Polysaccharide-based prodrugs formed via pH-responsive covalent interactions can be used to prepare nanoparticles for drug delivery to tumor cells. This study reports the synthesis of cashew gum-doxorubicin prodrugs via Schiff base (CG-S-DOX) and amide bonds (CG-A-DOX), both of which exhibit pH-responsive behavior. Synthesis was confirmed using spectroscopic techniques. Drug-binding content and efficiency were higher for CG-S-DOX than for CG-A-DOX. The capacity of the nanoparticles to self-organize in aqueous media was confirmed using fluorescence spectroscopy, dynamic light scattering, and atomic force microscopy. Both prodrugs possessed sizes < 200 nm and showed responsive doxorubicin-release profiles in the acidic tumor cell microenvironment. Compared with free DOX, the CG-S-DOX and CG-A-DOX prodrug had significantly reduced cytotoxicity against non-tumor cells (L929). CG-S-DOX, but not CG-A-DOX, showed antitumor activity against HCT-116 (human colorectal cancer) and MCF-7 (human breast cancer) cells. An uptake assay confirmed that the nanoparticles were easily taken up by HCT-116 cells. These results together with the great reduction in cytotoxicity against non-tumor cells, confirm the potential of CG-S-DOX prodrug nanoparticles as a reliable and efficient system for the effective delivery of doxorubicin to tumor cells. Polysaccharidebased Polysaccharide based pHresponsive pH gumdoxorubicin gum CGSDOX CG S DOX (CG-S-DOX CGADOX, CGADOX A , (CG-A-DOX) behavior techniques Drugbinding Drug binding CGADOX. DOX. selforganize self organize spectroscopy scattering microscopy 20 doxorubicinrelease release microenvironment nontumor non L929. L929 L . (L929) CGSDOX, HCT116 HCT 116 HCT-11 human cancer MCF7 MCF 7 MCF- (CG-A-DOX 2 L92 (L929 HCT11 11 HCT-1 L9 (L92 HCT1 1 HCT- (L9 (L

Thermo-responsive copolymers grafted with N-isopropylacrylamide (NIPAm) are excellent candidates for drug release. Dextran sulfate (DS) acts as a specific ligand in inflamed regions, turning it highly useful as a target for drug delivery. DS was associated with NIPAm to produce amphiphilic graft copolymers prepared via free radicals. The molar ratio of feed reagents NIPAm/DS varied from 1 (DS-g-PNIPAm) to 4 (DS-g-4PNIPAm). The synthesis was confirmed by spectroscopic techniques (Fourier transform infrared (FTIR) and nuclear magnetic resonance (NMR)). All copolymers showed self-organization capacity in an aqueous medium in temperatures higher than 34 °C, and sizes less than 300 nm. DS-g-3PNIPAm exhibited stability in water and in phosphate buffer at pH 7.4. Scanning electron microscopy confirmed their spherical shape. This copolymer showed specificity to leukemic cells, and normal cells’ proliferation. Methotrexate (MTX) is a very low water-soluble drug used for rheumatoid arthritis and cancer. Unfortunately, MTX have severe collateral effects. MTX-loaded nanoparticles can overcome such issues as well as enhance bioactivity and stability. The MTX was encapsulated and delivered from the DS-g-3PNIPAm with potential target delivery due to the presence of DS. Comparison with MTX encapsulated in other nanoparticles reveals that the DS-g-PNIPam presents the best performance among the thermo-responsive and the second among the target MTX nanocarriers. Thermoresponsive Thermo responsive Nisopropylacrylamide N isopropylacrylamide (NIPAm release (DS regions radicals NIPAmDS DSgPNIPAm g PNIPAm (DS-g-PNIPAm DSg4PNIPAm. DSg4PNIPAm 4PNIPAm . (DS-g-4PNIPAm) Fourier FTIR (FTIR NMR. NMR (NMR)) selforganization self organization 3 C °C 30 nm DSg3PNIPAm 3PNIPAm 74 7 7.4 shape cells proliferation (MTX watersoluble soluble cancer Unfortunately effects MTXloaded loaded DSgPNIPam PNIPam thermoresponsive thermo nanocarriers DSg (DS-g-4PNIPAm (NMR) 7. (NMR

Eggshell (ES) is an abundant waste material which is mainly composed of calcium carbonate. A superabsorbent hydrogel composite based on poly(acrylamide-co-potassium acrylate) as matrix containing 17 wt.% of chicken ES powder as a filler was synthesized and compared with the gel without filler. The characterization was carried out by Fourier transform infrared (FTIR), scanning electron microscopy with energy dispersive X-ray spectroscopy (SEM/EDX), thermogravimetric analysis (TGA), X-ray diffraction (XRD), rheological analysis and kinetics studies. The dispersion of ES in the polymeric matrix was homogeneous. The interaction between the acrylate and calcium cation was detected by FTIR analysis. The composite improved the gel strength and the absorption of water and saline solution increased by 100 and 41%, respectively. The high values for the swelling, the homogeneous structure and the good mechanical properties obtained with the incorporation of a relatively high content of a low-cost waste material indicate that this composite is suitable for application in the agriculture. In addition, this approach provides a more ecologically sound and useful destination for eggshell residue.

Carbon quantum dots (C-dots) with average size of 9 nm were synthesized from an aqueous solution of raw cashew gum (RCG) using a novel and fast microwave-assisted technique which involves two steps. In the first step (partial depolymerization in solution) some monomer units are formed through the autohydrolysis of CG and a small amount of 5-hydroxymethyl furfural can be obtained. The second step involves polycondensation/polymerization to give rise to a polyfuranic structure followed by aromatization/carbonization and nuclear burst. At the end of the process a composite of partially depolymerized CG and C-dot was formed. A mechanism involved in microwave-assisted two-steps synthesis was suggested. Although no passivation reagent was used, an intensely blue photoluminescent material in UV light was obtained. C-dot was characterized by spectroscopy in the medium infrared, thermal analysis, gel permeation chromatography, transmission electron microscopy, zeta potential, and photoluminescence.

A novel superabsorbent hydrogel (SH) composite based on a poly(acrylamide-co-acrylate) matrix filled with nontronite (NONT), a Fe(III)-rich member of the smectite group of clay minerals, is described in this manuscript. A variety of techniques, including FTIR, XRD, TGA, and SEM/EDX, were utilized to characterize this original composite. Experimental data confirmed the SH composite formation and suggested NONT was completely dispersed in the polymeric matrix. Additionally, NONT improved the water uptake capacity of the final material, which exhibited fast absorption, low sensitivity to the presence of salt, high water retention and a pH sensitive properties. These preliminary data showed that the original SH composite prepared here possesses highly attractive properties for applications in areas such as the agriculture field, particularly as a soil conditioner.

Hidrogéis superabsorventes à base de acrilamida e acrilato compósito com bentonita ou dolomita foram sintetizados e caracterizados por espectroscopia no infravermelho com transformada de Fourier (FTIR), microscopia eletrônica de varredura (SEM) e difratometria de raios X (XRD). A proporção ideal de acrilamida para acrilato foi determinada em 1:1. A presença de 10% (m/m) de bentonita no hidrogel poli(acrilamida) posteriormente hidrolisado com NaOH aumentou o grau de intumescimento de 1173 para 1270 g água g-1 gel. Sendo o acrilato obtido por hidrólise, a lavagem do hidrogel para remoção do excesso de hidróxido mostrou ser um contrassenso considerando o objetivo de economizar água. A constante de velocidade de intumescimento inicial e o tempo para atingir o equilíbrio assim como a capacidade de absorção de água (1058 g água g-1 gel) indicam o hidrogel composto do compósito poli(acrilamida-co-acrilato de potássio) contendo 10% de dolomita como material potencial para ser utilizado como condicionador de solo. O benefício esperado em termos do uso eficiente de água deverá contribuir para a sustentabilidade da água.

Superabsorbent hydrogels based on an acrylamide/acrylate composite with bentonite or dolomite were synthesized and characterized by Fourier transform infrared (FTIR) spectroscopy, scanning electron microscopy (SEM) and X-ray diffractometry (XRD). The ideal proportion of acrylamide to acrylate was determined as 1:1. The presence of 10% (m/m) bentonite in the polyacrylamide hydrogel further hydrolyzed with NaOH increased the swelling degree from 1173 to 1270 g water g-1 gel. Being the acrylate obtained by hydrolysis, the hydrogel washing for removal of the alkali excess showed to be a drawback considering the goal of saving water. The initial swelling rate constant and the time required to reach the equilibrium as well as the water absorption capacity (1058 g water g-1 gel) indicate the hydrogel comprised of the poly(acrylamide-co-potassium acrylate) composite containing 10% dolomite as a potential material for use as a soil conditioner. The expected benefit in terms of the efficient use of water should contribute to the water sustainability.

Superabsorbent hydrogels based on poly (acrylamide-co-acrylate) and different kaolins, were prepared by free-radical aqueous copolymerization. FTIR and WAXS techniques were employed for characterization of a series of hydrogels, obtained by varying the percentage of clay, crosslinking and constitution of kaolin. The water absorbency at equilibrium (Weq) decreased with increasing clay content and the amount of crosslinking agent. Superabsorbent hydrogel (Weq > 1084 g H2O/g gel) was obtained as 10 wt% of white kaolin and 0.05 mol% of crosslinking agent were used. The hydrogel proved sensitive to pH variation and the presence of salts.

Hydrogels have been prepared by free-radical solution copolymerization of acrylamide and sodium acrylate (NaAc), with molar ratio ranging from 25/75 to 80/20, respectively, using methylene bisacrylamide as the crosslinking agent. A FTIR spectroscopy procedure to determine the acrylate/acrylamide ratio in these hydrogels was proposed based on absorbance at 1410 cm-1 (nCOO-) and 2940 cm-1 (nCH and nCH2). A straight line with a good linear correlation coefficient (0.998) was obtained by plotting the acrylate content (Ac%) versus relative absorbance (Arel = A1410/A2940). Results were confirmed by the amount of sodium cation released in acid medium determined by atomic absorption spectrometry.

A goma do cajueiro (GC) foi sulfatada em piridina:formamida usando ácido clorossulfônico como reagente. A confirmação da sulfatação foi obtida por espectroscopia no infravermelho com transformada de Fourier (FTIR) pelo aparecimento da frequência de vibração em 1259 cm-1 devido ao estiramento assimétrico S=O. Os graus de sulfatação foram de 0,02, 0,24 e 0,88, determinados pela percentagem de enxofre. Os dados de ressonância magnética nuclear (RMN) 1D e 2D mostram que a sulfatação ocorreu nos carbonos primários do polissacarídeo. Um aumento de no mínimo 4% na viscosidade da solução foi observado após a sulfatação. Análise termogravimétrica (TGA) indica que o derivado é estável até cerca de 200ºC. A comparação entre os derivados sulfatados e carboximetilados foi feita no intuito de verificar a possibilidade de formação de complexos polieletrolíticos, já realizada com os carboximetilados.

Cashew gum (CG) was sulfated in pyridine:formamide using chlorosulfonic acid as the reagent. Confirmation of sulfation was obtained by Fourier transform infrared (FTIR) spectroscopy through the presence of an asymmetrical S=O stretching vibration at 1259 cm-1. The degrees of substitution were 0.02, 0.24 and 0.88 determined from the sulfur percentage. 1D and 2D nuclear magnetic resonance (NMR) data showed that the sulfation occurred at primary carbons. An increase of at least 4% of the solution viscosity was observed due to sulfation. The thermal gravimetric curves (TGA) indicate that the derivatives are stable up to ca. 200ºC. The sulfated CG is compared to carboxymethylated CG in order to verify the possibility of the use of the former in the preparation of polyelectrolyte complexes; the latter is already being used for this application.

Ophthalmic viscosurgical devices (OVD) are materials injected in intraocular space during cataract removal to reduce trauma in the patient's eye. Three Brazilian commercially available OVDs (Medilon®, Metilcelulose® and Ofthyal®) were evaluated as well as formulations based on Dimorphandra gardneriana galactomannan. Viscosity and viscoelastic parameters, such as viscosity at zero shear, pseudoplasticity index, elastic and viscous moduli, relaxation time, were determined and compared. Characteristics of an effective OVD were proposed. None of the Brazilian devices studied fulfill the rheological requirements. Only the galactomannan at 3% concentration showed potential to be used as effective OVD.

A brief comment about general characteristics of polysaccharide was presented. Brazilian trade of polysaccharides was obtained from the "Ministério de Desenvolvimento, Indústria e Comércio Exterior" - Brazil. A list of these products was prepared and their price and amount analyzed in the period of 1998-2007. Some chemical properties and application of polysaccharides from our biodiversity was described. In this review they were classified by origin, in vegetal (exudate, seed, fruit, seaweed), animal and bacteria source. There is a trade deficit that can be reverted if part of the accumulated scientific knowledge was used to promote the national economic development in the field.

A goma do cajueiro, um polissacarídeo exsudado da árvore Anacardium ocidentale, foi oxidada com o reagente TEMPO e o produto (CGOX) foi caracterizado por técnicas espectroscópicas (FT-IR e RMN), análises cromatográficas (HPLC e GPC), viscosidade e análise térmica (TGA). O rendimento do produto da reação foi de 96%. O teor de ácido urônico da goma nativa (7,2%) aumentou para 36% após a reação. O grau de oxidação, tendo como base as unidades de galactose e glucose livres, foi de 68%. Os dados de RMN mostraram que a oxidação ocorreu preferencialmente nos carbonos primários das unidades de galactose. A grande diferença entre o valor esperado de etaCGOX/etaCG e o valor observado indica que a degradação, durante a oxidação, ocorreu em grande extensão. A presença de impurezas orgânicas e inorgânicas no novo polieletrólito foi detectada por TGA. A goma do cajueiro após a modificação com TEMPO apresentou mais baixa estabilidade térmica que a goma nativa, indicada pelos valores de temperatura inicial de decomposição e IPDT.

Cashew gum (CG), an exudate polysaccharide from Anacardium ocidentale trees, was oxidized with TEMPO reagent and the 7product (CGOX) characterized by spectroscopic techniques (FT-IR and NMR), chromatographic analyses (HPLC and GPC), viscosity measurements and thermal analysis (TGA). The yield of the reaction product was 96%. The uronic acid content in starting gum (7.2 m%) was increased to 36 m%. The degree of oxidation based on free galactose and glucose units was 68%. NMR data show that oxidation occurred preferentially at primary carbons of galactose units. High degradation degree after oxidation was estimated by the difference on the expected and observed etaCGOX/etaCG ratio. The presence of organic and inorganic impurities in the new polyelectrolyte was detected by TGA. A less thermally stable cashew gum is formed after the oxidation with TEMPO based on initial decomposition temperature and IPDT.

LCC (Líquido da Castanha de Caju), ou CNSL (Cashew Nut Shell Liquid), é uma mistura de meta-alquilfenóis, que variam no grau de insaturação do grupo ligado ao núcleo benzênico. A degradação térmica do poli(1,4-cis-isopreno) sintético a 140 °C foi estudada na presença do LCC técnico e de alguns derivados (cardanol, cardanol hidrogenado e cardanol hidrogenado e alquilado), através de FTIR. A quantidade de grupamentos OH/OOH e C=O formados e de C=C consumidos foi determinada durante a degradação. Todos os materiais aumentaram o tempo de indução e diminuíram as constantes aparentes de velocidade. Com base nos parâmetros cinéticos, a ordem de atividade antioxidante é: LCC >> cardanol <FONT FACE=Symbol>@</FONT> cardanol hidrogenado e alquilado > cardanol hidrogenado. O efeito do LCC pode ser atribuído à contribuição extra de seus outros componentes, além do cardanol, e à insaturação na longa cadeia lateral. Essa maior atividade é importante, considerando que o LCC tem mais baixo custo do que seus derivados.

CNSL is a mixture of meta-alkylphenols with variable degree of unsaturation attached to the benzene ring. The kinetic study of the thermal degradation at 140 °C of synthetic cis-1,4-polyisoprene film, in the presence of technical CNSL and some derivatives (cardanol, hydrogenated cardanol and alkylated hydrogenated cardanol) was carried out by FTIR. The amount of OH/OOH and C=O formed and also of C=C consumed during the degradation was determined. All materials increase the induction period and decrease the apparent rate constants of thermal-oxidation. Based on kinetic parameters, the order of antioxidant activity was: CNSL >> cardanol <FONT FACE=Symbol>@</FONT> hydrogenated and alkylated cardanol > hydrogenated cardanol. The effect of CNSL could be attributed to the extra contribution of the other components besides cardanol and to the unsaturation on the long side chain. This greater activity is important because CNSL is much more cost effective than its derivatives.

The teaching apprenticeship established by CAPES for post-graduation scholarship beholders has been discussed and the criterion adopted for the implementation in the post-graduation in Inorganic Chemistry Program presented. A teaching plan for the new subject is proposed, based on the experience gained through a first group. An instrument for evaluation of the student's performance has been developed and analyzed. Aspects like knowledge, clearness, enthusiasm, confidence, good manage on the audio-visual resources, class length are mentioned by degree of importance and the major difficulties faced and pointed out by the students.

A redução da massa molar e consequentemente da viscosidade são efeitos observados quando soluções poliméricas são submetidas a ultrasom de alta intensidade. A degradação por ultrasom de soluções toluênicas de borracha natural da seringueira (Hevea brasiliensis) foi estudada por GPC. Os efeitos da temperatura e do tempo de irradiação sobre a polidispersão da borracha foram estudados.

The reduction of molar mass and consequent decrease in viscosity are evident effects when polymeric solutions are submitted to high intensity ultrasound. The ultrasonic degradation of natural rubber (NR) from Hevea brasiliensis, in tolueno, was studied by GPC. The effects of temperature and time of irradiation on polydispersion of NR were analysed.