Abstract This paper documents an increase in the number of observed explosive cyclones (EC) at King George Island, South Shetland Islands, Antarctica, over the 1989‒2020 period. In ECs at 60o latitudes the surface atmospheric pressure drops ≥24 hPA in 24 hours. The annual EC frequency time series shows a significant positive trend of ~2.7 cyclones/decade, with a break in 2003 and average numbers of 7.3 and 11.8 events before and after that break, respectively. The increase follows closely earlier documented global sea surface temperature (SST) anomaly trends for the 1981‒2018 period, partially attributed to global warming and to the Pacific Decadal Oscillation (PDO). Connections between EC frequency and SST might occur through variations in SST in the southeastern Pacific and southwestern Atlantic, with anomalous cold conditions favoring an increase in ECs. We also found close relations between the number of ECs with simultaneous occurrences of PDO and Atlantic multidecadal oscillation in opposite phases, so that after 2003 they were in the cold and warm phases, respectively, and vice-versa before 2003. Both low-frequency modes seem to modulate the number of ECs. As per the authors knowledge these results have not been discussed before and may help climate modeling studies and weather forecasts.

RESUMO A determinação do acúmulo de nutrientes durante o ciclo vegetativo é essencial para estabelecer o manejo nutricional. Objetivou-se avaliar o acúmulo de matéria seca e a exigência nutricional, estabelecendo as curvas de absorção, a época ideal de manejo e a ordem de extração dos elementos. O experimento foi conduzido em casa de vegetação com delineamento experimental inteiramente casualizado com oito períodos de coleta aos 10, 20, 30, 40, 50, 60, 70 e 80 dias após a emergência (DAE), com quatro repetições. Em cada período, ocorreu uma coleta de forma destrutiva, para determinar a matéria seca e, assim, estimar o conteúdo de macro e micronutrientes. Foram ajustados, quando significativos, modelos não lineares para explicar o acúmulo de matéria seca e absorção de nutrientes. A equação sigmoidal foi o modelo que melhor representou a curva de crescimento das plantas de feijão-de-metro com acúmulo máximo de biomassa aos 80 DAE de 177,5 g planta- ¹. A fase de maior exigência nutricional da cultura é no período de 20 a 45 DAE (início das fases de florescimento e frutificação), onde deve ser realizado o manejo nutricional. A ordem decrescente da extração total de macronutrientes pela planta no final do ciclo foi de K>Ca=N>S=P>Mg com respectivos valores de 2.668,3 mg planta-¹, 2.331,1 mg planta-¹, 2.279,2 mg planta-¹, 507,5 mg planta-¹, 496,3 mg planta-¹ e 213,2 mg planta-¹, e de micronutrientes Fe>B>Mn>Zn>Cu, com 10.933,1 µg planta-¹, 6.310,8 µg planta-¹, 4.746,8 µg planta-¹, 2.854,1 µg planta-¹ e 717,1 µg planta-¹, respectivamente.

ABSTRACT Knowing about the nutrient uptake during plant cycle is essential for nutrient management decisions. We evaluated dry matter accumulation and nutrient demand, and it to determine the uptake curves, the ideal phase for management, and element extraction order for yard long beans. The experiment was carried out in a greenhouse. The experimental design was completely randomized, with eight collection periods, at 10, 20, 30, 40, 50, 60, 70 and 80 days after emergence (DAE), and four replicates. For each period, destructive sampling was performed and the sample’s dry matter content was determined, so that it could be used to estimate macro- and micronutrient contents. When significant, nonlinear models were adjusted to explain dry matter accumulation and nutrient uptake. The sigmoidal equation was the model which best depicted the growth curve for yard long bean, which reached a maximum biomass accumulation of 177.5 g plant-¹ at 80 DAE. The crop's most demanding phase in terms of nutritional requirements is from 20 to 45 DAE, which is the ideal phase for nutrient management. The element extraction order at the end of the plant's cycle was K>Ca=N>S=P>Mg (macronutrients) with values of 2,668.3 mg plant-¹, 2,331.1 mg plant-¹, 2,279.2 mg plant-¹, 507.5 mg plant-¹, 496.3 mg plant-¹ and 213.2 mg plant-¹, and Fe>B>Zn>Mn>Cu (micronutrients), with 10,933.1 µg plant-¹, 6,310.8 µg plant-¹, 4,746.8 µg plant-¹, 2,854.1 µg plant-¹ and 717.1 µg plant-¹, respectively.

This paper describes the synthesis of four new organotin compounds of general formula: (Ph4P)[Sn(Cy)3(RSO2N=CS2)] [Ph4P = tetraphenylphosphonium cation, Cy = cyclohexyl, R = C6H5 (1), 4-ClC6H4 (2), 4-BrC6H4 (3) and 4-IC6H4 (4)]. They were obtained by the reaction between four different potassium N-R-sulfonyldithiocarbimate salts and tricyclohexyltin chloride in methanol, and were isolated as tetraphenylphosphonium salts. The elemental analyses of C, H, N and the data of high-resolution mass spectrometry were consistent with the proposed formulae. The 119Sn NMR spectra and 119Sn Mössbauer spectroscopic data were consistent with the presence of tetracoordinated tin(IV) species in solution and in the solid state. The electrolytic molar conductance and the integration curves in the 1H NMR spectra are in accord with the 1:1 proportion between the tetraphenylphosphonium cations and the complex anions. The activity of the new compounds in the vulcanization of nitrile rubber was evaluated and the results were compared to those achieved with the commercial accelerators: N-tert-butyl-2-benzothiazolesulfenamide (TBBS), tetramethylthiuram disulfide (TMTD) and zinc diethyldithiocarbamate (ZEDC).

Six new salts of organometallic complexes of tin(IV) with the general formulae: (Ph4P)2[Sn(Bu)2(RSO2N=CS2)2] and [Fe(phen)3][Sn(Bu)2(RSO2N=CS2)2] [Ph4P = tetraphenylphosphonium, R = CH3 (1), C2H5 (2) and C4H9 (3); Fe(phen)3 = tris(1,10-phenanthroline)iron(II), R = CH3 (4), C2H5 (5) and C4H9 (6)] were synthetized from potassium dithiocarbimates (RSO2N=CS2K2.H2O) in reaction with dichlorobis-n-butyltin(IV) and tetraphenylphosphonium chloride (1-3) in N,N-dimethylformamide or tris(1,10-phenanthroline)iron(II) (4-6) in methanol. The new compounds were characterized by elemental analysis of Fe and Sn, and by vibrational, Mössbauer and nuclear magnetic resonance of 1H, 13C and 119Sn spectroscopies. High-resolution mass spectra in the negative and positive modes were also obtained. The elemental analyses and the exact masses obtained for the cations and the complex anions were consistent with the proposed formulae. The Mössbauer spectroscopic data were consistent with the presence of tin(IV) with coordination numbers between 4 and 5 (compounds 1-6), and of hexacoordinated iron(II) (compounds 4-6). The 1H and 13C NMR spectra presented all the expected signals for the cations and anions, and the signals observed in the 119Sn NMR spectra indicated an equilibrium between tetra- and pentacoordination around the tin atoms in solution. The in vitro activity of the new compounds was evaluated against Botrytis cinerea and Colletotrichum acutatum.

<p>Botrytis blight or gray mold is a highly destructive disease caused by <italic>Botrytis</italic> spp., that infects flowers, trees vegetables, fruit, especially grapevines and strawberry. Three new compounds with general formula (A)₂[Zn(4-FC₆H₄SO₂N=CS₂)₂], where A = PPh₃CH₃ (<bold>2a</bold>), PPh₃C₂H₅ (<bold>2b</bold>), PPh₃C₄H₉ (<bold>2c</bold>), and the previously published compounds where A = PPh₄ (<bold>2d</bold>) and NBu₄ (<bold>2e</bold>), were synthesized by the reaction of 4-fluorophenylsulfonyldithiocarbimate potassium dihydrate and zinc(II) acetate dihydrate with the appropriate counter cations (A) halides. The new compounds were characterized by infrared, ¹H and ¹³C NMR spectroscopies. All these salts inhibited the growth of <italic>Botrytis cinerea</italic>, with compounds <bold>2c</bold> and <bold>2d</bold> showing greater antifungal activity than zinc dimethyldithiocarbamate, the active principle of the fungicide Ziram. The bis(dithiocarbimate)zincate(II) salts are also active against the bacteria <italic>Escherichia coli</italic> and <italic>Staphylococcus aureus</italic>.</p>

Four new compounds with the general formula [Fe(phen)3][Zn(RSO2N=CS2)2], where phen = 1,10-phenanthroline, R = 4-FC6H4 (1), 4-ClC6H4 (2), 4-BrC6H4 (3) and 4-IC6H4 (4), respectively, were obtained by the reaction of the appropriate potassium N-R-sulfonyldithiocarbimate (RSO2N=CS2K2) and tris(1,10-phenanthroline)iron(II) sulfate, with zinc(II) acetate dihydrate in dimethylformamide. The elemental analyses and the IR data were consistent with the formation of the expected complexes salts. The ¹H and 13C NMR spectra showed the signals for the cationic iron(II) complex and dithiocarbimate moieties. The molar conductance data were consistent with the 1:1 cation:anion complexes in 1-4. The antifungal activities of the compounds were tested in vitro against Candida albicans, Candida tropicalis and Colletotrichum gloeosporioides.

O ZNIBU, acelerador de caráter lento foi avaliado neste trabalho em composições de polibutadieno. Este acelerador foi sintetizado com o objetivo de substituir, ou reduzir, o uso de alguns aceleradores comerciais muito utilizados em composições elastoméricas mas que, por serem formadores de nitrosaminas, podem ser prejudiciais à saúde. A fim de corrigir o caráter de acelerador lento do ZNIBU, este composto foi utilizado em conjunto com o acelerador comercial CBS (N-ciclohexil-2-benzotiazol-2-sulfenamida). Foi observado que pequenas quantidades dos dois aceleradores não são efetivas na aceleração da vulcanização nas composições do tipo goma pura. No entanto a presença de negro de fumo exerce um efeito positivo sobre a velocidade. As propriedades mecânicas estudadas mostram que o ZNIBU aumenta a resistência à tração da goma pura (35%), em comparação com a composição similar vulcanizada com CBS e, na presença do negro de fumo, este aumento é ainda mais expressivo (175%). Quanto à resistência ao rasgamento, a vulcanização com o ZNIBU forneceu o mais baixo valor da propriedade para a goma pura, enquanto que a composição com negro de fumo apresentou o mais alto valor.

ZNIBU, a slow accelerator, was evaluated in polybutadiene compositions. This accelerator was synthesized intending to replace or reduce the use of some very used commercial accelerators in rubber compositions which, due to their nitrosamine-forming potential, can be harmful to health. In order to correct for the slow accelerating character ZNIBU was used in combination with the commercial accelerator CBS (N-cyclohexyl-2-benzothiazole-2-sulfenamide). It was observed that small amounts of the accelerators are not effective in the vulcanization accelerating process of gum type compositions. Nevertheless, the presence of carbon black exerts a positive effect on the reaction rate. The investigated mechanical properties show that ZNIBU improves stress strength of the pure gum (35%), when compared with a similar composition vulcanized with CBS and, in the presence of carbon black, the increase is even more expressive (175%). As for the tear strength, the ZNIBU vulcanization provided the lowest value for the pure gum composition while the carbon black-filled composition presented the highest value for this property.

O efeito do tipo de acelerador no processo de vulcanização de compostos de borracha nitrílica com dois teores de acrilonitrila foi investigado. Dois aceleradores comerciais, dissulfeto de 2,2'-dibenzotiazol (MBTS) e bis (dimetilditiocarbamato) de zinco (ZDMC), de grupos químicos diferentes, tiazol e ditiocarbamato, respectivamente, foram selecionados e comparados com o composto bis (4 metilfenilsulfonilditiocarbimato-)zincato (II) de tetrabutilamônio (ZNIBU). Os resultados mostram que o tipo de acelerador não só afeta as características de cura, como também tem grande influência nas propriedades físicas. Entre os aceleradores estudados, MBTS foi o menos adequado para a formulação utilizada. Surpreendentemente, verificou-se que o ZNIBU mostrou comportamento intermediário, sendo mais eficaz do que o MBTS e menos eficiente que o ZDMC, considerado um ultra-acelerador, em relação ao tempo ótimo de vulcanização.

The effect of the type of accelerator on the vulcanization process of nitrile rubber compounds with two acrilonitrile amounts was investigated. Two commercial accelerators benzothiazole (MBTS) and zinc dimethyldithiocarbamate (ZDMC), from different chemical groups, thiazole and dithiocarbamate, respectively, were selected and compared with the compound bis (4 methylphenylsulfonyldithiocarbimato-)zincate (II) of tetrabutylammoniun (ZNIBU). The results show that the type of accelerator not only affects the cure characteristics, but also has great influence on the physical properties. Among the accelerators studied, MBTS was found to be the least adequate for the formulation used as far as rheometric parameters are concerned. Surprisingly, it was found that ZNIBU showed an intermediate behavior, being more efficient than MBTS but not as much as ZDMC, considered an ultra accelerator, as for the optimum cure time.

Para avaliação da segurança e eficácia do tratamento com toxina botulínica A (TB-A) na espasticidade na paralisia cerebral (PC), foram selecionadas 20 crianças com a forma diplegia espástica. Todos os pacientes receberam injeções nos gastrocnêmios e sóleos, 15 receberam doses nos adutores da coxa. A dose total variou de 70 a 140 Us (99,75±16,26 U), 7,45±2,06 U/Kg por paciente. O tratamento com a TB-A melhorou significativamente a deambulação e o padrão de marcha. Houve também significativa alteração da distância tornozelo-solo e aumento da amplitude de movimento da articulação do tornozelo. Essas mudanças estruturais dos pés se mantiveram até o final do acompanhamento. O mesmo não foi observado com parâmetros funcionais. Três pacientes apresentaram fraqueza em membros inferiores. Conclui-se que a TB-A, em uma única aplicação, é segura e eficaz. Há modificação sustentada da estrutura motora dos membros inferiores, porém mudanças funcionais são temporárias, durante o pico de ação do medicamento.

We evaluated the safety and effectiveness of botulinum toxin A (BoNT/A) in the treatment of spasticity in 20 children with spastic diplegic cerebral palsy (CP). All the patients received injections in the gastrocnemius and soleus, and 15 received injections in the adductors. The total dose varied from 70 to 140 U (99.75±16.26 U), or 7.45±2.06 U/kg per patient. The treatment improved the patients' walking and gait pattern significantly. There was also a significant alteration in the heel-ground distance and increased motion of the ankle joint. These structural changes in the feet were sustained until the end of the follow-up, although the same was not observed for the functional parameters. Three patients complained of weakness in the lower limbs. In conclusion, BoNT/A is safe and effective when used in a single session of injections and produces a sustained structural modification of the lower limbs. However, functional changes are temporary and are only observed during the peak effect of the drug.

Neste trabalho a substância ZNIBU [bis(4-metilfenilditiocarbimato)zincato(II) de tetrabutilamônio] foi usada em formulações de borracha natural (NR) e o seu efeito como acelerador de vulcanização foi investigado. As composições, vulcanizadas com a substância em questão, foram submetidas a testes mecânicos e os resultados comparados com os de outras composições vulcanizadas com os aceleradores comerciais CBS (N-ciclohexil-2-benzotiazol-2-sulfenamida), TMTD (dissulfeto de tetrametiltiuram) e MBTS (dissulfeto de benzotiazol). Propriedades como dureza, resiliência e densidade foram avaliadas em presença ou não da carga negro de fumo.

The acceleration potential of ZNIBU [tetrabutyl ammonium bis(4-methylphenyldithiocarbimatozincate(II))] in the vulcanization process of natural rubber compounds was investigated. The vulcanized compounds were tested for hardness, resilience and density and compared with those vulcanized with commercial accelerators such as CBS (N-cyclohexyl-2-benzothiazolesulphenamide), TMTD (tetramethyl thiuram disulphide) and MBTS (dibenzothiazole disulphide). The new accelerator tested was found to be too slow for a commercial application, but its properties were similar to those of other accelerators.