Chromatographic properties of hydrogenated microdiamond synthesized by high pressure and high temperature.

Adsorption and chromatographic properties of oxidized and hydrogenated 'high pressure and high temperature' synthesised diamond (HPHT) are studied using high-performance liquid chromatography. The retention factors of organic cation (benzyltributylammonium chloride), weak base (aniline), weak acid (benzoic acid), strong acid (benzenesulfonic acid), hydrophobic toluene, and hydrophilic uracil are obtained at varied pH, organic solvent content, and ionic strength of mobile phase. Both adsorbents exhibited moderate polarity with a mixed-mode retention mechanism with a combination of electrostatic, hydrophobic and hydrophilic interactions. Unexpectedly, hydrogenated HPHT revealed significant anion-exchange properties under acidic conditions and cation-exchange properties under alkaline conditions, while only cation-exchange selectivity was noted for oxidized HPHT across the enntire pH range. The retention factors obtained for a set of model compounds including n-alkyl-, polymethyl-, nitro- and halogenated benzenes correlated well with their hydrophobicity (logP) values. The thermal stability of the adsorbent and immutability of retention mechanisms involved was confirmed by linear van't Hoff plots for the investigated compounds.

Recent advances and applications of synthetic diamonds in solid-phase extraction and high-performance liquid chromatography.

Since the advent of diamond-based adsorbents in the late 1960s, the interest in their use for solid-phase extraction (SPE) and high-performance liquid chromatography (HPLC) has steadily increased. This is primarily due to their unique properties, such as extreme chemical and thermal stability, high mechanical strength and biocompatibility, and complex mixed-mode retention mechanisms. Currently, the most commonly used synthetic diamonds in SPE and HPLC are detonation nanodiamonds (DND), high-pressure high-temperature (HPHT) diamonds, and chemical vapour deposition (CVD) diamonds. These diamonds have been either used as individual particles (in both modified and unmodified forms), or for surface modification, or entrapped within composites and core-shell particles to develop new diamond-based adsorbents. These diamond-based adsorbents have been used for a variety of applications, including streamlined proteome analysis; extraction of anions, cations, actinides, uranium, lanthanides, alkaline earth metals, transition metals, and post-transition metals; and development of reversed-phase, normal phase, hydrophilic interaction, ion chromatography, and mixed-mode liquid chromatography columns, to name but a few. These varied applications of different types of diamonds are typically governed by their specific properties. This review discusses the various surface and bulk properties of DND, HPHT diamonds, and CVD diamonds that facilitate or limit their use in different SPE and HPLC based applications.

Ion chromatographic determination of hydrazine in excess ammonia for monitoring graphene oxide reduction reaction.

A new ion chromatography method has been developed to study graphene oxide (GO) reduction by monitoring hydrazine concentration in the GO suspension. The method is based on ion chromatographic separation of hydrazine (from excess ammonia) and its selective determination by electrochemical detection. The developed analytical protocol overcame the significant practical challenges of atmospheric hydrazine oxidation and minimised the matrix interference in both separation and detection which result from the excess of ammonium with respect to hydrazine (up to 5.8 × 104 times) in GO reduction experiments. Chromatographic separations were achieved using a high capacity IonPac CS16 cation-exchange column with a 30 mM methanesulfonic acid (MSA) eluent, within an analysis time of less than 20 min. Detection of hydrazine as hydrazinium ion using electrochemical detector was linear between 10 µM and 4 mM, with LOD and LOQ values of 3 µM and 10 µM, respectively. Standard additions confirmed 103 ±â€¯0.8% recovery. The developed method was successfully used to determine the point of complete GO reduction with hydrazine. Reaction curves for GO reduction generated using the method were compared to results from Fourier-transform infrared spectroscopy and Raman spectroscopy to verify the utility of the approach.

Chromatographic behaviour of synthetic high pressure high temperature diamond in aqueous normal phase chromatography.

The chromatographic properties of high pressure high temperature synthesised diamond (HPHT) are investigated under the conditions of hydrophilic interaction liquid chromatography (HILIC). A 50×4.6mm ID stainless steel column packed with HPHT particles of mean diameter 1.6µm and specific surface area 5.1m2g-1 is used. According to the results of acid-base titration with NaOH the purified HPHT batch contains 4.59µeqg-1 of protogenic, mainly carboxyl- and hydroxyl-, groups, which make this polar adsorbent suitable for use as a stationary phase in HILIC. The retention behaviour of several classes of polar compounds including benzoic and benzenesulfonic acids, nitro- and chlorophenols, various organic bases, and quaternary ammonium compounds are studied using acetonitrile and methanol based mobile phases containing 5-30v/v% of water. The effects of the buffer pH and concentration, column temperature and organic solvent content on retention of model compounds are also investigated. It is shown that both pH and acetonitrile/methanol ratio in the mobile phase can be used to vary the separation selectivity. Molecular adsorption mechanism (related to aqueous normal phase mode), rather than partitioning is established to be responsible for the retention.

Flow-dependent separation selectivity for organic molecules on metal-organic frameworks containing adsorbents.

A new flow-dependent separation selectivity (FDSS) effect was discovered in isocratic HPLC. Significant changes in chromatographic selectivity were achieved by simple variation of the mobile phase flow rate. The FDSS effect was observed for a core-shell stationary phase using silica particles as a core and a Zr-based metal-organic framework (UiO-66) as a shell.

Chromatographic performance of synthetic polycrystalline diamond as a stationary phase in normal phase high performance liquid chromatography.

The chromatographic properties of high pressure high temperature synthesised diamond (HPHT) are investigated in normal phase mode of high performance liquid chromatography. Purified nonporous irregular shape particles of average particles size 1.2 µm and specific surface area 5.1 m(2) g(-1) were used for packing 100×4.6 mm ID or 50×4.6 mm ID stainless steel columns. The retention behaviour of several classes of compounds including alkyl benzenes, polyaromatic hydrocarbons (PAH), alkylphenylketones, phenols, aromatic acids and bases were studied using n-hexane-2-propanol mixtures as mobile phase. The results are compared with those observed for microdispersed sintered detonation nanodiamond (MSDN) and porous graphitic carbon (PGC). HPHT diamond revealed distinctive separation selectivity, which is orthogonal to that observed for porous graphitic carbon; while selectivities of HPHT diamond and microdispersed sintered detonation nanodiamonds are similar. Owing to non-porous particle nature, columns packed with high pressure high temperature diamond exhibited excellent mass transfer and produce separations with maximum column efficiency of 128,200 theoretical plates per meter.

Diamond based adsorbents and their application in chromatography.

The idea of using diamond and diamond containing materials in separation sciences has attracted a strong interest in the past decade. The combination of a unique range of properties, such as chemical inertness, mechanical, thermal and hydrolytic stability, excellent thermal conductivity with minimal thermal expansion and intriguing adsorption properties makes diamond a promising material for use in various modes of chromatography. This review summarises the recent research on the preparation of diamond and diamond based stationary phases, their properties and chromatographic performance. Special attention is devoted to the dominant retention mechanisms evident for particular diamond containing phases, and their subsequent applicability to various modes of chromatography, including chromatography carried out under conditions of high temperature and pressure.

The importance of chain length for the polyphosphate enhancement of acidic potassium permanganate chemiluminescence.

Sodium polyphosphate is commonly used to enhance chemiluminescence reactions with acidic potassium permanganate through a dual enhancement mechanism, but commercially available polyphosphates vary greatly in composition. We have examined the influence of polyphosphate composition and concentration on both the dual enhancement mechanism of chemiluminescence intensity and the stability of the reagent under analytically useful conditions. The average chain length (n) provides a convenient characterisation, but materials with similar values can exhibit markedly different distributions of phosphate oligomers. There is a minimum polyphosphate chain length (∼6) required for a large enhancement of the emission intensity, but no further advantage was obtained using polyphosphate materials with much longer average chain lengths. Providing there is a sufficient average chain length, the optimum concentration of polyphosphate is dependent on the analyte and in some cases, may be lower than the quantities previously used in routine detection. However, the concentration of polyphosphate should not be lowered in permanganate reagents that have been partially reduced to form high concentrations of the key manganese(III) co-reactant, as this intermediate needs to be stabilised to prevent formation of insoluble manganese(IV).