 1b) and several activated cyclopropanes, N -
tosylaziridine, and thiirane with 1a. Epoxides cyclohexene oxide, styrene oxide,
epibromohydrin, and 2,2-dimethyloxirane were found to undergo ring-opening when
reacted with 1a and derivatives [Pt2(μ-S)(μ-S C6H10OH)(PPh3)4]BPh4 (5[BPh4],
[Pt2(μ-S)(μ-S C8H8OH)(PPh3)4]BETI (6[BETI]), [Pt2(μ-S CH2CH(OH)CH2 μ-S)-
(PPh3)4][PF6]2 (3[PF6]2), and [Pt2(μ-S)(μ-S CH2C(Me)2OH)(PPh3)4]BPh4 (7 [BPh4])
were respectively isolated and structurally characterised with 31P{1H} and 195Pt nu-
clear magnetic resonance (NMR) spectroscopy, and for 5, 3 and 7 single crystal X-
ray diffraction (XRD) studies. 6 was found to be a mixture of isomers, and crystals
suitable for a single crystal XRD experiment were not obtained. Both styrene oxide
and epibromohydrin underwent ring-opening when reacted with 1b and the respec-
tive derivatives [Pt2(μ-Se)(μ-Se C8H8OH)(PPh3)4]+ and [Pt2(μ-Se CH2CH(OH)-
CH2 μ-Se)(PPh3)4]2+ were characterised by ESIMS. The fully substituted epoxide
2,3-dimethyl-2,3-epoxybutane did not undergo ring-opening when treated with 1a
in refluxing methanol for several hours. 5,6-Epoxy-5,6-dihydro-[1,10]-phenanthro-
line resulted in ring-opening when reacted with 1a however the resulting deriva-
tive [Pt2(μ-S)(μ-S C12H8N2O)(PPh3)4]+ (8) was found to decompose readily in
solution. Cyclopropanes cyclopropyl methyl ketone and trans-1,2-dibenzoylcyclo-
propane did not undergo ring-opening when reacted with 1a. The more activated
2,2,3,3-tetracyanocyclopropane and diethylcyclopropane-1,2-dicarboxylate both re-
i
sulted in ring-opening when reacted with 1a resulting in the isolation of deriva-
tives [Pt2(μ-S)(μ-S C(CN)2)(PPh3)4] (12) and [Pt2(μ-S)(μ-S C2H4CH(CO2Et)2)-
(PPh3)4]BETI (11[BETI]) respectively which were structurally characterised by het-
eronuclear NMR spectroscopy (12 31P{1H}, 195Pt{1H}; 11 1H, 31P{1H}) and single
crystal XRD studies. 12 was found to have a carbanionic center and is proposed
to result from an intramolecular rearrangement of the initially formed [Pt2(μ-S)(μ-
S C(CN)2C(CN)2CH3)(PPh3)4]+ (31). Bromomethylcyclopropane did not result
in ring-opening when reacted with 1a, however alkylation resulted in [Pt2(μ-S)(μ-
S CH2C3H5)(PPh3)4]+ (10) which was isolated as 10[BPh4] and structurally char-
acterised by 31P{1H}-NMR spectroscopy and single crystal XRD. 10[BPh4] did not
undergo ring-opening when refluxed in methanol. N -tosylaziridine resulted in the
ring-opened derivative [Pt2(μ-S)(μ-S C2H4NHtosyl)(PPh3)4]+ (13) when reacted
with 1a and was isolated as 13[PF6] and structurally characterised by 31P{1H}-NMR
spectroscopy and single crystal XRD. Thiirane appeared to rapidly undergo ring-
opening when reacted with 1a however only polymeric decomposition species were
detected by ESIMS. The previously reported reaction of 1a and 2-chloro-N -methyl-
pyridinium iodide (14[I]) was reexamined. Salts of 14 sans iodide were synthesized
using alkylating agents trimethyloxonium tetrafluoroborate or dimethyl sulfate giv-
ing 14[BF4] or 14[CH3SO4] respectively. The reaction of 1a and 14 was found to
result in the dicationic complex [Pt2(μ-S)(μ-S C6H7N)(PPh3)4]2+ (2) which was
isolated as the bis-hexafluorophosphate salt 2[PF6]2 and structurally characterised
with 31P{1H}-NMR spectroscopy, 195Pt{1H}-NMR spectroscopy, and single crystal
XRD. The 2-mercapto-N -methylpyridinium ligand in 2 was proposed to be an ex-
cellent leaving group and the reaction of 2 with excess bromide resulted in the isola-
tion of the mixed-bridged complex [Pt2(μ-S)(μ-Br)(PPh3)4]BPh4 (16[BPh4]) which
was structurally characterised with 31P{1H}-NMR spectroscopy and single crystal
XRD. The thiols N -acetylcysteamine, 2-mercapto-1-methylimidazole, and 2-amino-
thiophenol were reacted with 2 to give [Pt2(μ-S)(μ-S C2H4NHC( O)CH3)(PPh3)4]+
(38), [Pt2(μ-S)(μNS-S C3H2N2CH3)(PPh3)4]+ (17), and [Pt2(μ-S)(μ-S C6H4NH2)-
ii
(PPh3)4]+ (39) respectively which were isolated as 38[BF4], 17[BETI], and 39[BF4].
17[BETI] was structurally characterised (31P{1H}-NMR spectroscopy, 195Pt{1H}-
NMR spectroscopy, single crystal XRD) and found to contain a novel 6-membered
Pt-S-Pt-S-C-N heterocycle. 38 was characterised using NMR spectroscopy (1H, 13C,
31P{1H}, and 195Pt{1H}). 39 was characterised using 31P{1H}-NMR spectroscopy.
2 was reacted with selenourea resulting in the detection by ESIMS of the mixed-
bridged [Pt2(μ-S)(μ-Se)(PPh3)4]+ (23) which decomposed over the course of several
days to 1a and 1b. When the diaryldichalcogenides Ph2Se2, Ph2Te2, di-4-ethoxy-
phenyl-ditelluride were reduced with hydrazine to the corresponding chalcogeno-
late anion and reacted with 2, substitution of the 2-mercapto-N -methylpyridinium
zwitterion resulted and mixed-bridged derivatives [Pt2(μ-S)(μ-E R)(PPh3)4]+ (E-
R = Se-Ph, 18; Te-Ph, 47; Te-C6H4-OEt, 19) detected by ESIMS. 18[BF4] and
19[BF4] were isolated and structurally characterised with heteronuclear NMR spec-
troscopy (31P{1H}-NMR, 195Pt{1H}-NMR) and single crystal XRD. A bridging hy-
drazine species was observed when reacting 2 with hydrazine reduced diaryldichalco-
genides, and the reaction between 2 and hydrazine was found to result in [Pt2-
(μ-S)(μ-NH NH2)(PPh3)4]+ (21) which was isolated as 21[BPh4] and structurally
characterised with 31P{1H} and 195Pt{1H}-NMR spectroscopy

text: ESIMS targeted synthesis of novel {Pt2S2} derivatives Electrospray ionisation mass spectrometry (ESIMS) was used to investigate ring-
opening reactions of several epoxides with the nucleophilic dinuclear PtII
complexes
[Pt2(μ-E)2(PPh3)4] (E = S, 1a; Se, 1b) and several activated cyclopropanes, N -
tosylaziridine, and thiirane with 1a. Epoxides cyclohexene oxide, styrene oxide,
epibromohydrin, and 2,2-dimethyloxirane were found to undergo ring-opening when
reacted with 1a and derivatives [Pt2(μ-S)(μ-S C6H10OH)(PPh3)4]BPh4 (5[BPh4],
[Pt2(μ-S)(μ-S C8H8OH)(PPh3)4]BETI (6[BETI]), [Pt2(μ-S CH2CH(OH)CH2 μ-S)-
(PPh3)4][PF6]2 (3[PF6]2), and [Pt2(μ-S)(μ-S CH2C(Me)2OH)(PPh3)4]BPh4 (7 [BPh4])
were respectively isolated and structurally characterised with 31P{1H} and 195Pt nu-
clear magnetic resonance (NMR) spectroscopy, and for 5, 3 and 7 single crystal X-
ray diffraction (XRD) studies. 6 was found to be a mixture of isomers, and crystals
suitable for a single crystal XRD experiment were not obtained. Both styrene oxide
and epibromohydrin underwent ring-opening when reacted with 1b and the respec-
tive derivatives [Pt2(μ-Se)(μ-Se C8H8OH)(PPh3)4]+ and [Pt2(μ-Se CH2CH(OH)-
CH2 μ-Se)(PPh3)4]2+ were characterised by ESIMS. The fully substituted epoxide
2,3-dimethyl-2,3-epoxybutane did not undergo ring-opening when treated with 1a
in refluxing methanol for several hours. 5,6-Epoxy-5,6-dihydro-[1,10]-phenanthro-
line resulted in ring-opening when reacted with 1a however the resulting deriva-
tive [Pt2(μ-S)(μ-S C12H8N2O)(PPh3)4]+ (8) was found to decompose readily in
solution. Cyclopropanes cyclopropyl methyl ketone and trans-1,2-dibenzoylcyclo-
propane did not undergo ring-opening when reacted with 1a. The more activated
2,2,3,3-tetracyanocyclopropane and diethylcyclopropane-1,2-dicarboxylate both re-
i
sulted in ring-opening when reacted with 1a resulting in the isolation of deriva-
tives [Pt2(μ-S)(μ-S C(CN)2)(PPh3)4] (12) and [Pt2(μ-S)(μ-S C2H4CH(CO2Et)2)-
(PPh3)4]BETI (11[BETI]) respectively which were structurally characterised by het-
eronuclear NMR spectroscopy (12 31P{1H}, 195Pt{1H}; 11 1H, 31P{1H}) and single
crystal XRD studies. 12 was found to have a carbanionic center and is proposed
to result from an intramolecular rearrangement of the initially formed [Pt2(μ-S)(μ-
S C(CN)2C(CN)2CH3)(PPh3)4]+ (31). Bromomethylcyclopropane did not result
in ring-opening when reacted with 1a, however alkylation resulted in [Pt2(μ-S)(μ-
S CH2C3H5)(PPh3)4]+ (10) which was isolated as 10[BPh4] and structurally char-
acterised by 31P{1H}-NMR spectroscopy and single crystal XRD. 10[BPh4] did not
undergo ring-opening when refluxed in methanol. N -tosylaziridine resulted in the
ring-opened derivative [Pt2(μ-S)(μ-S C2H4NHtosyl)(PPh3)4]+ (13) when reacted
with 1a and was isolated as 13[PF6] and structurally characterised by 31P{1H}-NMR
spectroscopy and single crystal XRD. Thiirane appeared to rapidly undergo ring-
opening when reacted with 1a however only polymeric decomposition species were
detected by ESIMS. The previously reported reaction of 1a and 2-chloro-N -methyl-
pyridinium iodide (14[I]) was reexamined. Salts of 14 sans iodide were synthesized
using alkylating agents trimethyloxonium tetrafluoroborate or dimethyl sulfate giv-
ing 14[BF4] or 14[CH3SO4] respectively. The reaction of 1a and 14 was found to
result in the dicationic complex [Pt2(μ-S)(μ-S C6H7N)(PPh3)4]2+ (2) which was
isolated as the bis-hexafluorophosphate salt 2[PF6]2 and structurally characterised
with 31P{1H}-NMR spectroscopy, 195Pt{1H}-NMR spectroscopy, and single crystal
XRD. The 2-mercapto-N -methylpyridinium ligand in 2 was proposed to be an ex-
cellent leaving group and the reaction of 2 with excess bromide resulted in the isola-
tion of the mixed-bridged complex [Pt2(μ-S)(μ-Br)(PPh3)4]BPh4 (16[BPh4]) which
was structurally characterised with 31P{1H}-NMR spectroscopy and single crystal
XRD. The thiols N -acetylcysteamine, 2-mercapto-1-methylimidazole, and 2-amino-
thiophenol were reacted with 2 to give [Pt2(μ-S)(μ-S C2H4NHC( O)CH3)(PPh3)4]+
(38), [Pt2(μ-S)(μNS-S C3H2N2CH3)(PPh3)4]+ (17), and [Pt2(μ-S)(μ-S C6H4NH2)-
ii
(PPh3)4]+ (39) respectively which were isolated as 38[BF4], 17[BETI], and 39[BF4].
17[BETI] was structurally characterised (31P{1H}-NMR spectroscopy, 195Pt{1H}-
NMR spectroscopy, single crystal XRD) and found to contain a novel 6-membered
Pt-S-Pt-S-C-N heterocycle. 38 was characterised using NMR spectroscopy (1H, 13C,
31P{1H}, and 195Pt{1H}). 39 was characterised using 31P{1H}-NMR spectroscopy.
2 was reacted with selenourea resulting in the detection by ESIMS of the mixed-
bridged [Pt2(μ-S)(μ-Se)(PPh3)4]+ (23) which decomposed over the course of several
days to 1a and 1b. When the diaryldichalcogenides Ph2Se2, Ph2Te2, di-4-ethoxy-
phenyl-ditelluride were reduced with hydrazine to the corresponding chalcogeno-
late anion and reacted with 2, substitution of the 2-mercapto-N -methylpyridinium
zwitterion resulted and mixed-bridged derivatives [Pt2(μ-S)(μ-E R)(PPh3)4]+ (E-
R = Se-Ph, 18; Te-Ph, 47; Te-C6H4-OEt, 19) detected by ESIMS. 18[BF4] and
19[BF4] were isolated and structurally characterised with heteronuclear NMR spec-
troscopy (31P{1H}-NMR, 195Pt{1H}-NMR) and single crystal XRD. A bridging hy-
drazine species was observed when reacting 2 with hydrazine reduced diaryldichalco-
genides, and the reaction between 2 and hydrazine was found to result in [Pt2-
(μ-S)(μ-NH NH2)(PPh3)4]+ (21) which was isolated as 21[BPh4] and structurally
characterised with 31P{1H} and 195Pt{1H}-NMR spectroscopy

year: 2024-10-18

title: Assessment of effects of proposed treated wastewater discharge to the Te Arikiroa Thermal Channel and Sulphur Bay (Lake Rotorua)

authors: Dada, Ayokunle Christopher

abstract: After 2019, irrigation operations at the Land Treatment System (LTS) in the Whakarewarewa Forest are scheduled to cease. A number of options and locations have been considered for the discharge of the treated wastewater when the current discharge consent ceases. Following consultations and technical assessments, the preferred option of Rotorua Lakes Council is to upgrade the existing plant to a full Membrane Bioreactor Plant with the addition of an Ultraviolet Disinfection System (or alternative treatment to achieve an equivalent performance in terms of treated wastewater quality). Under this arrangement, wastewater would be subjected to biological, chemical and physical treatment processes, and the treated wastewater discharged through Te Arikiroa Thermal Channel to Sulphur Bay. Rotorua Lakes Council is thus undertaking an environmental impact assessment study to determine the effects of discharging treated wastewater to the thermal channel and Puarenga Bay (Lake Rotorua), with particular reference to aesthetic, water quality and ecological considerations. These considerations include potential effects related to faecal indicator bacteria, nutrient concentrations, metals, dissolved oxygen, and taonga species (native species of cultural significance).
The assessment focused on:
(i)	The projected treated wastewater characteristics;

(ii)	Existing conditions of the receiving water;

(iii)	The sensitivity of the receiving water and the impact of the proposed discharge on water quality and taonga species (native species of cultural significance) in Te Arikiroa Thermal Channel and Sulphur Bay.

The main techniques used to inform the assessment in this study were:
1) Analysis of historical water quality data, 2011-2014;
2) Collection of additional water quality data at Te Arikiroa Thermal Channel and Sulphur Bay and along a transect to quantify spatial variability (sampling in 2016 and 2017);
3) Mass balance dilution modelling to predict water quality in the Te Arikiroa Thermal Channel and Sulphur Bay (Lake Rotorua), at a site outside of the assumed mixing zone;
4) Lake ecosystem modelling conducted by Abell et al. (2015) to assess effects related to eutrophication;
5) Background review of biological information and field investigations for taonga species at Sulphur Bay and Te Arikiroa Thermal Channel (2017).

text: Assessment of effects of proposed treated wastewater discharge to the Te Arikiroa Thermal Channel and Sulphur Bay (Lake Rotorua) After 2019, irrigation operations at the Land Treatment System (LTS) in the Whakarewarewa Forest are scheduled to cease. A number of options and locations have been considered for the discharge of the treated wastewater when the current discharge consent ceases. Following consultations and technical assessments, the preferred option of Rotorua Lakes Council is to upgrade the existing plant to a full Membrane Bioreactor Plant with the addition of an Ultraviolet Disinfection System (or alternative treatment to achieve an equivalent performance in terms of treated wastewater quality). Under this arrangement, wastewater would be subjected to biological, chemical and physical treatment processes, and the treated wastewater discharged through Te Arikiroa Thermal Channel to Sulphur Bay. Rotorua Lakes Council is thus undertaking an environmental impact assessment study to determine the effects of discharging treated wastewater to the thermal channel and Puarenga Bay (Lake Rotorua), with particular reference to aesthetic, water quality and ecological considerations. These considerations include potential effects related to faecal indicator bacteria, nutrient concentrations, metals, dissolved oxygen, and taonga species (native species of cultural significance).
The assessment focused on:
(i)	The projected treated wastewater characteristics;

(ii)	Existing conditions of the receiving water;

(iii)	The sensitivity of the receiving water and the impact of the proposed discharge on water quality and taonga species (native species of cultural significance) in Te Arikiroa Thermal Channel and Sulphur Bay.

The main techniques used to inform the assessment in this study were:
1) Analysis of historical water quality data, 2011-2014;
2) Collection of additional water quality data at Te Arikiroa Thermal Channel and Sulphur Bay and along a transect to quantify spatial variability (sampling in 2016 and 2017);
3) Mass balance dilution modelling to predict water quality in the Te Arikiroa Thermal Channel and Sulphur Bay (Lake Rotorua), at a site outside of the assumed mixing zone;
4) Lake ecosystem modelling conducted by Abell et al. (2015) to assess effects related to eutrophication;
5) Background review of biological information and field investigations for taonga species at Sulphur Bay and Te Arikiroa Thermal Channel (2017).

year: 2018