离子液基体系Cyanex923(925)/[C_8mim][PF_6]和TBP/[A336][NO_3]萃取钪的研究

对Cyanex923(925)/[C8mim][PF6]和TBP/[A336][NO3]两个离子液基体系在萃取Sc(Ⅲ)中的应用进行了研究。实验表明,由于空间位阻较小,Cyanex923在[C8mim][PF6]中对Sc(Ⅲ)的萃取能力明显优于Cyanex925。温度对Cyanex923/[C8mim][PF6]体系萃取Sc(Ⅲ)的影响较小。与[C8mim][PF6]相反,[A336][NO3]在水中的浓度随酸度增加逐步减少。TBP/[A336][NO3]对Sc(Ⅲ)具有较高的萃取率。

Comparative study of PHBV/TBP and PHBV/BPA blends

In order to clarify the effects of phenols on properties of polyesters, the blends of poly[(3-hydroxybutyrate)-co-(3-hydroxyvalerate)] (PHBV) with 4,4'-dihydroxydiphenylpropane (BPA) and p-tert-butylphenol (TBP) were studied. The FTIR spectra revealed that there was strong hydrogen-bond (H-bond) interaction between PHBV and both phenols. By evaluating the fraction of H-bonded C = O in the blend, it was concluded that BPA showed a stronger tendency than TBP to form H-bonds with PHBV. Accordingly, BPA formed a stronger suppression than TBP on the crystallization of PHBV. When 30 wt% BPA or 50 wt% TBP were added into PHBV, the crystallization of PHBV was completely suppressed in the DSC cooling scan. As the phenol content was increased, the T-g of PHBV/TBP blend decreased while the T-g of PHBV/BPA blend increased. This difference indicated that TBP and BPA acted as plasticizer and physical crosslinking agent, respectively.

The structural basis for the oriented assembly of a TBP/TFB/promoter complex

Recently the definition of the metazoan RNA polymerase II and archaeal core promoters has been expanded to include a region immediately upstream of the TATA box called the B recognition element (BRE), so named because eukaryal transcription factor TFIIB and its archaeal orthologue TFB interact with the element in a sequence-specific manner. Here we present the 2.4-Å crystal structure of archaeal TBP and the C-terminal core of TFB (TFBc) in a complex with an extended TATA-box-containing promoter that provides a detailed picture of the stereospecific interactions between the BRE and a helix–turn–helix motif in the C-terminal cyclin repeat of TFBc. This interaction is important in determining the level of basal transcription and explicitly defines the direction of transcription.

High-resolution mapping of nucleoprotein complexes by site-specific protein-DNA photocrosslinking: organization of the human TBP-TFIIA-TFIIB-DNA quaternary complex.

We have used a novel site-specific protein-DNA photocrosslinking procedure to define the positions of polypeptide chains relative to promoter DNA in binary, ternary, and quaternary complexes containing human TATA-binding protein, human or yeast transcription factor IIA (TFIIA), human transcription factor IIB (TFIIB), and promoter DNA. The results indicate that TFIIA and TFIIB make more extensive interactions with promoter DNA than previously anticipated. TATA-binding protein, TFIIA, and TFIIB surround promoter DNA for two turns of DNA helix and thus may form a "cylindrical clamp" effectively topologically linked to promoter DNA. Our results have implications for the energetics, DNA-sequence-specificity, and pathway of assembly of eukaryotic transcription complexes.

Physical and functional interaction of the archaeal single-stranded DNA-binding protein SSB with RNA polymerase

Archaeal transcription utilizes a complex multisubunit RNA polymerase and the basal transcription factors TBP and TF(II)B, closely resembling its eukaryal counterpart. We have uncovered a tight physical and functional interaction between RNA polymerase and the single-stranded DNA-binding protein SSB in Sulfolobus solfataricus. SSB stimulates transcription from promoters in vitro under TBP-limiting conditions and supports transcription in the absence of TBP. SSB also rescues transcription from repression by reconstituted chromatin. We demonstrate the potential for promoter melting by SSB, suggesting a plausible basis for the stimulation of transcription. This stimulation requires both the single-stranded DNA-binding domain and the acidic C-terminal tail of the SSB. The tail forms a stable interaction with RNA polymerase. These data reveal an unexpected role for single-stranded DNA-binding proteins in transcription in archaea.

An evaluation of the Australian Capital Territory Sexual Assault Reform Program (SARP): Final Report

In 2005 the Australian Capital Territory (ACT) Office of the Director of Public Prosecutions (DPP) and the Australian Federal Police (AFP) produced a report, Responding to sexual assault: The challenge of change (DPP & AFP 2005), which made 105 recommendations for reforming the way sexual offence cases are handled by the ACT’s criminal justice system. The Sexual Assault Reform Program (SARP) is one key initiative developed in response to these recommendations. Managed by the ACT Justice and Community Safety Directorate (JACS), SARP’s main objective is to improve aspects of the criminal justice system relating to: processes and support for victims of sexual offences as they progress through the system; attrition in sexual offence matters in the criminal justice system; and coordination and collaboration among the agencies involved. In November 2007 the ACT Attorney-General announced $4 million of funding for several SARP reforms. This funding provided for additional victim support staff; a dedicated additional police officer, prosecutor and legal policy officer; and an upgrade of equipment for the Supreme Court and Magistrates Court, including improvements in technology to assist witnesses in giving evidence, and the establishment of an off-site facility to allow witnesses to give evidence from a location outside of the court. In addition, the reform agenda included a number of legislative amendments that changed how evidence can be given by victims of sexual and family violence offences, children and other vulnerable witnesses. The primary objectives of these legislative changes are to provide an unintimidating, safe environment for vulnerable witnesses (including sexual offence complainants) to give evidence and to obtain prompt statements from witnesses to improve the quality of evidence captured (DPP 2009: 13). The current evaluation The funding for SARP reforms also provided for a preliminary evaluation of the reforms; this report outlines findings from the evaluation. The evaluation sought to address whether the program has met its key objectives: better support for victims, lower attrition rates and improved coordination and collaboration among agencies involved in administering SARP. The evaluation was conducted in two stages and involved a mixed-methods approach. During stage 1 key indicators for the evaluation were developed with stakeholders. During stage 2 quantitative data were collected by stakeholders and provided to the AIC for analysis. Qualitative interviews were also conducted with service delivery providers, and with a small number (n=5) of victim/survivors of sexual offences whose cases had recently been resolved in the ACT criminal justice system. The current evaluation is preliminary in nature. As the SARP reforms will take time to become entrenched within the ACT’s criminal justice system, some of the impacts of the reforms may not yet be evident. Nonetheless, this evaluation provides an insight into how well the SARP reforms have been implemented to date, as well as key areas that could be addressed in the future. Key findings from the preliminary evaluation are outlined briefly below.

Role of TATATAA element in the regulation of tRNA(1)(Gly) gene expression in Bombyx mori is position dependent

Transcription of tRNA genes by RNA polymerase III is controlled by the internal conserved sequences within the coding region and the immediate upstream flanking sequences. A highly transcribed copy of glycyl tRNA gene tRNA1(Gly)-1 from Bombyx mori is down regulated by sequences located much farther upstream in the region -150 to -300 nucleotides (nt), with respect to the +1 nt of tRNA. The negative regulatory effect has been narrowed down to a sequence motif 'TATATAA', a perfect consensus recognised by the TATA binding protein, TBP. This sequence element, when brought closer to the transcription start point, on the other hand, exerts a positive effect by promoting transcription of the gene devoid of other cis regulatory elements. The identity of the nuclear protein interacting with this 'TATATAA' element to TBP has been established by antibody and mutagenesis studies. The 'TATATAA' element thus influences the transcription of tRNA genes positively or negatively in a position-dependent manner either by recruitment or sequestration of TBP from the transcription machinery.

Synthesis, Structure, Spirocyclization Mechanism, and Glutathione Peroxidase-like Antioxidant Activity of Stable Spirodiazaselenurane and Spirodiazatellurane

The first examples of stable spirodiazaselenurane and spirodiazatellurane were synthesized by oxidative spirocyclization of the corresponding diaryl selenide and telluride and were structurally characterized. X-ray crystal structures of the spirodiazaselenurane and spirodiazatellurane suggest that the structures are distorted trigonal bipyramidal (TBP) with the electronegative nitrogen atoms occupying the apical positions and two carbon atoms and the lone pair of Se/Te occupying the equatorial positions. Interestingly, the spirodiazatellurane underwent spontaneous chiral resolution during crystallization, and the absolute configurations of its enantiomers were confirmed by single-crystal X-ray analyses. A detailed mechanistic study indicates that the cyclization to spirodiazaselenurane and spirodiazatellurane occurs via selenoxide and telluroxide intermediates. The chalcogenoxides cyclize to the corresponding spiro compounds in a stepwise manner via the involvement of hydroxyl chalcogenurane intermediates, and the activation energy for them spirocyclization reaction decreases in the order S > Se > Te. In addition to the synthesis, characterization, and mechanism of cyclization, the glutathione peroxidase (GPx) mimetic activity of the newly synthesized compounds was evaluated. These studies suggest that the tellurium compounds are more effective as GPx mimics than their selenium counterparts due to the fast oxidation of the tellurium center in the presence of peroxide and the involvement of an efficient redox cycle between the telluride and telluroxide intermediate.

An Alternate Route to High-Quality ZnSe and Mn-Doped ZnSe Nanocrystals

We report here a synthetic route for high-quality Mn-doped ZnSe nanocrystals using selenourea as a selenium source, avoiding the more conventional route-using tributylphosphine (TBP) that restricts the growth of spherical ZnSe nanocrystals below 5 nm in size, besides being highly toxic and pyrophoric. Spherical ZnSe nanocrystals with unprecendented sizes (up to 12 nm) are synthesized, the large size of the host helps to keep dopant ions well inside the nanocrystal leading to intense and stable dopant emission. Mn-doped ZnSe nanocrystals with more than 50% quantum yield (QY) are synthesized in this method and found to be stable both in aqueous and nonaqueous dispersions for months.