Synthesis and characterization of copoly(arylene sulfide)s

Copolymerizations of p-dichlorobenzene (DCB)/4-bromophenyl ether (BPE), DCB/4,4′-dibromobiphenyl (DBB), and DBB/BPE pairs with sodium sulfide under high temperature (270–290°C) utilizing N-methyl-2-pyrrolidinone (NMP) as solvent were carried out to give C(DCB/BPE), C(DCB/DBB), and C(DBB/BPE) copolymers, respectively. The reactivity of dihaloaromatic monomers toward thiolate anion in the polycondensation reaction followed the order DBB > DCB > BPE. The reactivity gap between DBB and DCB toward thiolate anion seemed to be smaller than that between BPE and DCB, resulting in both high yield and high molecular weight in the C(DCB/DBB) copolymers compared to C(DCB/BPE) copolymers. The copolymerization of DBB/BPE pair with sodium sulfide, which has larger reactivity gap than the DCB/DBB or DCB/BPE pair, gave mixtures of PBS and PPSE homopolymers especially in the range of 50–80 mol % BPE in the feed. The C(DCB/DBB) and C(DCB/BPE) copolymers, however, exhibited random copolymer character in all comonomer ratios in the feed as evidenced by copolymer composition and DSC data. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 2311–2317, 1999     

Plasmonic Hotspots in Air: An Omnidirectional Three‐Dimensional Platform for Stand‐Off In‐Air SERS Sensing of Airborne Species

Molecular‐level airborne sensing is critical for early prevention of disasters, diseases, and terrorism. Currently, most 2D surface‐enhanced Raman spectroscopy (SERS) substrates used for air sensing have only one functional surface and exhibit poor SERS‐active depth. “Aerosolized plasmonic colloidosomes” (APCs) are introduced as airborne plasmonic hotspots for direct in‐air SERS measurements. APCs function as a macroscale 3D and omnidirectional plasmonic cloud that receives laser irradiation and emits signals in all directions. Importantly, it brings about an effective plasmonic hotspot in a length scale of approximately 2.3 cm, which affords 100‐fold higher tolerance to laser misalignment along the z‐axis compared with 2D SERS substrates. APCs exhibit an extraordinary omnidirectional property and demonstrate consistent SERS performance that is independent of the laser and analyte introductory pathway. Furthermore, the first in‐air SERS detection is demonstrated in stand‐off conditions at a distance of 200 cm, highlighting the applicability of 3D omnidirectional plasmonic clouds for remote airborne sensing in threatening or inaccessible areas.     

Catholyte‐Free Electrocatalytic CO2 Reduction to Formate

Electrochemical reduction of carbon dioxide (CO₂) into value‐added chemicals is a promising strategy to reduce CO₂ emission and mitigate climate change. One of the most serious problems in electrocatalytic CO₂ reduction (CO₂R) is the low solubility of CO₂ in an aqueous electrolyte, which significantly limits the cathodic reaction rate. This paper proposes a facile method of catholyte‐free electrocatalytic CO₂ reduction to avoid the solubility limitation using commercial tin nanoparticles as a cathode catalyst. Interestingly, as the reaction temperature rises from 303 K to 363 K, the partial current density (PCD) of formate improves more than two times with 52.9 mA cm^?2, despite the decrease in CO₂ solubility. Furthermore, a significantly high formate concentration of 41.5 g L^?1 is obtained as a one‐path product at 343 K with high PCD (51.7 mA cm^?2) and high Faradaic efficiency (93.3 %) via continuous operation in a full flow cell at a low cell voltage of 2.2 V.     

Selective Binding of Open Frameworks Assembled from Nickel(II) Macrocyclic Complexes with Organic and Inorganic Guests

Inclusion studies for metal-organic open-frameworks, [Ni(C_10}H₂₄N₄)(H₂O)₂]₃[BTC]₂·24H₂O (1) and [Ni(C₁₀H₂₆N₆)]₃ [BTC]₂·18H₂O(2) (BTC^3- = 1,3,5-benzenetricarboxylate) with various organic andinorganic guest molecules have been carried out. 1 is the previously reportedmolecular floral lace with 1-D channels, where positively charged macrocyclic layersand negatively charged BTC^3- layers are alternately packed by hydrogen bondinginteractions. 2 is assembled in this study from nickel(II) hexaazamacrocyclic complexcontaining methyl pendant arms and BTC^3-. The X-ray structure of 2 shows thatthe nickel(II) complex and BTC^3- form a 2-D coordination polymer. The XRPD patternsof 2 indicate that framework of 2 is slightly deformed upon removal of waterguest molecules but restored upon rebinding of water. The host solid 1 binds MeOHin toluene, and 1,3,5-trihydroxybenzene (THB) and 4-hydroxyacetophenone (HAP) in EtOH/toluene (v/v = 1/4) solutions. The binding constants (K_f) of 1 forMeOH, THB, and HAP are 66.4 M^-1, 259 M^-1, and 13.9 M^-1,respectively. In the range of high concentration of the guest, however, the host showsvarious binding curves depending upon the types of guest. It binds PhOH in toluene,showing a sigmoid curve. It also binds transition metal complexes such as[Cu(NH₃)₄](ClO₄)₂, [Cu(ethylenediamine)₂](ClO₄)₂,[Cu(histamine)₂](ClO₄)₂, and[Cu(N,N'-bis(3-aminopropyl)ethylenediamine)](ClO₄)₂ in MeCN, with K_f values of 645 M^-1, 9.52 M^-1, 37.2 M^-1, and 6.00 M^-1,respectively. The host solid 2 binds selectively PhOH over PhCl and PhBr, showing that hydrogen bonding interaction between the host and guest plays an important role in the selectivity.     

Differential stable isotope labeling of peptides for quantitation and de novo sequence derivation.

We have demonstrated the use of per-methyl esterification of peptides for relative quantification of proteins between two mixtures of proteins and automated de novo sequence derivation on the same dataset. Protein mixtures for comparison were digested to peptides and resultant peptides methylated using either d0- or d3-methanol. Methyl esterification of peptides converted carboxylic acids, such as are present on the side chains of aspartic and glutamic acid as well as the carboxyl terminus, to their corresponding methyl esters. The separate d0- and d3-methylated peptide mixtures were combined and the mixture subjected to microcapillary high performance liquid chromatography/tandem mass spectrometry (HPLC/MS/MS). Parent proteins of methylated peptides were identified by correlative database searching of peptide tandem mass spectra. Ratios of proteins in the two original mixtures could be calculated by normalization of the area under the curve for identical charge states of d0- to d3-methylated peptides. An algorithm was developed that derived, without intervention, peptide sequence de novo by comparison of tandem mass spectra of d0- and d3-peptide methyl esters.     

Studies on the Mass Spectra of N‐Aryl α,β‐Unsaturated γ‐Lactams

The mass spectra of a series of N‐aryl α,β‐unsaturated γ‐lactams were studied. Besides the molecular ion, the three characteristic fragments such as [M⁺‐29], [M⁺‐55], and [M⁺‐82] were commonly found in a series of N‐Aryl α,β‐unsaturated γ‐lactams in EI/MS. Further more the mechanism for the interpretation of these fragments is also de scribed.     

The effect of the curing agent content on the curing and liquid‐crystalline phase of liquid‐crystalline epoxy resin

The effect of the curing agent content on the curing behavior and liquid‐crystalline (LC) phase of the liquid‐crystalline epoxy (LCE) resin 4,4′‐di(2,3‐epoxypropyloxy)phenyl benzoate was studied. Diaminodiphenylester (DDE) was used as a curing agent. The curing behavior was observed via differential scanning calorimetry, and the LC phase was investigated with a polarized optical microscopy. The LC phase in the LCE/DDE mixture with a high DDE content was developed during curing. The onset time was inversely proportional to the DDE content. The mesophase stability of LCE/DDE was enhanced by the addition of large amounts of DDE. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 39: 374–379, 2001     

A metacognitive-based instruction for Primary Four students to approach non-routine mathematical word problems

Many Primary Four students (fourth graders) in Singapore have difficulties initiating or persevering in the problem-solving process even though the curriculum has focused on problem solving since 1992. This study served to examine the role of metacognition in self-regulated problem solving. The study, a quasi-experimental pretest–posttest design involving a convenience sample of 63 students from two intact mixed-ability Primary Four classes, examined the impact of using a metacognitive scheme that focuses on the understanding and planning stages of Pòlya’s four-stage approach on students’ mathematical problem-solving behavior, performance and attitudes. The findings revealed that the metacognitive-based scheme had a positive impact on students’ understanding of the problem posed, solution planning, confidence in and personal control of problem-solving behavior and emotions. It had also helped them to initiate and persevere in the problem-solving process to achieve a higher level of problem-solving success. Limitations and instructional implications are discussed.     

Teacher preparation for a problem-solving curriculum in Singapore

Problem solving is at the heart of the Singapore Mathematics curriculum. However, it remains a challenge for teachers to realise this curricular goal in practice. Here, we review the efforts of Singapore mathematics teacher educators in incorporating problem-solving (teaching) competency in teacher education and PD programmes. We discuss conceptual and practical issues, actions taken and changes made in building teachers?? capacity to enact a problem-solving curriculum in a school-based design experiment project. In the project, teachers learnt problem solving, observed and then carried out lessons, using the ??Mathematics Practical????akin to the science practical??as key to instruction and assessment.