Universality of cauliflower-like fronts: from nanoscale thin films to macroscopic plants

Chemical vapor deposition (CVD) is a widely used technique to grow solid materials with accurate control of layer thickness and composition. Under mass-transport-limited conditions, the surface of thin films thus produced grows in an unstable fashion, developing a typical motif that resembles the familiar surface of a cauliflower plant. Through experiments on CVD production of amorphous hydrogenated carbon films leading to cauliflower-like fronts, we provide a quantitative assessment of a continuum description of CVD interface growth. As a result, we identify non-locality, non-conservation and randomness as the main general mechanisms controlling the formation of these ubiquitous shapes.We also show that the surfaces of actual cauliflower plants and combustion fronts obey the same scaling laws, proving the validity of the theory over seven orders of magnitude in length scales. Thus, a theoretical justification is provided, which had remained elusive so far, for the remarkable similarity between the textures of surfaces found for systems that differ widely in physical nature and typical scales.Publicad

Jednostavna i brza metoda određivanja udjela ukupnih karotenoida u liofiliziranoj marelici (Prunus armeniaca L.) pomoću refleksne kolorimetrije i fotoakustične spektroskopije

Photoacoustic spectroscopy (PAS) and reflectance colorimetry are suggested as new tools for the analysis of total carotenoids in lyophilized apricot powders. The data obtained by these two techniques from seven apricot cultivars were compared to those acquired by spectrophotometry and high-performance liquid chromatography (HPLC). Best correlations were found between the total carotenoid (TC) content (obtained by VIS spectrophotometry: 1.2–3.4 mg per 100 g of fresh mass) and colorimetric index a* (a* represents the redness of the investigated sample), as well as either argon-ion laser- or xenon-lamp-based PAS. In all three cases linear correlations were comparable. However, according to the sensitivity and precision data, expressed via limit of detection (LOD) and measurement repeatability, the Xe-lamp-based PAS is a preferred approach, followed by colorimetric index a* and Ar-ion laser PAS. Both PAS methods exhibit practically the same Pearson\u27s correlation coefficient (R=0.987 and R=0.991) values. Nevertheless, residual sum of squares (RSS) and residual standard deviation of the linear regression (sy/x) differ markedly. For Xe-lamp-based PAS these parameters were much lower than in the case of Ar-ion laser PAS. Likewise, analysis imprecision amounted to relative standard deviation (RSD) of 1–3 % for Xe-lamp PAS and 2–6 % for Ar-ion laser PAS. On the other hand, as expected, the calibration sensitivity achieved for the PAS signal induced by an Ar-ion laser at 481 nm was substantially higher than that of a Xe-lamp at 470 nm. Nevertheless, according to much lower sy/x, the corresponding LOD for Xe-lamp PAS was still two times lower than that of Ar-ion-based laser PAS (0.59 vs. 1.10 mg per 100 g). Unlike this, Ar-ion laser PAS showed more favourable instrumental precision and standard error of the weighed mean when compared to the Xe-lamp PAS (0.1–0.6 and 0.1–0.3 % vs. 0.5–8.0 and 0.4–1.7 %, respectively). As far as colorimetric indices are concerned, only a* proved to be analytically useful; excellent R but rather modest RSS and sy/x resulted in LOD value of 0.70 mg per 100 g and acceptable analysis imprecision of up to 3 %. The outcome of this research provides sufficient amount of evidence that analytical methods such as reflectance colorimetry and PAS without the use of any chemicals are feasible for reliable quantification of total carotenoids in freeze-dried apricot homogenates.Fotoakustična spektroskopija (PAS) i refleksna kolorimetrija predložene su kao nove metode određivanja udjela ukupnih karotenoida u liofiliziranom prahu marelice. Rezultati dobiveni ispitivanjem sedam kultivara marelice ovim dvjema tehnikama uspoređeni su s onima dobivenim konvencionalnom vidljivom spektrofotometrijom i tekućinskom kromatografijom visoke djelotvornosti (HPLC). Najbolje su korelacije dobivene između udjela ukupnih karotenoida (vidljivom je spektrofotometrijom utvrđen udjel od 1,2 do 3,4 mg u 100 g svježe mase) i kolorimetrijskog indeksa a* (parametar crvenila ispitanog uzorka), te metodom PAS s argonskim laserom ili ksenonskom lampom kao izvorom zračenja. U sva su tri slučaja dobivene usporedljive linearne korelacije. Međutim, s obzirom na osjetljivost i preciznost rezultata izraženih pomoću granice detekcije i ponovljivosti mjerenja, najboljom se pokazala metoda PAS sa ksenonskom lampom, zatim kolorimetrijski indeks a* i naposljetku metoda PAS s argonskim laserom. Obje su metode PAS imale podjednake Pearsonove koeficijente korelacije (R=0,987 i R=0,991). Ipak, rezidualna suma kvadrata (RSS) i rezidualna standardna devijacija linijske regresije (sy/x) značajno su se razlikovale. Za metodu PAS sa ksenonskom lampom ovi su parametri bili znatno manji nego za metodu PAS s argonskim laserom. Također, nepreciznost je metode izražena pomoću relativne standardne devijacije (RSD) bila od 1 do 3 % za metodu PAS sa ksenonskom lampom i od 2 do 6 % za metodu PAS s argonskim laserom. S druge je pak strane, kao što je i bilo očekivano, kalibracijska osjetljivost postignuta za signal PAS induciran argonskim laserom pri 481 nm bila znatno niža od one dobivene ksenonskom lampom pri 470 nm. Ipak, zahvaljujući bitno nižoj vrijednosti sy/x, granica detekcije metode PAS sa ksenonskom lampom (0,59 mg u 100 g) bila je dvostruko manja od one metode PAS s argonskim laserom (1,10 mg u 100 g). Nasuprot tomu, metoda PAS s argonskim laserom imala je bolju preciznost instrumenta (nepreciznost mjerenja od samo 0,1-0,6 %) i standardnu pogrešku ponderirane sredine (0,1-0,3 %), u usporedbi s metodom PAS sa ksenonskom lampom (0,5-8,0 % odnosno 0,4-1,7 %). Među kolorimetrijskim indeksima samo je indeks a* bio koristan za analizu; odlične vrijednosti R, ali skromne vrijednosti RSS i sy/x rezultirale su granicom detekcije od 0,70 mg u 100 g i prihvatljivom nepreciznošću mjerenja od najviše 3 %. Rezultati ovog istraživanja pokazuju da se analitičke tehnike, poput refleksne kolorimetrije i fotoakustične spektroskopije mogu primijeniti za pouzdano određivanje udjela ukupnih karotenoida u liofiliziranim homogenatima marelice, i to bez uporabe reagenasa

Jednostavna i brza metoda određivanja udjela ukupnih karotenoida u liofiliziranoj marelici (Prunus armeniaca L.) pomoću refleksne kolorimetrije i fotoakustične spektroskopije

Photoacoustic spectroscopy (PAS) and reflectance colorimetry are suggested as new tools for the analysis of total carotenoids in lyophilized apricot powders. The data obtained by these two techniques from seven apricot cultivars were compared to those acquired by spectrophotometry and high-performance liquid chromatography (HPLC). Best correlations were found between the total carotenoid (TC) content (obtained by VIS spectrophotometry: 1.2–3.4 mg per 100 g of fresh mass) and colorimetric index a* (a* represents the redness of the investigated sample), as well as either argon-ion laser- or xenon-lamp-based PAS. In all three cases linear correlations were comparable. However, according to the sensitivity and precision data, expressed via limit of detection (LOD) and measurement repeatability, the Xe-lamp-based PAS is a preferred approach, followed by colorimetric index a* and Ar-ion laser PAS. Both PAS methods exhibit practically the same Pearson\u27s correlation coefficient (R=0.987 and R=0.991) values. Nevertheless, residual sum of squares (RSS) and residual standard deviation of the linear regression (sy/x) differ markedly. For Xe-lamp-based PAS these parameters were much lower than in the case of Ar-ion laser PAS. Likewise, analysis imprecision amounted to relative standard deviation (RSD) of 1–3 % for Xe-lamp PAS and 2–6 % for Ar-ion laser PAS. On the other hand, as expected, the calibration sensitivity achieved for the PAS signal induced by an Ar-ion laser at 481 nm was substantially higher than that of a Xe-lamp at 470 nm. Nevertheless, according to much lower sy/x, the corresponding LOD for Xe-lamp PAS was still two times lower than that of Ar-ion-based laser PAS (0.59 vs. 1.10 mg per 100 g). Unlike this, Ar-ion laser PAS showed more favourable instrumental precision and standard error of the weighed mean when compared to the Xe-lamp PAS (0.1–0.6 and 0.1–0.3 % vs. 0.5–8.0 and 0.4–1.7 %, respectively). As far as colorimetric indices are concerned, only a* proved to be analytically useful; excellent R but rather modest RSS and sy/x resulted in LOD value of 0.70 mg per 100 g and acceptable analysis imprecision of up to 3 %. The outcome of this research provides sufficient amount of evidence that analytical methods such as reflectance colorimetry and PAS without the use of any chemicals are feasible for reliable quantification of total carotenoids in freeze-dried apricot homogenates.Fotoakustična spektroskopija (PAS) i refleksna kolorimetrija predložene su kao nove metode određivanja udjela ukupnih karotenoida u liofiliziranom prahu marelice. Rezultati dobiveni ispitivanjem sedam kultivara marelice ovim dvjema tehnikama uspoređeni su s onima dobivenim konvencionalnom vidljivom spektrofotometrijom i tekućinskom kromatografijom visoke djelotvornosti (HPLC). Najbolje su korelacije dobivene između udjela ukupnih karotenoida (vidljivom je spektrofotometrijom utvrđen udjel od 1,2 do 3,4 mg u 100 g svježe mase) i kolorimetrijskog indeksa a* (parametar crvenila ispitanog uzorka), te metodom PAS s argonskim laserom ili ksenonskom lampom kao izvorom zračenja. U sva su tri slučaja dobivene usporedljive linearne korelacije. Međutim, s obzirom na osjetljivost i preciznost rezultata izraženih pomoću granice detekcije i ponovljivosti mjerenja, najboljom se pokazala metoda PAS sa ksenonskom lampom, zatim kolorimetrijski indeks a* i naposljetku metoda PAS s argonskim laserom. Obje su metode PAS imale podjednake Pearsonove koeficijente korelacije (R=0,987 i R=0,991). Ipak, rezidualna suma kvadrata (RSS) i rezidualna standardna devijacija linijske regresije (sy/x) značajno su se razlikovale. Za metodu PAS sa ksenonskom lampom ovi su parametri bili znatno manji nego za metodu PAS s argonskim laserom. Također, nepreciznost je metode izražena pomoću relativne standardne devijacije (RSD) bila od 1 do 3 % za metodu PAS sa ksenonskom lampom i od 2 do 6 % za metodu PAS s argonskim laserom. S druge je pak strane, kao što je i bilo očekivano, kalibracijska osjetljivost postignuta za signal PAS induciran argonskim laserom pri 481 nm bila znatno niža od one dobivene ksenonskom lampom pri 470 nm. Ipak, zahvaljujući bitno nižoj vrijednosti sy/x, granica detekcije metode PAS sa ksenonskom lampom (0,59 mg u 100 g) bila je dvostruko manja od one metode PAS s argonskim laserom (1,10 mg u 100 g). Nasuprot tomu, metoda PAS s argonskim laserom imala je bolju preciznost instrumenta (nepreciznost mjerenja od samo 0,1-0,6 %) i standardnu pogrešku ponderirane sredine (0,1-0,3 %), u usporedbi s metodom PAS sa ksenonskom lampom (0,5-8,0 % odnosno 0,4-1,7 %). Među kolorimetrijskim indeksima samo je indeks a* bio koristan za analizu; odlične vrijednosti R, ali skromne vrijednosti RSS i sy/x rezultirale su granicom detekcije od 0,70 mg u 100 g i prihvatljivom nepreciznošću mjerenja od najviše 3 %. Rezultati ovog istraživanja pokazuju da se analitičke tehnike, poput refleksne kolorimetrije i fotoakustične spektroskopije mogu primijeniti za pouzdano određivanje udjela ukupnih karotenoida u liofiliziranim homogenatima marelice, i to bez uporabe reagenasa

Porphyrin–nanodiamond hybrid materials—active, stable and reusable cyclohexene oxidation catalysts

funded by FCT-Foundation for Science and Technology, I.P., under projects UIDB/00313/2020; PTDC/QUI-OUT/27996/2017 (DUALPI); POCI-01-0145-FEDER-027996; POCI-01-0145-FEDER-016387; UIDB/50006/2020 (Associate Laboratory for Green Chemistry-LAQV); MATIS (CENTRO-010145-FEDER-00014); Base Funding-UIDB/50020/2020 of the Associate Laboratory LSRE-LCM-funded by national funds through FCT/MCTES (PIDDAC); and 5625-DRI-DAAD-2020/21. SACC also acknowledges FCT Investigador FCT program (IF/01381/2013/CP1160/CT0007) and Scientific Employment Stimulus -Institutional Call (CEECINST/00102/2018). The authors also thank Fundacao de Amparo a Pesquisa do Estado de Sao Paulo (FAPESP) for CEPOF 2013/07276-1, and INCT "Basic Optics and Applied to Life Sciences" (FAPESP 2014/50857-8, CNPq 465360/2014-9). A.R.L. Caires acknowledges CAPES-PrInt funding program (grant number 88887.353061/2019-00 and 88881.311921/2018-01). J.G.B. thanks the Dutch Research Council (NWO) for funding as a part of the Open Technology Programme (project number 16361). L.D. Dias thanks FAPESP for the Post-doc grant 2019/13569-8. F.M.S.R. thanks FCT for the PhD grant (PD/BD/114340/2016).The quest for active, yet “green” non-toxic catalysts is a continuous challenge. In this work, covalently linked hybrid porphyrin–nanodiamonds were prepared via ipso nitro substitution reaction and characterized by X-ray photoelectron spectroscopy (XPS), fluorescence spectroscopy, infrared spectroscopy (IR) and thermogravimetry-differential scanning calorimetry (TG-DSC). The amine-functionalized nanodiamonds (ND@NH2 ) and 2-nitro-5,10,15,20-tetra(4-trifluoromethylphenyl)porphyrin covalently linked to nanodiamonds (ND@βNH-TPPpCF3 ) were tested using Allium cepa as a plant model, and showed neither phytotoxicity nor cytotoxicity. The hybrid nanodiamond–copper(II)–porphyrin material ND@βNH-TPPpCF3-Cu(II) was also evaluated as a reusable catalyst in cyclohexene allylic oxidation, and displayed a remarkable turnover number (TON) value of ≈265,000, using O2 as green oxidant, in the total absence of sacrificial additives, which is the highest activity ever reported for said allylic oxidation. Additionally, ND@βNH-TPPpCF3-Cu(II) could be easily separated from the reaction mixture by centrifugation, and reused in three consecutive catalytic cycles without major loss of activity.publishersversionpublishe

Correlation of trans-Lycopene Measurements by the HPLC Method with the Optothermal and Photoacoustic Signals and the Color Readings of Fresh Tomato Homogenates

The trans-lycopene content of fresh tomato homogenates was assessed by means of the laser photoacoustic spectroscopy, the laser optothermal window, micro-Raman spectroscopy, and colorimetry; none of these methods require the extraction from the product matrix prior to the analysis. The wet chemistry method (high-performance liquid chromatography) was used as the absolute quantitative method. Analytical figures of merit for all methods were compared statistically; best linear correlation was achieved for the chromaticity index a* and chroma C*

Atomic force microscopy studies on the surface morphology of {111} tabular AgBr crystals

Both ex situ and in situ atomic force microscopy have been applied to study the (1 1 1) and (1 0 0) surfaces of tabular silver bromide crystals grown from dimethyl sulphoxide-water solutions. This resulted in observations of monosteps, macrosteps, etch pits, pinning of steps and nucleated crystals showing twin planes. These examinations indicate that the growth and dissolution of both the (1 0 0) and the polar (1 1 1) faces occur via steps in many configurations. The registered 40-nm distance between the parallel twin planes of the nucleated crystals agrees with transmission electron microscopy measurements done on tabular crystals grown by the industrial double-jet precipitation method. (C) 2000 Elsevier Science B.V. All rights reserved.status: publishe

Diamond deposition on modified silicon substrates: Making diamond atomic force microscopy tips for nanofriction experiments

Fine-crystalline diamond particles are grown on standard Si atomic force microscopy tips, using hot filament-assisted chemical vapor deposition. To optimize the conditions for diamond deposition, first a series of experiments is carried out using silicon substrates covered by point-topped pyramids as obtained by wet chemical etching. The apexes and the edges of the silicon pyramids provide favorable sites for diamond nucleation and growth. The investigation of the deposited polycrystallites is done by means of optical microscopy, scanning electron microscopy and micro-Raman spectroscopy. The resulting diamond-terminated tips are tested in ultra high vacuum using contact-mode atomic force microscope on a stepped surface of sapphire showing high stability, sharpness, and hardness. (C) 2003 American Institute of Physics.status: publishe

Morphology and growth mechanism of multiply twinned AgBr and AgCl needle crystals

In this study the morphology and growth mechanism of AgX (X = Cl, Br) needle crystals will be revealed. The silver halide needles are grown by two different techniques. AgBr needles are grown with an extractive crystallization in a dimethylsulfoxide-water mixture and AgCl needles are grown from the vapor phase. All needles contain nonparallel twin planes. The morphology of the AgBr needles grown from dimethylsulfoxide is the same as the needles grown in the industrial precipitation process in water. The side faces of these solution grown needles are built up of relatively slowly growing {1 1 1} faces. Both needle tops are composed of three relatively fast growing {1 0 0} faces making a ridge structure. The vapor-grown needles have two different morphologics. For both types the side faces consist of four {1 1 1} and two {1 0 0} faces. All {1 1 1} faces are linked via twin planes to a fast growing {1 0 0} face. The preferential unidirectional growth of all needles is caused by cross-twinning. The preferential growth occurs along the intersection line of the twin planes. Between the twin planes a rough growing face appears on the needle top. This face is capable of increasing the growth rate of the other top faces owing to the substep mechanism. (C) 1999 Elsevier Science B.V. All rights reserved.status: publishe

Surface Wettability of Macroporous Anodized Aluminum Oxide

The correlation between the structural characteristics and the wetting of anodized aluminum oxide (AAO) surfaces with large pore sizes (>100 nm) is discussed. The roughness-induced wettability is systematically examined for oxide films grown by a two-step, high-field anodization in phosphoric acid of three different concentrations using a commercial aluminum alloy. This is done for the as-synthesized AAO layers, after various degrees of pore widening by a wet chemical etching in phosphoric acid solution, and upon surface modification by either Lauric acid or a silane. The as-grown AAO films feature structurally disordered pore architectures with average pore openings in the range 140–190 nm but with similar interpore distances of about 405 nm. The formation of such AAO structures induces a transition from slightly hydrophilic to moderately hydrophobic surfaces up to film thicknesses of about 6 μm. Increased hydrophobicity is obtained by pore opening and a maximum value of the water contact angle (WCA) of about 128° is measured for AAO arrays with a surface porosity close to 60%. Higher surface porosity by prolonged wet chemical etching leads to a rapid decrease in the WCA as a result of the limited pore wall thickness and partial collapse of the dead-end pore structures. Modification of the AAO surfaces by Lauric acid results in 5–30° higher WCA’s, whereas near-superhydrophobicity (WCA ∼146°) is realized through silane coating. The “rose petal effect” of strongly hydrophobic wetting with high adhesive force on the produced AAO surfaces is explained by a partial penetration of water through capillary action into the dead-end pore cavities which leads to a wetting state in-between the Wenzel and Cassie states. Moreover, practical guidelines for the synthesis of rough, highly porous AAO structures with controlled wettability are provided and the possibility of forming superhydrophobic surfaces is evaluated

Metallic Seed Nanolayers for Enhanced Nucleation of Nanocrystalline Diamond Thin Films

The enhancement of the nucleation and subsequent growth of nanocrystalline diamond (NCD) films with a submicrometer thickness control on silicon substrates is demonstrated by using a sputter deposition of six different metallic (Cr, Mo, Nb, Ti, V and W) seed nanolayers. The effectiveness of altered surface morphology and surface chemistry is discussed. We show that the number density of nanodiamond particles embedded on the nanorough metallic surfaces after an ultrasonic seeding step together with the dynamic surface chemistry during hot-filament chemical vapor deposition of diamond determine the nucleation kinetics, microstructure and surface topography of the NCD films. Overall, the smoothest NCD layer (root-mean-square roughness 10 nm) was obtained with the highest seed density of diamond nanoparticles anchored to the metallic (W) surface. In particular, the rapid carbide-forming metals Mo, Nb and W showed the highest number density of diamond crystallites formed during the NCD nucleation stage, which resulted in dense, uniform and very smooth NCD films. Much rougher NCD films (17–37 nm) were obtained on the Cr, Ti, and V nanolayers that did not form carbides rapidly. Importantly, the carbon phase purity of the grown NCD films remains unaffected by the presence of different metallic seed nanolayers. Furthermore, we have assessed that the metallic nanolayer surface morphology does not play a relevant role in the enhancement of the seeding step