Recombinant Trichoderma harzianum endoglucanase I (Cel7B) is a highly acidic and promiscuous carbohydrate-active enzyme.

Trichoderma filamentous fungi have been investigated due to their ability to secrete cellulases which find various biotechnological applications such as biomass hydrolysis and cellulosic ethanol production. Previous studies demonstrated that Trichoderma harzianum IOC-3844 has a high degree of cellulolytic activity and potential for biomass hydrolysis. However, enzymatic, biochemical, and structural studies of cellulases from T. harzianum are scarce. This work reports biochemical characterization of the recombinant endoglucanase I from T. harzianum, ThCel7B, and its catalytic core domain. The constructs display optimum activity at 55 °C and a surprisingly acidic pH optimum of 3.0. The full-length enzyme is able to hydrolyze a variety of substrates, with high specific activity: 75 U/mg for ß-glucan, 46 U/mg toward xyloglucan, 39 U/mg for lichenan, 26 U/mg for carboxymethyl cellulose, 18 U/mg for 4-nitrophenyl ß-D-cellobioside, 16 U/mg for rye arabinoxylan, and 12 U/mg toward xylan. The enzyme also hydrolyzed filter paper, phosphoric acid swollen cellulose, Sigmacell 20, Avicel PH-101, and cellulose, albeit with lower efficiency. The ThCel7B catalytic domain displays similar substrate diversity. Fluorescence-based thermal shift assays showed that thermal stability is highest at pH 5.0. We determined kinetic parameters and analyzed a pattern of oligosaccharide substrates hydrolysis, revealing cellobiose as a final product of C6 degradation. Finally, we visualized effects of ThCel7B on oat spelt using scanning electron microscopy, demonstrating the morphological changes of the substrate during the hydrolysis. The acidic behavior of ThCel7B and its considerable thermostability hold a promise of its industrial applications and other biotechnological uses under extremely acidic conditions.

Zein and hydroxypropyl methylcellulose acetate succinate microfibers combined with metronidazole benzoate and/or metronidazole-incorporated cellulose nanofibrils for potential periodontal treatment.

The development of flexible and porous materials to control antibacterial delivery is a pivotal endeavor in medical science. In this study, we aimed to produce long and defect-free fibers made of zein and hydroxypropyl methylcellulose acetate succinate (HPMCAS) to be used as a platform for the release of metronidazole (MDZ) and metronidazole benzoate (BMDZ) to be potentially used in periodontal treatment. Microfibers prepared via electrospinning under a 2:3 (w/w) zein to HPMCAS ratio, containing 0.5 % (w/w) poly(ethylene oxide) (PEO) and 1 % (w/w) cellulose nanofibril (CNF) were loaded with 40 % (w/w) MDZ, 40 % (w/w) BMDZ, or a combination of 20 % (w/w) of each drug. The addition of CNF improved the electrospinning process, resulting in long fibers with reduced MDZ and BMDZ surface crystallization. MDZ- and BMDZ-incorporated fibers were semicrystalline and displayed commendable compatibility among drugs, nanocellulose and polymeric chains. Release tests showed that zein/HPMCAS/PEO fibers without CNF and with 20 % (w/w) MDZ/ 20 % (w/w) BMDZ released the drug at a slower and more sustained rate compared to other samples over extended periods (up to 5 days), which is a favorable aspect concerning periodontitis treatment.

"Attacking-Attacking" Anti-biofouling Strategy Enabled by Cellulose Nanocrystals-Silver Materials.

The development of high-performance anti-biofouling surfaces is paramount for controlling bacterial attachment and biofilm growth in biomedical devices, food packing, and filtration membranes. Cellulose nanocrystals (CNCs), a carbon-nanotube-like nanomaterial, have emerged as renewable and sustainable antimicrobial agents. However, CNCs inactivate bacteria under contact-mediated mechanisms, limiting its antimicrobial property mostly to the attached bacteria. This study describes the combination of CNCs with silver nanoparticles (CNC/Ag) as a strategy to increase their toxicity and anti-biofouling performance. CNC/Ag-coated surfaces inactivated over 99% of the attached Escherichia coli and Bacillus subtilis cells compared to 66.9 and 32.9% reduction shown by the pristine CNC, respectively. CNC/Ag was also very toxic to planktonic cells, displaying minimal inhibitory of 25 and 100 µg/mL against B. subtilis and E. coli, respectively. CNC/Ag seems to inactivate bacteria through an "attacking-attacking" mechanism where CNCs and silver nanoparticles play different roles. CNCs can kill bacteria by piercing the cell membrane. This physical membrane stress-mediated mechanism is demonstrated as lipid vesicles release their encapsulated dye upon contact with CNCs. Once the cell membrane is punctured, silver ions can enter the cell passively and compromise the integrity of DNA and other organelles. Inside the cells, Ag+ may damage the cell membrane by selectively interacting with sulfur and nitrogen groups of enzymes and proteins or by harming DNA via accumulation of reactive oxygen species. Therefore, CNC/Ag toxicity seems to combine the puncturing effect of the needle-like CNC and the silver's ability to impair the cell membrane and DNA functionalities.

Antisolvent versus ultrasonication: Bottom-up and top-down approaches to produce lignin nanoparticles (LNPs) with tailored properties.

In spite of the increasing amount of literature on the production and application of lignin nanoparticles (LNPs), little or no attention has been paid so far to the influence of different production methods on the properties of these nanostructures. Herein, we propose a comprehensive study to assess the impact of several factors on the color, morphology, colloidal stability, antioxidant capacity, and UV-shielding performance of LNPs. LNPs were obtained by two different routes: a bottom-up approach based on the self-assembly in a solvent-antisolvent system with acetone/lignin/water; or a top-down approach based on the ultrasonication of never-dried lignin aqueous suspensions. The starting lignin was extracted from elephant grass leaves or stems, so that the influence of anatomical origin and molecular weight could also be investigated. Moreover, lignin was oxidized prior to being converted into LNPs, allowing for comparisons between different oxidation degrees. This study showed that interesting properties of LNPs can be easily tailored and combined focusing on the various applications of these versatile nanostructures. In a model application, different types of LNPs were incorporated into poly(vinyl alcohol)-based nanocomposites, modulating the UV-protection capability of the polymer matrix.

Cellulose nanofibers production using a set of recombinant enzymes.

Cellulose nanofibers (CNF) are renewable and biodegradable nanomaterials with attractive barrier, mechanical and surface properties. In this work, three different recombinant enzymes: an endoglucanase, a xylanase and a lytic polysaccharide monooxygenase, were combined to enhance cellulose fibrillation and to produce CNF from sugarcane bagasse (SCB). Prior to the enzymatic catalysis, SCB was chemically pretreated by sodium chlorite and KOH, while defibrillation was accomplished via sonication. We obtained much longer (µm scale length) and more thermostable (resisting up to 260 °C) CNFs as compared to the CNFs prepared by TEMPO-mediated oxidation. Our results showed that a cooperative action of the set of hydrolytic and oxidative enzymes can be used as a "green" treatment prior to the sonication step to produce nanofibrillated cellulose with advanced properties.

Design of experiments driven optimization of alkaline pretreatment and saccharification for sugarcane bagasse.

To maximize the sugar release from sugarcane bagasse, a high-resolution Fractional Factorial Design (FFD) was combined with a Central Composite Orthogonal (CCO) design to simultaneously evaluate a wide range of variables for alkaline pretreatment (NaOH: 0.1-1 mol/L, temperature: 100-220 °C, and time: 20-80 min) and enzymatic saccharification (enzyme loading: 2.5-17.5%, and reaction volume: 550-850 µL). A total of 46 experimental conditions were evaluated and the maximum sugar yield (423 mg/g) was obtained after 18 h enzymatic hydrolysis under optimized conditions (0.25 mol/L NaOH at 202 °C for 40 min, with 12.5% of enzyme loading). Biomass compositional analyses showed that the pretreatments strongly removed lignin (up to 70%), silica (up to 80%) and promoted cellulose enrichment (25-110%). This robust design of experiments resulted in maximizing enzymatic hydrolysis efficiency of sugarcane bagasse and further indicated that this combined approach is versatile for other lignocellulosic biomasses.

Morphology and self-arraying of SDS and DTAB dried on mica surface.

Dewetting phenomena produce interesting patterns that may impart new properties to solid surfaces. Sodium dodecyl sulfate (SDS) and dodecyltrimethylammonium bromide (DTAB) aqueous solutions, dried on mica surfaces under different drying conditions, undergo dewetting events forming structured deposits that were imaged by scanning electron microscopy (SEM), atomic force (AFM) and Kelvin force microscopy (KFM). Dry SDS, in most situations, displays long branched stripes formed due to fingering instability, while DTAB undergoes stick-slip motion forming patterns of parallel continuous or split stripes. In both systems, independently of drying conditions, surfactants pack forming lamellar structures, but with different orientations: SDS lamellae are aligned parallel to the substrate whereas DTAB lamellae are normal to the mica plane. Electric potential maps of SDS obtained by KFM show well-defined electrostatic patterns: surfactant layers deposited on mica are overall negative with a larger excess of negative charge in the interlamellar space than in the lamellar faces.

Molecular mapping by low-energy-loss energy-filtered transmission electron microscopy imaging.

Structure-function relationships in supramolecular systems depend on the spatial distribution of molecules, ions, and particles within complex arrays. Imaging the spatial distribution of molecular components within nanostructured solids is the objective of many recent techniques, and a powerful tool is electron spectroscopy imaging in the transmission electron microscope (ESI-TEM) in the low-energy-loss range, 0-80 eV. This technique was applied to particulate and thin film samples of dielectric polymers and inorganic compounds, providing excellent distinction between areas occupied by various macromolecules and particles. Domains differentiated by small changes in molecular composition and minor differences in elemental contents are clearly shown. Slight changes in the molecules produce intensity variations in molecular spectra that are in turn expressed in sets of low-energy-loss images, using the standard energy-filtered transmission electron microscopy (EFTEM) procedures. The molecular map resolution is in the nanometer range and very close to the bright-field resolution achieved for the same sample, in the same instrument. Moreover, contrast is excellent, even though sample exposure to the electron beam is minimal.

Effect of hydrogen-bonding complexation on the interfacial behavior of poly(isoprene)-b-poly(ethylene oxide) and poly(isoprene)-b-poly(acrylic acid) Langmuir monolayers.

The effect of hydrogen-bonding complexation on the interfacial behavior of poly(isoprene)-b-poly(ethylene oxide) (PI-b-PEO) diblock copolymer at the air-water interface has been investigated by Langmuir balance and neutron reflectivity. PI-b-PEO forms Langmuir monolayers with PI as the anchoring block. Introduction of a second diblock, poly(isoprene)-b-poly(acrylic acid) (PI-b-PAA) yields PI-b-PEO/PI-b-PAA mixed layers with interfacial behavior that is pH-dependent. At pH 10.0 and 5.7, the compression (pi-A) isotherms exhibit three regions that are characteristic of PEO-type tethered layers, (i) a low-pressure 2-D "pancake" region (region I), (ii) a pseudoplateau where PEO segments desorb and are immerse in the subphase (region II), and (iii) a steep pressure rise region commonly considered as the "brush" regime (region III). At pH 2.5, on the other hand, the pi-A isotherm shows only two regions, (I) and (III). This novel behavior is attributed to hydrogen-bonding complexation between the undissociated carboxylic acids and the PEO, forming very compact layers. It appears that desorption of PEO segments is hindered as a consequence of this complexation. Furthermore, no brush-like structure is observed in region III of the isotherml; thus, the steep rise in surface pressure in this case arises primarily from interactions of the anchoring block. The hydrogen-bonded complex of PI-b-PEO/PI-b-PAA monolayers thus shows enhanced surface stability.

Tuning the structure of thermosensitive gold nanoparticle monolayers.

Gold nanoparticles grafted with poly(N-isopropylacrylamide) (PNIPAM) are rendered amphiphilic and thermosensitive. When spread on the surface of water, they form stable Langmuir monolayers that exhibit surface plasmon resonance. Using Langmuir balance and contrast-matched neutron reflectivity, the detailed structural properties of these nanocomposite monolayers are revealed. At low surface coverage, the gold nanoparticles are anchored to the interface by an adsorbed PNIPAM layer that forms a thin and compact pancake structure. Upon isothermal compression (T=20 degrees C), the adsorbed layer thickens with partial desorption of polymer chains to form brush structures. Two distinct polymer conformations thus coexist: an adsorbed conformation that assures stability of the monolayer, and brush structures that dangle in the subphase. An increase in temperature to 30 degrees C results in contractions of both adsorbed and brush layers with a concomitant decrease in interparticle distance, indicating vertical as well as lateral contractions of the graft polymer layer. The reversibility of this thermal response is also shown by the contraction-expansion of the polymer layers in heating-cooling cycles. The structure of the monolayer can thus be tuned by compression and reversibly by temperature. These compression and thermally induced conformational changes are discussed in relation to optical properties.

Low-energy preparation of cellulose nanofibers from sugarcane bagasse by modulating the surface charge density.

In this work, cellulose nanofibers (CNF) were obtained from sugarcane bagasse (SC) without high-energy mechanical treatments, using TEMPO-mediated oxidation. Variable NaClO concentrations were used to impart electrostatic repulsion between surface charged groups thus facilitating fibril separation. CNFs with diameters in the 3-5 nm range were obtained by oxidation of SC pulp with NaClO at 25 and 50 mmol/g. After a 30 min -sonication step, these CNFs were broken down into cellulose nanocrystals (CNC) by mechanical action. Both CNF and CNC preparation by this method are possible in SC due to its particular cell wall morphology and were not achieved in eucalyptus biomass, which is more recalcitrant. This work provided thus a new pathway to modulate the final morphology of cellulose particles by combining a low recalcitrant raw material with different surface charge densities.

Combined approaches to obtain cellulose nanocrystals, nanofibrils and fermentable sugars from elephant grass.

This work is focused in methodologies to obtain cellulose nanocrystals, cellulose nanofibrils, soluble lignin and fermentable sugars from elephant grass, aiming a more integral use of this biomass. To improve hydrolysis, three different pretreatments for biomass delignification and bleaching were compared: 1. Concentrated alkaline peroxide (CP); 2. Diluted alkaline peroxide (DP); and 3. Acid-alkali (AA) pretreatment. Cellulose nanocrystals were obtained from elephant grass leaves by acid hydrolysis, with a 12-16% w/w yield considering the initial biomass weight, and presented high crystallinity index (CI=72-77%) and aspect ratios (30-44), depending on the pretreatment approach. Together with the cellulose nanocrystals, other useful by-products were obtained, such as cellulose nanofibrils (3.8%-9.7% w/w yield), extractives (12.3%), liquors rich in hydrolysed lignin (16.0-21.1%) and sugars (22.1-25.2%). The results presented herewith should contribute to the economic viability and the sustainability of this biomass fractionation process.

Optimization of biomass pretreatments using fractional factorial experimental design.

BACKGROUND: Pretreatments are one of the main bottlenecks for the lignocellulose conversion process and the search for cheaper and effective pretreatment methodologies for each biomass is a complex but fundamental task. Here, we used a 2ν5-1 fractional factorial design (FFD) to optimize five pretreatment variables: milling time, temperature, double treatment, chemical concentration, and pretreatment time in acid-alkali (EA) and acid-organosolv (EO) pretreatments, applied to elephant grass leaves. RESULTS: FFD allowed optimization of the pretreatment conditions using a reduced number of experiments and allowed the identification of secondary interactions between the factors. FFD showed that the temperature can be kept at its lower level and that the first acid step can be eliminated in both pretreatments, without significant losses to enzymatic hydrolysis. EA resulted in the highest release of reducing sugars (maximum of 205 mg/g substrate in comparison to 152 mg/g in EO and 40 mg/g in the untreated sample), using the following conditions in the alkali step: [NaOH] = 4.5% w/v; 85 °C and 100 min after ball milling the sample. The factors statistically significant (P < 0.05) in EA pretreatment were NaOH concentration, which contributes to improved hydrolysis by lignin and silica removal, and the milling time, which has a mechanical effect. For EO samples, the statistically significant factors to improved hydrolysis were ethanol and catalyst concentrations, which are both correlated to higher cellulose amounts in the pretreated substrates. The catalyst is also correlated to lignin removal. The detailed characterization of the main hemicellulosic sugars in the solids after pretreatments revealed their distinct recalcitrance: glucose was typically more recalcitrant than xylose and arabinose, which could be almost completely removed under specific pretreatments. In EA samples, the removal of hemicellulose derivatives was very dependent on the acid step, especially arabinose removal. CONCLUSION: The results presented herewith contribute to the development of more efficient and viable pretreatments to produce cellulosic ethanol from grass biomasses, saving time, costs and energy. They also facilitate the design of enzymatic cocktails and a more appropriate use of the sugars contained in the pretreatment liquors, by establishing the key recalcitrant polymers in the solids resulting from each processing step.

Catalytic Upstream Biorefining through Hydrogen Transfer Reactions: Understanding the Process from the Pulp Perspective.

Catalytic upstream biorefining (CUB) encompasses processes for plant biomass deconstruction through the early-stage conversion of lignin by the action of a hydrogenation catalyst. CUB processes produce lignin as an extensively depolymerised product (i.e., a viscous lignin oil) and render highly delignified pulps. In this report, we examine CUB from the pulp perspective. Notably, Raney Ni plays an indirect role in the processes that occur within the lignocellulose matrix. As there are negligible points of contact between the poplar wood chips and Raney Ni, the catalyst action is limited to the species leached from the matrix into the liquor. Nevertheless, the substantial changes in the liquor composition (through the decomposition of carboxylic acids and H-transfer reductive processes on the lignin fragments) have significant implications for the pulp composition, degree of polymerisation and morphology. Compared with organosolv pulps, CUB pulps show higher xylan retention, higher delignification, and higher polymerisation degree. Moreover, the correlation between these properties and the performance of the enzymatic hydrolyses of CUB and organosolv pulps reveals that the high susceptibility of CUB pulps is mostly caused by their lower residual lignin contents.

Supercritical carbon dioxide extraction of capsaicinoids from malagueta pepper (Capsicum frutescens L.) assisted by ultrasound.

Extracts from malagueta pepper (Capsicum frutescens L.) were obtained using supercritical fluid extraction (SFE) assisted by ultrasound, with carbon dioxide as solvent at 15MPa and 40°C. The SFE global yield increased up to 77% when ultrasound waves were applied, and the best condition of ultrasound-assisted extraction was ultrasound power of 360W applied during 60min. Four capsaicinoids were identified in the extracts and quantified by high performance liquid chromatography. The use of ultrasonic waves did not influence significantly the capsaicinoid profiles and the phenolic content of the extracts. However, ultrasound has enhanced the SFE rate. A model based on the broken and intact cell concept was adequate to represent the extraction kinetics and estimate the mass transfer coefficients, which were increased with ultrasound. Images obtained by field emission scanning electron microscopy showed that the action of ultrasonic waves did not cause cracks on the cell wall surface. On the other hand, ultrasound promoted disturbances in the vegetable matrix, leading to the release of extractable material on the solid surface. The effects of ultrasound were more significant on SFE from larger solid particles.

Evaluating the composition and processing potential of novel sources of Brazilian biomass for sustainable biorenewables production.

BACKGROUND: The search for promising and renewable sources of carbohydrates for the production of biofuels and other biorenewables has been stimulated by an increase in global energy demand in the face of growing concern over greenhouse gas emissions and fuel security. In particular, interest has focused on non-food lignocellulosic biomass as a potential source of abundant and sustainable feedstock for biorefineries. Here we investigate the potential of three Brazilian grasses (Panicum maximum, Pennisetum purpureum and Brachiaria brizantha), as well as bark residues from the harvesting of two commercial Eucalyptus clones (E. grandis and E. grandis x urophylla) for biofuel production, and compare these to sugarcane bagasse. The effects of hot water, acid, alkaline and sulfite pretreatments (at increasing temperatures) on the chemical composition, morphology and saccharification yields of these different biomass types were evaluated. RESULTS: The average yield (per hectare), availability and general composition of all five biomasses were compared. Compositional analyses indicate a high level of hemicellulose and lignin removal in all grass varieties (including sugarcane bagasse) after acid and alkaline pretreatment with increasing temperatures, whilst the biomasses pretreated with hot water or sulfite showed little variation from the control. For all biomasses, higher cellulose enrichment resulted from treatment with sodium hydroxide at 130°C. At 180°C, a decrease in cellulose content was observed, which is associated with high amorphous cellulose removal and 5-hydroxymethyl-furaldehyde production. Morphological analysis showed the effects of different pretreatments on the biomass surface, revealing a high production of microfibrillated cellulose on grass surfaces, after treatment with 1% sodium hydroxide at 130°C for 30 minutes. This may explain the higher hydrolysis yields resulting from these pretreatments, since these cellulosic nanoparticles can be easily accessed and cleaved by cellulases. CONCLUSION: Our results show the potential of three Brazilian grasses with high productivity yields as valuable sources of carbohydrates for ethanol production and other biomaterials. Sodium hydroxide at 130°C was found to be the most effective pretreatment for enhanced saccharification yields. It was also efficient in the production of microfibrillated cellulose on grass surfaces, thereby revealing their potential as a source of natural fillers used for bionanocomposites production.

Effects of pretreatment on morphology, chemical composition and enzymatic digestibility of eucalyptus bark: a potentially valuable source of fermentable sugars for biofuel production - part 1.

BACKGROUND: In recent years, the growing demand for biofuels has encouraged the search for different sources of underutilized lignocellulosic feedstocks that are available in sufficient abundance to be used for sustainable biofuel production. Much attention has been focused on biomass from grass. However, large amounts of timber residues such as eucalyptus bark are available and represent a potential source for conversion to bioethanol. In the present paper, we investigate the effects of a delignification process with increasing sodium hydroxide concentrations, preceded or not by diluted acid, on the bark of two eucalyptus clones: Eucalyptus grandis (EG) and the hybrid, E. grandis x urophylla (HGU). The enzymatic digestibility and total cellulose conversion were measured, along with the effect on the composition of the solid and the liquor fractions. Barks were also assessed using Fourier-transform infrared spectroscopy (FTIR), solid-state nuclear magnetic resonance (NMR), X-Ray diffraction, and scanning electron microscopy (SEM). RESULTS: Compositional analysis revealed an increase in the cellulose content, reaching around 81% and 76% of glucose for HGU and EG, respectively, using a two-step treatment with HCl 1%, followed by 4% NaOH. Lignin removal was 84% (HGU) and 79% (EG), while the hemicellulose removal was 95% and 97% for HGU and EG, respectively. However, when we applied a one-step treatment, with 4% NaOH, higher hydrolysis efficiencies were found after 48 h for both clones, reaching almost 100% for HGU and 80% for EG, in spite of the lower lignin and hemicellulose removal. Total cellulose conversion increased from 5% and 7% to around 65% for HGU and 59% for EG. NMR and FTIR provided important insight into the lignin and hemicellulose removal and SEM studies shed light on the cell-wall unstructuring after pretreatment and lignin migration and precipitation on the fibers surface, which explain the different hydrolysis rates found for the clones. CONCLUSION: Our results show that the single step alkaline pretreatment improves the enzymatic digestibility of Eucalyptus bark. Furthermore, the chemical and physical methods combined in this study provide a better comprehension of the pretreatment effects on cell-wall and the factors that influence enzymatic digestibility of this forest residue.

Surface mechanical properties of thin polymer films investigated by AFM in pulsed force mode.

Atomic force microscopy in the pulsed force mode (PFM) is applied in this work to the study of thin dewetting patterns formed by drying an aqueous solution of poly(N-isopropylacrylamide) (PNIPAM) and sodium dodecyl sulfate (SDS) on mica. This technique allows the automated acquisition of typically 4 x 10(6) force-distance curves on the sample surface together with maps showing nanodomains differentiated by their stiffness and adhesion to the tip. Topography images of dry films revealed a morphology formed by droplets distributed on the substrate. Adhesion and stiffness images with good lateral resolution show droplets containing polymer and surfactant contrasting with the substrate and also nanosized heterogeneities inside these droplets. They also revealed very small dewetted structures which could not be observed in the topography map by noncontact AFM. Adhesion interactions between the AFM tip and the polymer or the dewetted mica substrate were measured in terms of adhesion force and detachment energy, and can be used as new information to understand dewetting patterns containing silica particles, PNIPAM, and SDS. Other surface mechanical parameters such as stiffness, maximum indentation, hardness, compliance, hysteresis, and Young's modulus were obtained by sampling many points and used to characterize the PNIPAM/SDS films formed in the dewetting process.

Liquid templating for nanoparticle organization into complex patterns.

Dewetting of thin films of charged polymer solutions produces complex patterns that can be applied to direct nanoparticle organization on solid substrates. The morphology produced by dewetting can be controlled by the solution properties, temperature, and substrate wetting. In this work, new results on this liquid-template self-assembly system are presented, with special emphasis on producing large arrays of organized nanoparticles. On a hydrophilic substrate with complete wetting, the patterns include polygonal networks and parallel-track arrays that extend over several hundreds of microns. These large structures are formed under well-controlled drying conditions and characterized by scanning electron microscopy, which is better suited for the examination of large as well as small areas than atomic force microscopy. On partial wetting substrates, new patterns are observed, including a complex set of parallel curved bands with variable particle number densities.