Sucralose as an oxidative-attenuation tracer for characterizing the application of in situ chemical oxidation for the treatment of 1,4-dioxane.

In situ chemical oxidation (ISCO) has become a widely used soil and groundwater remediation method. Oxidative-attenuation tracers can be used to provide real-time, explicit delineation of contaminant mass-transfer and transformation behavior during an ISCO remediation project. The objective of this study was to evaluate the potential of employing sucralose, a widely used artificial sweetener, as an oxidative-attenuation tracer to characterize the remediation efficiency of 1,4-dioxane (dioxane) by persulfate-based ISCO. Batch and miscible-displacement experiments were conducted to examine the degradation rate and transport behavior of sucralose compared to that of dioxane. Comparable magnitudes and rates of degradation were observed for sucralose and dioxane in batch-reactor experiments with soil and persulfate. The breakthrough curves of sucralose and dioxane transport in a soil-packed column were coincident. The retardation factors were 1.1 for both compounds, indicating limited sorption for both sucralose and dioxane by the soil. Limited degradation was observed in the miscible-displacement experiments, consistent with the short residence time compared to the half-lives of sucralose and dioxane. Persulfate transport and decomposition behavior in the soil-packed columns was similar in the presence of sucralose or dioxane. A simulated tracer test was conducted to illustrate the application of sucralose as an oxidative-attenuation tracer at the pilot scale. These results demonstrate the potential of sucralose as an oxidative-attenuation tracer to support the robust design of ISCO applications for dioxane. The oxidative-attenuation tracer test method is anticipated to be an effective approach for characterizing mass-removal behavior of other emerging contaminants with appropriate selection of tracer.

Structural Features of Alkaline Dioxane Lignin and Residual Lignin from Eucalyptus grandis × E. urophylla.

In the present study, lignin from eucalyptus was extracted with 80% alkaline dioxane (0.05 M NaOH) from ball-milled wood and subsequently fractionated by gradient acid precipitation from the filtrate. Meanwhile, the residual lignin was prepared by a double enzymatic hydrolysis process. The yield of the lignin extracted by alkaline dioxane (LA-2) was 29.5%. The carbohydrate contents and molecular weights of the gradient acid precipitated lignin fractions gradually decreased from 4.90 to 1.36% and from 7770 to 5510 g/mol, respectively, with the decline of the pH value from 6 to 2. Results from two-dimensional heteronuclear single quantum coherence nuclear magnetic resonance (NMR) and 31P NMR spectroscopy showed an evident reduction of ß- O-4 ' linkages with the pH value decrease, while the contents of aliphatic -OH, phenolic -OH, and carboxylic groups displayed an increasing trend. Moreover, the residual lignin exhibited the highest molecular weight (11690 g/mol), the most abundant ß- O-4 ' linkages (71.1%), and the highest S/G ratio (4.68).

Isoamericanoic Acid B from Acer tegmentosum as a Potential Phytoestrogen.

Phytoestrogens derived from plants have attracted the attention of the general public and the medical community due to their potentially beneficial role in relieving menopausal symptoms. The deciduous tree Acer tegmentosum Maxim (Aceraceae) has long been utilized in Korean folk medicine to alleviate many physiological disorders, including abscesses, surgical bleeding, and liver diseases. In order to explore structurally and/or biologically new constituents from Korean medicinal plants, a comprehensive phytochemical study was carried out on the bark of A. tegmentosum. One new phenolic compound with a 1,4-benzodioxane scaffold, isoamericanoic acid B (1), as well as with nine known phenolic compounds (2⁻10), were successfully isolated from the aqueous extracts of the bark of A. tegmentosum. A detailed analysis using 1D and 2D NMR spectroscopy, electronic circular dichroism (ECD) spectral data, and LC/MS afforded the unambiguous structural determination of all isolated compounds, including the new compound 1. In addition, compounds 2, 4, 5, and 9 were isolated and identified from the bark of A. tegmentosum for the first time. All isolated compounds were tested for their estrogenic activities using an MCF-7 BUS cell proliferation assay, which revealed that compounds 1, 2, and 10 showed moderate estrogenic activity. To study the mechanism of this estrogenic effect, a docking simulation of compound 1, which showed the best estrogenic activity, was conducted with estrogen receptor (ER) -α and ER-ß, which revealed that it interacts with the key residues of ER-α and ER-ß. In addition, compound 1 had slightly higher affinity for ER-ß than ER-α in the calculated Gibbs free energy for 1:ER-α and 1:ER-ß. Thus, the present experimental evidence demonstrated that active compound 1 from A. tegmentosum could be a promising phytoestrogen for the development of natural estrogen supplements.

Hyperdioxane A, a Conjugate of Dibenzo-1,4-dioxane and Sesquiterpene from Hypericum ascyron.

Two new dibenzo-1,4-dioxane derivatives, hyperdioxanes A (1) and B (2), were isolated from the roots of a Hypericaceous plant, Hypericum ascyron. Hyperdioxane A (1) is a conjugate of dibenzo-1,4-dioxane and sesquiterpene with an unprecedented heptacyclic ring system. The structures of 1 and 2 were assigned by detailed spectroscopic analyses, including application of a modified Mosher's method. A possible biogenetic pathway of hyperdioxane A (1) from hyperdioxane B (2) and a sesquiterpene, eremophil-9,11(13)-dien-8ß,12-olide (3), is presented.

Development of Fully Degradable Phosphonium-Functionalized Amphiphilic Diblock Copolymers for Nucleic Acids Delivery.

To expand the range of functional polymer materials to include fully hydrolytically degradable systems that bear bioinspired phosphorus-containing linkages both along the backbone and as cationic side chain moieties for packaging and delivery of nucleic acids, phosphonium-functionalized polyphosphoester- block-poly(l-lactide) copolymers of various compositions were synthesized, fully characterized, and their self-assembly into nanoparticles were studied. First, an alkyne-functionalized polyphosphoester- block-poly(l-lactide) copolymer was synthesized via a one pot sequential ring opening polymerization of an alkyne-functionalized phospholane monomer, followed by the addition of l-lactide to grow the second block. Second, the alkynyl side groups of the polyphosphoester block were functionalized via photoinitiated thiol-yne radical addition of a phosphonium-functionalized free thiol. The polymers of varying phosphonium substitution degrees were self-assembled in aqueous buffers to afford formation of well-defined core-shell assemblies with an average size ranging between 30 and 50 nm, as determined by dynamic light scattering. Intracellular delivery of the nanoparticles and their effects on cell viability and capability at enhancing transfection efficiency of nucleic acids (e.g., siRNA) were investigated. Cell viability assays demonstrated limited toxicity of the assembly to RAW 264.7 mouse macrophages, except at high polymer concentrations, where the polymer of high degree of phosphonium functionalization induced relatively higher cytotoxicity. Transfection efficiency was strongly affected by the phosphonium-to-phosphate (P+/P-) ratios of the polymers and siRNA, respectively. The AllStars Hs Cell Death siRNA complexed to the various copolymers at a P+/P- ratio of 10:1 induced comparable cell death to Lipofectamine. These fully degradable nanoparticles might provide biocompatible nanocarriers for therapeutic nucleic acid delivery.

Anti-MRSA activity of oxysporone and xylitol from the endophytic fungus Pestalotia sp. growing on the Sundarbans mangrove plant Heritiera fomes.

Heritiera fomes Buch.-Ham., a mangrove plant from the Sundarbans, has adapted to a unique habitat, muddy saline water, anaerobic soil, brackish tidal activities, and high microbial competition. Endophytic fungal association protects this plant from adverse environmental conditions. This plant is used in Bangladeshi folk medicine, but it has not been extensively studied phytochemically, and there is hardly any report on investigation on endophytic fungi growing on this plant. In this study, endophytic fungi were isolated from the surface sterilized cladodes and leaves of H. fomes. The antimicrobial activities were evaluated against two Gram-positive and two Gram-negative bacteria and the fungal strain, Candida albicans. Extracts of Pestalotia sp. showed activities against all test bacterial strains, except that the ethyl acetate extract was inactive against Escherichia coli. The structures of the purified compounds, oxysporone and xylitol, were elucidated by spectroscopic means. The anti-MRSA potential of the isolated compounds were determined against various MRSA strains, that is, ATCC 25923, SA-1199B, RN4220, XU212, EMRSA-15, and EMRSA-16, with minimum inhibitory concentration values ranging from 32 to 128 µg/ml. This paper, for the first time, reports on the anti-MRSA property of oxysporone and xylitol, isolation of the endophyte Pestalotia sp. from H. fomes, and isolation of xylitol from a Pestalotia sp.

Ring opening polymerisation of lactide with uranium(iv) and cerium(iv) phosphinoaryloxide complexes.

The C3-symmetric uranium(iv) and cerium(iv) complexes Me3SiOM(OArP)3, M = U (1), Ce (2), OArP = OC6H2-6-tBu-4-Me-2-PPh2, have been prepared and the difference between these 4f and 5f congeners as initiators for the ring opening polymerisation (ROP) of l-lactide is compared. The poorly controlled reactivity of the homoleptic analogue U(OArP)4 (3) demonstrates the importance of the M-OSiMe3 initiating group. The incorporation of a nickel atom in 1 to form the U-Ni heterobimetallic complex Me3SiOU(OArP)3Ni (4) may be the first example of the use of the inverse trans influence to switch the reactivity of a complex. This would imply the formation of the U-Ni bond strengthens the U-OSiMe3 bond to such an extent that the ROP catalysis is switched off. Changing the conditions to immortal polymerisation dramatically increases polymerisation rates, and switches the order, with the Ce complex now faster than the U analogue, suggesting ligand protonolysis to afford a more open coordination sphere. For the ROP of rac-lactide, uranium complex 1 promotes heterotacticity at the highest levels of stereocontrol yet reported for an actinide complex.

Development of a membrane of poly (L-co-D,L lactic acid-co-trimethylene carbonate) with aloe vera: An alternative biomaterial designed to improve skin healing.

The search for new therapies and drugs that act as topical agents to relieve pain and control the infectious processes in burns always attracted interest in clinical trials. As an alternative to synthetic drugs, the use of natural extracts is useful in the development of new strategies and formulations for improving the life quality. The aim of this study was to develop a wound dressing using Poly(L-co-D,L lactic acid-co-TMC) (PLDLA-co-TMC) containing aloe vera (AV). This natural plant extract is known for its modulatory effects under healing process. The membrane of PLDLA-co-TMC+aloe vera was prepared at different concentrations of AV (5, 10, 15 and 50%). The FTIR showed no change in the PLDLA-co-TMC spectrum after AV addition, while the swelling test showed changes only in PLDLA-co-TMC+AV at 50%. The wettability measurements showed decrease in the contact angle in all samples after the AV addition in the polymer, while the AV release test showed that PLDLA-co-TMC+50%AV sample has higher AV release rate than the sample with other AV concentrations. The SEM analysis showed that AV was homogeneously distributed at 5% only. Tensile tests demonstrated an increase in the Young's modulus and a reduction in the elongation till rupture of the PLDLA-co-TMC after the addition of AV. Biocompatibility in vitro evaluation with fibroblast cells seeded in the membranes of PLDLA-co-TMC+AV showed that the cells were able to adhere, proliferate and maintain mitochondrial activity in all AV concentrations tested. Due to the known skin medicinal properties attributed to AV and the results here obtained, we suggest that after in vivo trials, the PLDLA-co-TMC+AV should be a promising biomaterial for application as a device for skin curative and healing agent.

Kinetic Spectrophotometric Method for the 1,4-Diionic Organophosphorus Formation in the Presence of Meldrum's Acid: Stopped-Flow Approach.

The kinetics of the reaction between triphenylphosphine (TPP) and dimethyl acetylenedicarboxylate (DMAD) in the presence of Meldrum's acid (MA) for the generation of the 1,4-diionic organophosphorus compound has been investigated using the stopped-flow and UV-VIS spectrophotometry techniques. The first step of the reaction between TPP and DMAD for the generation of (I1) in ethanol was followed by the stopped-flow apparatus. This step was recognized as a fast step. The reaction between the intermediate (I1) and MA showed first-order kinetics, and it was followed by the UV-VIS spectrophotometry technique. The activation parameters for the slow step of the proposed mechanism were determined using two linearized forms of the Eyring equation. From the temperature, concentration and solvent studies, the activation energy (Ea = 20.16 kJ·mol-1) and the related activation parameters (ΔG‡ = 71.17 ± 0.015 kJ·mol-1, ΔS‡ = -185.49 ± 0.026 J·mol-1 and ΔH‡ =17.72 ± 0.007 kJ·mol-1) were calculated. The experimental data indicated that the reaction was zero-order in MA and second-order overall. The proposed mechanism was confirmed with the observed kinetic data obtained from the UV-VIS and stopped-flow techniques.

Antimicrobial Metabolites from a Marine-Derived Actinomycete in Vietnam's East Sea.

Two new compounds, a quinoline alkaloid (1) and a 1,4-dioxane derivative (2), were isolated from culture broth of the marine-derived actinomycete Micromonospora sp. (strain G019) by bioassay-guided fractionation. This actinomycete strain was isolated from sediment, collected at Cát Bà Peninsula, Vietnam. The taxonomic identification was achieved by analysis of 16S rRNA gene sequences. On the basis of morphological and phylogenetic evidence, strain G019 was assigned to the genus Micromonospora. The structures of 1 and 2 were established by spectroscopic data analysis, including one- and two-dimensional NMR, and MS. Compound 1 was found to have antibacterial activity against Escherichia coli (MIC: 48 µg/mL), Salmonella enterica (MIC: 96 µg/mL) and Enterococcus faecalis (MIC: 128 µg/mL), while compound 2 showed inhibitory activity against Enterococcusfaecalis (MIC: 32 µg/mL) and Candida albicans (MIC: 64 µg/mL).

Peroxone activated persulfate treatment of 1,4-dioxane in the presence of chlorinated solvent co-contaminants.

1,4-dioxane is often found as a co-contaminant with chlorinated volatile organic compounds (VOCs) at solvent release sites such as landfills, solvent recycling facilities, or fire training areas. Historically, soil and groundwater samples were not routinely analyzed for 1,4-dioxane and therefore the number of known 1,4-dioxane sites is still increasing. Due to its co-occurrence with chlorinated compounds, remediation strategies are needed that simultaneously treat both 1,4-dioxane as well as chlorinated VOC co-contaminants. In this proof of concept laboratory study, the fate of 1,4-dioxane was examined during the targeted destruction of aqueous phase VOC, using a peroxone activated persulfate (PAP) chemical oxidation method. Bench-scale experiments were carried out to evaluate the treatability of 1,4-dioxane as both a single-contaminant and in the presence of trichloroethene (TCE), and 1,1,1-trichloroethane (1,1,1-TCA). Possible dependencies on oxidant concentration and reaction kinetics were studied. The oxidative destruction of 1,4-dioxane, TCE and 1,1,1-TCA in single-contaminant batch systems followed pseudo-first-order reaction kinetics and even at the most dilute oxidant concentration lasted for at least 13 days. The rate of oxidation for each contaminant increased linearly with increasing persulfate concentration over the range of oxidant concentrations tested. The rate of oxidative destruction, from most easily degraded to least, was: TCE > 1,4-dioxane > 1,1,1-TCA. Oxidation rates were up to 87% slower in a mixture of these three compounds. Although additional tests are necessary, our data suggest that PAP oxidation of 1,4-dioxane might aid in the cleanup of VOC contaminated sites.

Effect of bioactive glass particles on osteogenic differentiation of adipose-derived mesenchymal stem cells seeded on lactide and caprolactone based scaffolds.

Incorporation of bioactive glass (BG) particles to synthetic polymer scaffolds is a promising strategy to improve the bioactivity of bioinert materials and to stimulate specific cell responses. In this study, the influence of incorporating BG particles to lactide and caprolactone based porous scaffolds on osteogenic differentiation of adipose-derived stem cells (ASCs) was analyzed. Accordingly, ASCs were seeded on poly(L-lactide) (PLLA), poly(ε-caprolactone) (PCL), or poly(L-lactide-co-ε-caprolactone) (PLCL) scaffolds containing 15 vol % of BG particles in two culture conditions: standard versus osteogenic culture medium. In standard culture medium, incorporation of BG to a PLLA scaffold increased the ALP activity with respect to its unfilled counterpart (ca. 1.2- and a 1.6-fold increase over 7 and 14 days, respectively). Moreover, in all the studied polymers the incorporation of BG induced a slightly higher production of mineralized matrix by ASCs, but the differences observed were not statistically significant. In the osteogenic medium, the effect of BG was masked by the effect of osteogenic supplements in the long-term. However, in the short-term (day 7), BG particles induced an early ALP activity of predifferentiated osteoblasts on PLLA and PCL scaffolds and higher matrix mineralization on PCL scaffolds. In summary, the addition of BG particles to PLLA and PCL scaffolds sustains ASC osteogenic differentiation, facilitates mineralization and induces the formation of a hydroxyapatite layer on the surface of the polymer scaffolds.

Preparation of gentamicin dioctyl sulfosuccinate loaded poly(trimethylene carbonate) matrices intended for the treatment of orthopaedic infections.

BACKGROUND: Infection is a common problem in trauma and orthopaedic surgery. Antibiotic-loaded biomaterials are used locally to clear infections as an adjunct to systemic antibiotics. Gentamicin-sulphate (GEN-SULPH) is commonly used in antibiotic-loaded biomaterials, although it displays high water solubility resulting in quick diffusion from the carrier. OBJECTIVE: Preparation of a lipophilic derivative of gentamicin to reduce solubility and obtain a slower release. Subsequently, entrapment of this lipophilic gentamicin within poly(trimethylene carbonate) (PTMC) matrices. METHODS: Hydrophobic ion-pairing was used to prepare lipophilic gentamicin (GEN-AOT). The susceptibility of Staphylococcus aureus NCTC 12973 and Staphylococcus epidermidis 103.1 for GEN-AOT was tested and the viability of fibroblasts upon exposure to GEN-AOT was assessed. GEN-AOT was then loaded into PTMC films. RESULTS: GEN-AOT was successfully prepared as confirmed by FTIR-spectroscopy. GEN-AOT was bactericidal for S. epidermidis and S. aureus at 0.5 µM and 8.5 µM, respectively. At 1.1 µM GEN-AOT no reduction in fibroblast viability was observed. At 11 µM the reduction was ∼50% . PTMC discs loaded with GEN-AOT were prepared by compression molding. CONCLUSIONS: Lipophilic GEN-AOT was at least as potent as GEN-SULPH. For S. epidermidis it was even more potent than GEN-SULPH. More than 50% fibroblast cell viability was maintained at bactericidal concentration for both bacterial strains.

Isolation and structural characterization of the milled wood lignin, dioxane lignin, and cellulolytic lignin preparations from brewer's spent grain.

The structure of the lignin from brewer's spent grain (BSG) has been studied in detail. Three different lignin preparations, the so-called "milled-wood" lignin (MWL), dioxane lignin (DL), and cellulolytic lignin (CEL), were isolated from BSG and then thoroughly characterized by pyrolysis GC/MS, 2D-NMR, and derivatization followed by reductive cleavage (DFRC). The data indicated that BSG lignin presents a predominance of guaiacyl units (syringyl/guaiacyl ratio of 0.4-0.5) with significant amounts of associated p-coumarates and ferulates. The flavone tricin was also present in the lignin from BSG, as also occurred in other grasses. 2D-NMR (HSQC) revealed that the main substructures present are ß-O-4' alkyl-aryl ethers (77-79%) followed by ß-5' phenylcoumarans (11-13%) and lower amounts of ß-ß' resinols (5-6%) and 5-5' dibenzodioxocins (3-5%). The results from 2D-NMR (HMBC) and DFRC indicated that p-coumarates are acylating the γ-carbon of lignin side chains and are mostly involved in condensed structures. DFRC analyses also indicated a minor degree of γ-acylation with acetate groups, which takes place preferentially on S lignin (6% of S units are acetylated) over G lignin (only 1% of G units are acetylated).

Novel, broad-spectrum anticonvulsants containing a sulfamide group: pharmacological properties of (S)-N-[(6-chloro-2,3-dihydrobenzo[1,4]dioxin-2-yl)methyl]sulfamide (JNJ-26489112).

Broad-spectrum anticonvulsants are of considerable interest as antiepileptic drugs, especially because of their potential for treating refractory patients. Such "neurostabilizers" have also been used to treat other neurological disorders, including migraine, bipolar disorder, and neuropathic pain. We synthesized a series of sulfamide derivatives (4-9, 10a-i, 11a, 11b, 12) and evaluated their anticonvulsant activity. Thus, we identified promising sulfamide 4 (JNJ-26489112) and explored its pharmacological properties. Compound 4 exhibited excellent anticonvulsant activity in rodents against audiogenic, electrically induced, and chemically induced seizures. Mechanistically, 4 inhibited voltage-gated Na(+) channels and N-type Ca(2+) channels and was effective as a K(+) channel opener. The anticonvulsant profile of 4 suggests that it may be useful for treating multiple forms of epilepsy (generalized tonic-clonic, complex partial, absence seizures), including refractory (or pharmacoresistant) epilepsy, at dose levels that confer a good safety margin. On the basis of its pharmacology and other favorable characteristics, 4 was advanced into human clinical studies.

Synthesis and antitumor activity of 1,3,4-oxadiazole possessing 1,4-benzodioxan moiety as a novel class of potent methionine aminopeptidase type II inhibitors.

A series of 1,3,4-oxadiazole derivatives containing 1,4-benzodioxan moiety (7a-7q) have been designed, synthesized and evaluated for their antitumor activity. Most of the synthesized compounds were proved to have potent antitumor activity and low toxicity. Among them, compound 7a showed the most potent biological activity against Human Umbilical Vein Endothelial cells, which was comparable to the positive control. The results of apoptosis and flow cytometry (FCM) demonstrated that compound 7a induce cell apoptosis by the inhibition of MetAP2 pathway. Molecular docking was performed to position compound 7a into MetAP2 binding site in order to explore the potential target.

5alpha,8alpha-epidioxysterols from a Formosan sponge, Axinyssa sp.

One new 5alpha,8alpha-epidioxysterol, 3-acetylaxinysterol (1), along with one known sterol, axinysterol (2), were isolated from a Formosan sponge, Axinyssa sp.. The structures of the compounds were determined by spectroscopic methods and the absolute configuration of 2 was further confirmed by single-crystal X-ray diffraction analysis for the first time. Compound 2 exhibited significant cytotoxicity against K562 and Molt 4 cancer cell lines.

Use of over the counter oral relief aids or dietary supplements for the ring-opening polymerization of lactide.

Over the counter oral relief aids or dietary supplements, namely calcium carbonate, calcium hydroxyapatite, magnesium oxide, zinc oxide, Tums® and Pepto-Bismol® have been investigated in the melt ring-opening polymerization of lactide and a direct comparison with that involving tin(II) octanoate has been made. Of these, Pepto-Bismol® is shown to be the most active and comparable to tin octanoate. The active ingredient in Pepto-Bismol® is bismuth subsalicylate and when this is employed as the initiator similar results are obtained in melt polymerizations which suggests it could be employed as an alternative to the commercially used tin(II) octanoate.

Probing hyperconjugation experimentally with the conformational deuterium isotope effect.

Hyperconjugation underlies many chemical phenomena of fundamental and practical importance. Owing to a great deal of interest in the anomeric effect, anomeric-like hyperconjugative effects have been thoroughly investigated in oxygen-containing systems. However, such interactions in the second- and third-row chalcogens are less well-understood and have generated some controversy. Here, we show that the conformational deuterium isotope effect, in combination with Saunders' isotopic perturbation method, permits sensitive and direct experimental probing of the conformational equilibria in dioxane, dithiane, and diselenane analogues by variable-temperature, dynamic NMR spectroscopy. We find that the magnitude of the conformational deuterium isotope effect is 252.1, 28.3, and 7.1 J/mol (±10%) for the oxygen, sulfur, and selenium analogues, respectively. These results reveal the periodic trend for hyperconjugation in the chalcogens, which reflect a decreasing n(x)→σ(C-H(D)) interaction throughout the period, as supported by IR spectroscopy and in agreement with DFT calculations and a natural bond order analysis.

Self-assembly and orientation of hydrogen-bonded oligothiophene polymorphs at liquid-membrane-liquid interfaces.

One of the challenges in organic systems with semiconducting function is the achievement of molecular orientation over large scales. We report here on the use of self-assembly kinetics to control long-range orientation of a quarterthiophene derivative designed to combine intermolecular π-π stacking and hydrogen bonding among amide groups. Assembly of these molecules in the solution phase is prevented by the hydrogen-bond-accepting solvent tetrahydrofuran, whereas formation of H-aggregates is facilitated in toluene. Rapid evaporation of solvent in a solution of the quarterthiophene in a 2:1:1 mixture of 1,4-dioxane/tetrahydrofuran/toluene leads to self-assembly of kinetically trapped mats of bundled fibers. In great contrast, slow drying in a toluene atmosphere leads to the homogeneous nucleation and growth of ordered structures shaped as rhombohedra or hexagonal prisms depending on concentration. Furthermore, exceedingly slow delivery of toluene from a high molecular weight polymer solution into the system through a porous aluminum oxide membrane results in the growth of highly oriented hexagonal prisms perpendicular to the interface. The amide groups of the compound likely adsorb onto the polar aluminum oxide surface and direct the self-assembly pathway toward heterogeneous nucleation and growth to form hexagonal prisms. We propose that the oriented prismatic polymorph results from the synergy of surface interactions rooted in hydrogen bonding on the solid membrane and the slow kinetics of self-assembly. These observations demonstrate how self-assembly conditions can be used to guide the supramolecular energy landscape to generate vastly different structures. These fundamental principles allowed us to grow oriented prismatic assemblies on transparent indium-doped tin oxide electrodes, which are of interest in organic electronics.