Facile preparation of embedded polar group-containing pentafluorophenyl stationary phases for highly selective separations of diverse analytes.

Pentafluorophenyl (PFP) stationary phase is one of the most important phases after the C18 phase in terms of its applications. Three embedded polar groups (EPG)-containing stationary phases were newly synthesized to act the EPGs as additional interaction sites. The silica surface was initially modified with (3-aminopropyl)trimethoxysilane (APS). The APS-modified silicas were coupled with 2,3,4,5,6-pentafluorobenzoic acid, 2,3,4,5,6-pentafluorophenylacetic acid, and 2,3,4,5,6-pentafluoro-anilino(oxo)acetic acid to obtain Sil-PFP-BA, Sil-PFP-AA, and Sil-PFP-AN phases, respectively. The new phases were characterized by elemental analysis, ATR-FTIR, scanning electron microscopy (SEM), and thermogravimetric analysis (TGA). The phases were evaluated with the Tanaka and Neue tests in reversed-phase liquid chromatography (RPLC). In addition, they were characterized as hydrophilic phases by the Tanaka test protocol used in hydrophilic interaction chromatography (HILIC) separation mode. The Sil-PFP-AA phase showed the highest molecular shape selectivity in RPLC, while Sil-PFP-AN achieved the highest separability in HILIC compared to the commercial PFP reference column. The Sil-PFP-AA phase was successfully applied for the analysis of capsaicinoids from real samples of fresh chili peppers (Capsicum spp.) in RPLC and the Sil-PFP-AN phase for vitamin C (ascorbic acid) in HILIC.

Surface Modification of Silica with ß-Alanine Derivatives for Unique Applications in Liquid Chromatography.

Column purchasing cost is an important issue for an analyst to analyze complex sample matrices. Here, we report the development of an amino acid (ß-alanine)-derived stationary phase (Sil-Ala-C12) with strategic and effective interaction sites (amide and urea as embedded polar groups with C12 alkyl chain) able to separate various kinds of analytes. Owing to the balanced hydrophobicity and hydrophilicity of the phase, it showed exceptional separation abilities in both reversed-phase high-performance liquid chromatography (RP-HPLC) as a hydrophobic phase and hydrophilic interaction chromatography (HILIC) as a hydrophilic phase. Remarkably, the baseline separation was achieved for the challenging ß- and γ-isomers of tocopherol. Usually, three columns such as pentafluorophenyl or C30, C18, and sulfobetaine HILIC are required for the analysis of vitamin E, capsaicinoids, and vitamin C in chili peppers (Capsicum spp.), respectively. However, only Sil-Ala-C12 was able to separate these analytes. A single column can serve 3-4 purposes, which suggests that Sil-Ala-C12 had the potential to reduce column purchasing costs.

Design of ß-Alanine-Derived Novel C18 Stationary Phase Containing Embedded Urea and Amide Groups for the Separation of Versatile Analytes.

Novel stationary phases have been emerging recently. A ß-alanine-derived embedded urea and amide group-containing C18 phase (Sil-Ala-C18) was prepared for the first time. The media were packed into a 150 × 2.1 mm HPLC column, and the newly designed column was evaluated with the Tanaka and Neue test protocols in reversed-phase liquid chromatography (RPLC) separation mode. Moreover, it was characterized by the Tanaka test protocol in hydrophilic interaction chromatography (HILIC) separation mode. The new phase was characterized by elemental analysis, attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR), scanning electron microscopy (SEM), thermogravimetric analysis (TGA), and solid-state 13C cross-polarization magic angle spinning (CP/MAS) NMR spectroscopy at variable temperatures. The chromatographic evaluation involved very good separation of nonpolar shape-constrained isomers, polar and basic compounds in RPLC, and highly polar compounds in HILIC compared to the commercial reference columns. The Sil-Ala-C18 phase was able to separate the challenging ß- and γ-isomers of tocopherol. The phase was also successfully applied for the separation of the isomers of tocopherol (vitamin E) and capsaicinoids from real samples of chili peppers (Capsicum spp.) in RPLC and ascorbic acid (vitamin C) in HILIC.

Ecofriendly pretreatment of cotton fabrics by ultrasonication and reusing bath chemicals.

The textile industries of Bangladesh contribute significantly to the country's economy, accounting for more than 40% of total annual export. The quest of new technologies for efficient water and energy use in cotton knit dyeing could result in significant water savings and improve environmental sustainability. Textile wet processing consumes a lot of utilities (water and energy), and the water generates a lot of waste, which enhances chemical consumption and effluent management costs. The cotton knit fabric used in this study was pretreated and dyed utilizing ultrasonication at a lower temperature than conventional pretreatment and dyeing techniques in an attempt to establish ecofriendly wet processing in the textile industry. The bath chemicals were reused up to two times before dyeing in conventional techniques, and fabric properties such as whiteness index, weight loss, bursting strength, color fastness to light, washing, perspiration, rubbing, color strength and durability, or dimensional stability were evaluated and compared with the values obtained by conventional techniques. The color matching of reactive dyed fabric for ultrasonic pretreated fabric with and without reusing bath chemicals was determined. The sonicated scoured and bleached fabric's whiteness index was found to be acceptable, with relatively low weight loss; however, the bursting strength was found to be increased. Color fastness to light, washing, perspiration, and rubbing were found to be comparable to the conventional technique for low temperature ultrasonicated pretreated and reuse-1 pretreated dyed knit fabric. The results also revealed that there was no color degradation during ultrasonication. FT-IR spectroscopy and scanning electron microscopy (SEM) revealed no significant changes in the chemical composition of cellulose or the fabric shape of pretreated and dyed cotton knit fabric after ultrasonication.

Progress in surface-modified silicas for Cr(VI) adsorption: A review.

Various toxic chemicals are discharging to the environment due to rapid industrialization and polluting soil, water, and air causing numerous diseases including life-threatening cancer. Among these pollutants, Cr(VI) or hexavalent chromium is one of the most carcinogenic and toxic contaminants hostile to human health and other living things. Therefore, along with other contaminants, the removal of Cr(VI) efficiently is very crucial to keep our environment neat and clean. On the other hand, silica has a lot of room to modify its surfaces as it is available with various sizes, shapes, pore sizes, surface areas etc. and the surface silanol groups are susceptible to design and prepare adsorbents for Cr(VI). This review emphases on the progress in the development of different types of silica-based adsorbents by modifying the surfaces of silica and their application for the removal of Cr(VI) from wastewater. Toxicity of Cr(VI), different silica surface modification processes, and removal techniques are also highlighted. The adsorption capacities of the surface-modified silica materials with other parameters are discussed extensively to understand how to select the best condition, silica and modifiers to achieve optimum removal performance. The adsorption mechanisms of various adsorbents are also discussed. Finally, future prospects are summarized and some suggestions are given to enhance the adsorption capacities of the surface-modified silica materials.

Remarkable enhancement of thermal stability of epoxy resin through the incorporation of mesoporous silica micro-filler.

For the first time, we incorporated mesoporous micro-silica (5 µm, pore size = 50 nm) as a filler in epoxy resin aiming to enter polymer into the pore of the silica. As expected, the thermal stability of the composite increased remarkably, followed by noteworthy thermal degradation kinetics when compared to the controlled cured epoxy resin. Composites were prepared by the direct dispersion of modified nano-silica, modified mesoporous micro-silica, unmodified mesoporous micro-silica, non-porous micro-silica, and irregular micro-silica of various pore sizes as fillers in diglycidyl ether of bisphenol-A epoxy resin via ultra-sonication and shear mixing, followed by oven-curing with 4,4-diaminodiphenyl sulfone. DSC and TGA analyses demonstrated a higher glass transition temperature (increased by 3.65-5.75 °C) and very high activation energy for thermal degradation (average increase = 46.2%) was obtained for the same unmodified silica composite compared to pure epoxy, respectively.

Preparation of bio-inspired trimethoxysilyl group terminated poly(1-vinylimidazole)-modified-chitosan composite for adsorption of chromium (VI) ions.

Chitosan and poly(1-vinylimidazole) are both potential adsorbents to remove Cr(VI). Here, we designed the preparation of new adsorbents by combining chitosan and poly(1-vinylimidazole) to get the synergistic effect for the removal of hexavalent chromium. Trimethoxysilyl group terminated poly(1-vinylimidazole)-modified-chitosan composite was successfully synthesized by one-step free radical polymerization based on the grafting backbone of chitosan and vinylimidazole. The resulting adsorbents were used for the removal of Cr(VI) ions from the aqueous solution. The modified chitosan composite was characterized by ATR, FTIR, BET isotherm studies, elemental analysis, TGA, DSC, FE-SEM, and EDX. ATR. FTIR results confirmed the presence of the imidazole group in modified chitosan. The adsorption results were described by the Langmuir isotherm model with a maximum adsorption capacity of 196.1 mg/g for modified chitosan, however, the chitosan yielded 151.5 mg/g. It has been observed that the adsorption of chromium fitted better with the pseudo-second-order kinetics. The modified chitosan composite exhibited greater adsorption capacity than chitosan for hexavalent chromium and has potential application for Cr(VI) removal from aqueous solution containing other common ions with regeneration ability. This novel approach of modifying chitosan with telomerized poly(1-vinyl imidazole) offers potential application in wastewater treatment of different industries releasing Cr (VI).

Facile preparation of an alternating copolymer-based high molecular shape-selective organic phase for reversed-phase liquid chromatography.

The synthesis of a new alternating copolymer-grafted silica phase is described for the separation of shape-constrained isomers of polycyclic aromatic hydrocarbons (PAHs) and tocopherols in reversed-phase high-performance liquid chromatography (RP-HPLC). Telomerization of the monomers (octadecyl acrylate and N-methylmaleimide) was carried out with a silane coupling agent; 3-mercaptopropyltrimethoxysilane (MPS), and the telomer (T) was grafted onto porous silica surface to prepare the alternating copolymer-grafted silica phase (Sil-alt-T). The new hybrid material was characterized by elemental analyses, diffuse reflectance infrared Fourier transform (DRIFT) spectroscopy, and solid-state 13C and 29Si cross-polarization magic-angle spinning (CP/MAS) NMR spectroscopy. The results of 13C CP/MAS NMR demonstrated that the alkyl chains of the grafted polymers in Sil-alt-T remained disordered, amorphous, and mobile represented by gauche conformational form. Separation abilities and molecular-shape selectivities of the prepared organic phase were evaluated by the separation of PAHs isomers and Standard Reference Material 869b, Column Selectivity Test Mixture for Liquid Chromatography, respectively and compared with commercially available octadecylsilylated silica (ODS) and C30 columns as well as previously reported alternating copolymer-based column. The effectiveness of this phase is also demonstrated by the separation of tocopherol isomers. Oriented functional groups along the polymer main chains and cavity formations are investigated to be the driving force for better separation with multiple-interactions with the solutes. One of the advantages of the Sil-alt-T phase to that of the previously reported phase is the synthesis of the telomer first and then immobilized onto silica surface. In this case, the telomer was characterized easily with simple spectroscopic techniques and the molecular mass and polydispersity index of the telomer were determined by size exclusion chromatography (SEC) before grafting onto silica surface. Moreover, both of the monomers were commercially available. Therefore, the technique of preparation was very facile and better separation was achieved with the Sil-alt-T phase compared to the ODS, C30 and other previously reported alternating copolymer-based columns.

Core-shell drug carrier from folate conjugated chitosan obtained from prawn shell for targeted doxorubicin delivery.

A multifunctional drug carrier with dual targeting (magnetic and folate-receptor) and pH sensitive core-shell hybrid nanomaterial has been developed to carry an anticancer drug doxorubicin.Superparamagnetic iron oxide nanoparticles (IONPs) were used as core of the carrier and cross-linked folate conjugated chitosan (FA-CS) was acted as shell in which doxorubicin was physically entrapped. Transmission electron microscopy (TEM) analysis confirmed the average particle size of IONPs and FA-CS coated IONPs 8.2 and 15.4 nm respectively. Magnetic measurement indicated that both the IONPs and FA-CS coated IONPs were superparamagnetic at room temperature with a magnetization value 57.72 and 37.44 emu/g respectively. At pH 5.8 (malignant tissue) showed a burst release of 30.05% of the doxorubicin in the first 4 h followed by a sustained release of 88.26% of drug over 72 h. From these results it is expected that doxorubicin loaded nanoparticles can be a promising drug carrier for the treatment of solid tumors with the ability to reduce toxic side effects of drugs by selective targeting and sustained release.

A WS2 nanosheet-based nanosensor for the ultrasensitive detection of small molecule-protein interaction via terminal protection of small molecule-linked DNA and Nt.BstNBI-assisted recycling amplification.

Small molecule-protein receptor interactions play vital regulatory roles in molecular diagnostics and therapeutics, chemical genetics, and drug development. However, the rapid, sensitive, low-cost, and selective detection of small molecule-protein receptor interaction remains a challenge. We report herein a new tungsten disulfide (WS2) nanosheet-based nanosensor for the ultrasensitive detection of small molecule-protein interaction via terminal protection of small molecule-linked DNA and Nt.BstNBI-assisted recycling amplification strategy. Taking the streptavidin (SA)-biotin system as a model, this assay exhibits high sensitivity with a detection limit of 5.3 pM. Besides a desirable sensitivity, the developed strategies also offer high selectivity, excellent reproducibility, low cost, and simplified operations, implying that these techniques may hold considerable potential for application in molecular diagnostics, biomedical research, genomic research as well as prediction of disease progression.

Versatile ligands for high-performance liquid chromatography: An overview of ionic liquid-functionalized stationary phases.

Ionic liquids (ILs), a class of unique substances composed purely by cation and anions, are renowned for their fascinating physical and chemical properties, such as negligible volatility, high dissolution power, high thermal stability, tunable structure and miscibility. They are enjoying ever-growing applications in a great diversity of disciplines. IL-modified silica, transforming the merits of ILs into chromatographic advantages, has endowed the development of high-performance liquid chromatography (HPLC) stationary phase with considerable vitality. In the last decade, IL-functionalized silica stationary phases have evolved into a series of branches to accommodate to different HPLC modes. An up-to-date overview of IL-immobilized stationary phases is presented in this review, and divided into five parts according to application mode, i.e., ion-exchange, normal-phase, reversed-phase, hydrophilic interaction and chiral recognition. Specific attention is channeled to synthetic strategies, chromatographic behavior and separation performance of IL-functionalized silica stationary phases.

A remarkable enhancement of selectivity towards versatile analytes by a strategically integrated H-bonding site containing phase.

A double ß-alanylated L-glutamide-derived organic phase has been newly designed and synthesized in such a way that integrated H-bonding (interaction) sites make it very suitable for the separation of versatile analytes, including shape-constrained isomers, and nonpolar, polar and basic compounds. The ß-alanine residues introduced into two long-chain alkyl group moieties provide ordered polar groups through H-bonding among the amide groups.

Design of C18 Organic Phases with Multiple Embedded Polar Groups for Ultraversatile Applications with Ultrahigh Selectivity.

For the first time, we synthesized multiple embedded polar groups (EPGs) containing linear C18 organic phases. The new materials were characterized by elemental analysis, IR spectroscopy, (1)H NMR, diffuse reflectance infrared Fourier transform (DRIFT), solid-state (13)C cross-polarization magic angle spinning (CP/MAS) NMR, suspended-state (1)H NMR, and differential scanning calorimetry (DSC). (29)Si CP/MAS NMR was carried out to investigate the degree of cross-linking of the silane and silane functionality of the modified silica. Solid-state (13)C CP/MAS NMR and suspended-state (1)H NMR spectroscopy indicated a higher alkyl chain order for the phase containing four EPGs than for the phase with three EPGs. To correlate the NMR results with temperature-dependent chromatographic studies, standard reference materials (SRM 869b and SRM 1647e), a column selectivity test mixture for liquid chromatography was employed. A single EPG containing the C18 phase was also prepared in a similar manner to be used as a reference column especially for the separation of basic and polar compounds in reversed-phase liquid chromatography (RPLC) and hydrophilic interaction liquid chromatography (HILIC), respectively. Detailed chromatographic characterization of the new phases was performed in terms of their surface coverage, hydrophobic selectivity, shape selectivity, hydrogen bonding capacity, and ion-exchange capacity at pH 2.7 and 7.6 for RPLC as well as their hydrophilicity, the selectivity for hydrophilic-hydrophobic substituents, the selectivity for the region and configurational differences in hydrophilic substituents, the evaluation of electrostatic interactions, and the evaluation of the acidic-basic nature for HILIC-mode separation. Furthermore, peak shapes for the basic analytes propranolol and amitriptyline were studied as a function of the number of EPGs on the C18 phases in the RPLC. The chromatographic performance of multiple EPGs containing C18 HILIC phases is illustrated by the separation of sulfa drugs, ß-blockers, xanthines, nucleic acid bases, nucleosides, and water-soluble vitamins. Both of the phases showed the best performance for the separation of shape-constrained isomers, nonpolar, polar, and basic compounds in RPLC- and HILIC-mode separation of sulfa drugs, and other polar and basic analytes compared to the conventional alkyl phases with and without embedded polar groups and HILIC phases. Surprisingly, one phase would be able to serve the performance of three different types of phases with very high selectivity, and we named this phase the "smart phase". Versatile applications with a single column will reduce the column purchasing cost for the analyst as well as achieve high separation, which is challenging with the commercially available columns.

Preparation and chromatographic evaluation of new branch-type diamide-embedded octadecyl stationary phase with enhanced shape selectivity.

A novel branch-type diamide-embedded octadecyl stationary phase was prepared by facile amidation. The preparation of this new phase involves the synthesis of new bifunctional silane ligand and surface modification of spherical silica via anchoring of silane coupling agent. The obtained diamide-embedded octadecyl stationary phase demonstrated excellent hydrophobic selectivity, as well as enhanced shape and planarity selectivity in comparison to commercial polymeric and monomeric C18 phases, respectively, as revealed by the systematic investigation into its liquid chromatographic retention of isomeric polycyclic aromatic hydrocarbons. The applicability of this new stationary phase was further testified by the effective separation of isomeric compounds belong to different chemical classes, including chain isomers of alkylbenzenes, and positional isomers of substituted aromatics. An in-depth analysis of the separation mechanisms other than molecular shape recognition involved in the new stationary phase was performed using a linear solvation energy relationships model and compared with its monoamide and pure C18 counterparts correspondingly. The performance of the new stationary phase in quantitative analysis of phenols from real-world samples was also evaluated.

Highly hydrophilic and nonionic poly(2-vinyloxazoline)-grafted silica: a novel organic phase for high-selectivity hydrophilic interaction chromatography.

A new hydrophilic and nonionic poly(2-vinyloxazoline)-grafted silica (Sil-VOX(n)) phase was synthesized and applied for the separation of nucleosides and nucleobases in hydrophilic interaction chromatography (HILIC). Polymerization and immobilization onto silica were confirmed by using characterization techniques including (1)H NMR spectroscopy, elemental analysis, and diffuse reflectance infrared Fourier transform spectroscopy. The hydrophilicity or wettability of Sil-VOX(n) was observed by measuring the contact angle (59.9°). The chromatographic results were compared with those obtained with a conventional HILIC silica column. The Sil-VOX(n) phase showed much better separation of polar test analytes than the silica column, and the elution order was different. Differences in selectivity between these two columns indicate that the stationary phase cannot function merely as an inert support for a water layer into which the solutes are partitioned from the bulk mobile phase. To elucidate the interaction mechanism, the separation of dihydroxybenzene isomers was performed on both columns in normal-phase liquid chromatography. Sil-VOX(n) was very sensitive to the dipole moments of the positional isomers of polycyclic aromatic compounds in normal-phase liquid chromatography. The interaction mechanism for Sil-VOX(n) in HILIC separation is also described.

Copolymer-grafted silica phase from a cation-anion monomer pair for enhanced separation in reversed-phase liquid chromatography.

This work reports a new imidazolium and L-alanine derived copolymer-grafted silica stationary phase for ready separation of complex isomers using high-performance liquid chromatography (HPLC). For this purpose, 1-allyl-3-octadecylimidazolium bromide ([AyImC18]Br) and N-acryloyl-L-alanine sodium salt ([AAL]Na) ionic liquids (IL) monomers were synthesized. Subsequently, the bromide counteranion was exchanged with the 2-(acrylamido)propanoate organic counteranion by reacting the [AyImC18]Br with excess [AAL]Na in water. The obtained IL cation-anion monomer pair was then copolymerized on mercaptopropyl-modified silica (Sil-MPS) via a surface-initiated radical chain-transfer reaction. The selective retention behaviors of polycyclic aromatic hydrocarbons (PAHs), including some positional isomers, steroids, and nucleobases were investigated using the newly obtained Sil-poly(ImC18-AAL), and octadecyl silylated silica (ODS) was used as the reference column. Interesting results were obtained for the separation of PAHs, steroids, and nucleobases with the new organic phase. The results showed that the Sil-poly(ImC18-AAL) presented multiple noncovalent interactions, including hydrophobic, π-π, carbonyl-π, and ion-dipole interactions for the separation of PAHs and dipolar compounds. Only pure water was sufficient as the mobile phase for the separation of the nucleobases. Ten nucleosides and bases were separated, using only water as the mobile phase, within a very short time using the Sil-poly(ImC18-AAL), which is otherwise difficult to achieve using conventional hydrophobic columns such as ODS. The combination of electrostatic and hydrophobic interactions are important for the effective separation of such basic compounds without the use of any organic additive as the eluent on the Sil-poly(ImC18-AAL) column.

Molecular orientation of gel forming compounds and their effect on molecular-shape selectivity in liquid chromatography.

Double-alkylated glutamic acid and aminoadipic acid derived gel systems (G1 and G2) have been prepared and then grafted onto silica particles. Gel-forming compounds-grafted silica particles (Sil-G1 and Sil-G2) were then applied for the liquid chromatographic separation of shape-constrained isomers of polycyclic aromatic hydrocarbons (PAHs) and tocopherols as stationary phases. G1 and G2 were analyzed before and after immobilization onto silica. Elemental analysis and thermogravimentric analysis (TGA) results showed almost the same amounts of organic phases were grafted in Sil-G1 and Sil-G2 phases. However, chromatographic results showed large differences of molecular-shape selectivity between the stationary phases. Little change in the chemical structures of the gel-forming compounds can change the molecular orientation as well as drastic change in molecular recognition in liquid chromatography. Molecular orientation of the functional groups affected the interaction mechanism for the separation of shape-constrained isomers. Comparison of the shape selectivity of Sil-G1 and Sil-G2 phases with other commercial columns is also described.

A new imidazolium-embedded C18 stationary phase with enhanced performance in reversed-phase liquid chromatography.

In this paper, a new imidazolium-embedded C(18) stationary phase (SiImC(18)) for reversed-phase high-performance liquid chromatography is described. 1-Allyl-3-octadecylimidazolium bromide ionic liquid compound having a long alkyl chain and reactive groups was newly prepared and grafted onto 3-mercaptopropyltrimethoxysilane-modified silica via a surface-initiated radical-chain transfer addition reaction. The SiImC(18) obtained was characterized by elemental analysis, infrared spectroscopy, thermogravimetric analysis, diffuse reflectance infrared Fourier transform, and solid-state (13)C and (29)Si cross-polarization/magic angle spinning nuclear magnetic resonance spectroscopy. The selectivity toward polycyclic aromatic hydrocarbons relative to that toward alkylbenzenes exhibited by SiImC(18) was higher than the corresponding selectivity exhibited by a conventional octadecyl silica (ODS) column, which could be explained by electrostatic π-π interaction cationic imidazolium and electron-rich aromatic rings. On the other hand, SiImC(18) also showed high selectivity for polar compounds, which was based on the multiple interaction and retention mechanisms of this phase with different analytes. 1,6-Dinitropyrene and 1,8-dinitropyrene, which form a positional isomer pair of dipolar compounds, were separated successfully with the SiImC(18) phase. Seven nucleosides and bases (i.e. cytidine, uracil, uridine, thymine, guanosine, xanthosine, and adenosine) were separated using only water as the mobile phase within 8min, which is difficult to achieve when using conventional hydrophobic columns such as ODS. The combination of electrostatic and hydrophobic interactions is important for the effective separation of such basic compounds without the use of any organic additive as the eluent in the octadecylimidazolium column.

Molecular shape recognition through self-assembled molecular ordering: evaluation with determining architecture and dynamics.

The relationship between molecular gel-forming compound-based double-alkylated L-glutamide-derived functional group-integrated organic phase (Sil-FIP) structure and chromatographic performance is investigated and compared with widely used alkyl phases (C(30), polymeric and monomeric C(18)) as references. The functional group-integrated molecular gel on silica is chemically designed newly in a way that the weak interaction sites are integrated with high orientation and high selectivity can be realized by multiple interactions with the solutes. Its functions can be emphasized by being immobilizable with a terminal carboxyl group and the fact that five amide bonds including ß-alanine subunit are integrated per molecule. Furthermore, its self-assembling function can be detected by monitoring of the chiroptical property. Temperature-dependent circular dichroism (CD) intensity was determined as an indicator of chirality for the gel forming compounds. (13)C cross-polarization magic angle spinning (CP/MAS) NMR spectra of the Sil-FIP phase indicate that predominance of gauche conformations exists at higher temperature (above 30 °C). (29)Si CP/MAS NMR were carried out to investigate the degree of cross-linking of the silane and silane functionality of the modified silica. Temperature-dependent (13)C CP/MAS NMR and suspended-state (1)H NMR measurements of the Sil-FIP phase exhibit the dynamic behavior of the alkyl chains. To correlate the NMR and CD results with temperature-dependent chromatographic studies, standard reference materials (SRM 869b and SRM 1647e), column selectivity test mixture for liquid chromatography was employed. Additional shape selectivity text mixtures were also used to clarify the mechanism of shape selectivity performance of Sil-FIP compared with commercially available columns. The evaluation with the spectroscopic and chromatographic analyses presents very important information on the surface morphology of the new organic phase and the molecular recognition process. Integrated and ordered functional groups were investigated to be the main driving force for very high molecular shape selectivity of the Sil-FIP phase.

Selectivity enhancement for the separation of tocopherols and steroids by integration of highly ordered weak interaction sites along the polymer main chain.

A novel alternating copolymer-based organic phase was synthesized using a new N-substituted maleimide monomer for the development of alternating copolymer-grafted silica for high-performance liquid chromatographic applications. This new monomer (DGMI) was copolymerized with octadecyl acrylate (ODA) from 3-mercaptopropyltrimethoxysilane-grafted silica to produce Sil-poly(ODA-alt-DGMI). The organic phase was characterized by the elemental analysis and the diffuse reflectance infrared Fourier transform spectroscopy. Tocopherol isomers and steroids were used as analytes for the evaluation of the chromatographic selectivity profiles of this novel stationary phase. The selectivity of this column was then compared with a polymeric ODS column and previously developed another alternating copolymer-grafted silica (without the glutamide-derived moiety) column, Sil-poly(ODA-alt-N-octadecylmaleimide). The complete baseline separation of tocopherol isomers in an isocratic mode has been achieved within 25 min with the Sil-poly(ODA-alt-DGMI). The separation of eight kinds of estrogenic steroids and corticoids has also been achieved in an isocratic mode with this column. Significant differences in separation selectivity between Sil-poly(ODA-alt-DGMI) and polymeric ODS columns were observed towards the steroids, and compared with the reference columns, a better separation profile for these analytes was obtained with the Sil-poly(ODA-alt-DGMI). The results of this investigation indicated that the enhancement of selectivity of Sil-poly(ODA-alt-DGMI) towards the test analytes arose from the multiple interaction mechanism such as hydrophobic effect, carbonyl-π and hydrogen-bonding interactions, and such integrated interactions originated from the addition of two amide groups in the N-substituted maleimide monomer.