Physical Vapor Deposited Thin Films of Lignins Extracted from Sugar Cane Bagasse: Morphology, Electrical Properties, and Sensing Applications

The concern related to the environmental degradation and to the exhaustion of natural resources has induced the research on biodegradable materials obtained from renewable sources, which involves fundamental properties and general application. In this context, we have fabricated thin films of lignins, which were extracted from sugar cane bagasse via modified organosolv process using ethanol as organic solvent. The films were made using the vacuum thermal evaporation technique (PVD, physical vapor deposition) grown up to 120 nm. The main objective was to explore basic properties such as electrical and surface morphology and the sensing performance of these lignins as transducers. The PVD film growth was monitored via ultraviolet-visible (UV-vis) absorption spectroscopy and quartz crystal microbalance, revealing a linear relationship between absorbance and film thickness. The 120 nm lignin PVD film morphology presented small aggregates spread all over the film surface on the nanometer scale (atomic force microscopy, AFM) and homogeneous on the micrometer scale (optical microscopy). The PVD films were deposited onto Au interdigitated electrode (IDE) for both electrical characterization and sensing experiments. In the case of electrical characterization, current versus voltage (I vs V) dc measurements were carried out for the Au IDE coated with 120 nm lignin PVD film, leading to a conductivity of 3.6 x 10(-10) S/m. Using impedance spectroscopy, also for the Au IDE coated with the 120 nm lignin PVD film, dielectric constant of 8.0, tan delta of 3.9 x 10(-3)) and conductivity of 1.75 x 10(-9) S/m were calculated at 1 kHz. As a proof-of-principle, the application of these lignins as transducers in sensing devices was monitored by both impedance spectroscopy (capacitance vs frequency) and I versus time dc measurements toward aniline vapor (saturated atmosphere). The electrical responses showed that the sensing units are sensible to aniline vapor with the process being reversible. AFM images conducted directly onto the sensing units (Au IDE coated with 120 nm lignin PVD film) before and after the sensing experiments showed a decrease in the PVD film roughness from 5.8 to 3.2 nm after exposing to aniline.

Isolation of Brazilian marine fungi capable of growing on DDD pesticide

The fungi Aspergillus sydowii Ce15, Aspergillus sydowii Ce19, Aspergillus sydowii Gc12, Bionectria sp. Ce5, Penicillium miczynskii Gc5, Penicillium raistrickii Ce16 and Trichoderma sp. Gc1, isolated from marine sponges Geodia corticostylifera and Chelonaplysylla erecta, were evaluated for their ability to grow in the presence of DDD pesticide. Increasing concentrations of DDD pesticide, i.e., 5.0 mg (1.56 x 10(-12) mmol), 10.0 mg (3.12 x 10(-2) mmol) and 15.0 mg (4.68 x 10(-2) mmol) in solid and liquid culture media were tested. The fungi Trichoderma sp. Gc1 and Penicillium miczynskii Gc5 were able to grow in the presence of up to 15.0 mg of DDD, suggesting their potential for biodegradation. A 100% degradation of DDD was attained in liquid culture medium when Trichoderma sp. Gc1 was previously cultivated for 5 days and supplemented with 5.0 mg of DDD in the presence of hydrogen peroxide. However, the quantitative analysis showed that DDD was accumulated on mycelium and biodegradation level reached a maximum value of 58% after 14 days.

Amino acids profile of sugar cane spirit (cachaca), rum, and whisky

An analytical procedure for the separation and quantification of 20 amino acids in cachacas has been developed involving C18 solid phase cleanup, derivatization with o-phthalaldehyde/2-mercaptoethanol, and reverse phase liquid chromatography with fluorescence detection. The detection limit was between 0.0050 (Cys) and 0.25 (Ser) mg L-1, whereas the recovery index varies from 69.5 (Lys) to 100 (Tyr)%. Relative standard deviations vary from 1.39 (Trp) to 13.4 (Glu)% and from 3.08 (Glu) to 13.5 (His) for the repeatability and intermediate precision, respectively. From the quantitative profile of amino acids in 41 cachacas, 5 turns, and 12 whisky samples, the following order of amino acids in significant quantities is observed: Gly = Ser < Cys < Ile < His < Pro = Asp < Asn < Tyr for cachaca; Phe < Glu = Gln = Val = Ala < His = Gly Thr = Arg = Tyr < Asn Ser = Lys = Pro < Cys = Asp for rum; and Ala = Asn < Trp < Gln = His = Met = Ile = Cys < Thr < Asp Leu < Phe = Lys < Ser = Gly = Tyr = Val < Glu = Pro < Arg for whisky samples. (C) 2007 Elsevier Ltd. All rights reserved.

Formation of Dextran Deposits in Brazilian Sugar Cane Spirits

The formation of dextran deposits in sugared Brazilian cachaca was studied as a function of the time considering the effects of temperature, molecular weight (M(w)), visible light, pH, and the presence of Ca, Mg, Cu, and Fe ions in the concentrations at which they are usually present in this beverage. At 25 degrees C and pH 4.4, the experimental half-lives (t(1/2)) for precipitation are 73 and 124 days for dextrans with M(w) 5.9 x 10(6) and 2.1 x 10(6) Da, respectively. For dextrans with M(w) 5.0 x 10(5) and 4.0 x 10(4) Da, the experimental t(1/2) values are >180 days. For a dextran with M(w) 2.1 x 10(6) Da a change in pH from 4.4 to 5.5 at 25 degrees C resulted in a t(1/2) decrease from 124 to 25 days. At pH 4.4 the visible light and the presence of metal ions in average concentrations usually found in cachacas do not exhibit noticeable influence on the rate of dextran precipitation.

Molecular mass distribution of dextran in Brazilian sugar and insoluble deposits of cachaca

The dextran molecular mass distribution profile in 77 sugar samples from Brazil and twelve insoluble deposits (alcoholic flocks) samples from sugared cachacas (Brazilian sugar cane spirit) is described in terms of number-average molecular mass M,,, weight-average molecular mass M(w), Z-average molecular mass M,, and polydispersity. The analyses were performed by size-exclusion chromatography, using a refractive index detector. In most of the sugar samples, it was possible to identify two major groups of dextrans with Mw averages of 5 x 10(6) and 5 x 10(4) Da. Based on the evaluated parameters, the dextran distribution profile is about the same in samples analyzed over five seasons, and, therefore, it is likely that the Brazilian product pattern will not change very much over the years. In insoluble deposits from sugared cachacas, dextrans with Mw values in the order of the 10(5) Da were the most frequent ones, being present in 58% of the samples. (c) 2008 Elsevier Ltd. All rights reserved.