The evolution of synthetic design toward the efficient synthesis of cyclobutane natural product(±)-piperarborenine B is demonstrated.Taking the advantages of good functional group compatibility of contractive syn...The evolution of synthetic design toward the efficient synthesis of cyclobutane natural product(±)-piperarborenine B is demonstrated.Taking the advantages of good functional group compatibility of contractive synthesis of cyclobutanes from pyrrolidines,stereoselective synthesis of unsymmetric highly functionalized cyclobutanes core of(±)-piperarborenine B was realized in one step.Also,an unprecedented carboxylic acid assisted-diastereoselective Kracho decarboxylation/transmethylation features a new strategy for a non-symmetrical cyclobutane core.The synthesis of(±)-piperarborenine B illustrates the advancement of methodology resulting in the improvement in synthetic efficiency.展开更多
In recent years,a significant number of investigations have discovered up to 200000 unsubmitted sexual assault kits(SAKs)in the US.While the public outcry was largely directed towards DNA analysis,the SAKs also contai...In recent years,a significant number of investigations have discovered up to 200000 unsubmitted sexual assault kits(SAKs)in the US.While the public outcry was largely directed towards DNA analysis,the SAKs also contained biological specimens specifically designated for toxicological analysis.Due to the sensitivity of analytes in potential drug facilitated sexual assaults,the preservation and maintenance of the specimens is crucial in providing accurate toxicological measurements.The investigations into the unsubmitted SAKs have identified subjective law enforcement officer(LEO)rationale for the unsubmitted kits,however the impact on toxicological specimens has not been examined.This brief review of policies and guidelines with respect to forensic specimens has identified potential sources of evidentiary degradation,despite the use of chemical preservatives.With respect to temperature-controlled environments,the variation in SAK submission policies established throughout the US are potentially detrimental to the preservation of toxicological evidence.Degradation as a result of time-delayed collection and poorly maintained storage temperatures plays a crucial role for/in the interpretation of qualitative and quantitative toxicological results.This review finds these delays can be addressed through modernisation of facilities;electronic tracking of unsubmitted SAKs;mandated transfer of biological evidence within 72 h;and documentation of temperature within the chain of custody or other records.Without identifying the range of temperatures in which the evidence was exposed,forensic toxicologists may unintentionally provide erroneous interpretations of toxicological analyses-potentially casting doubt on the survivor’s recall of events and negatively impacting future sexual assault investigations.展开更多
基金A.P.A.thanks for the support of the DFG(No.AN 1064/4–1)and the Boehringer Ingelheim Foundation(Plus 3).C.H.thanks the International Max Planck Research School for Living Matter(Dortmund,Germany).
文摘The evolution of synthetic design toward the efficient synthesis of cyclobutane natural product(±)-piperarborenine B is demonstrated.Taking the advantages of good functional group compatibility of contractive synthesis of cyclobutanes from pyrrolidines,stereoselective synthesis of unsymmetric highly functionalized cyclobutanes core of(±)-piperarborenine B was realized in one step.Also,an unprecedented carboxylic acid assisted-diastereoselective Kracho decarboxylation/transmethylation features a new strategy for a non-symmetrical cyclobutane core.The synthesis of(±)-piperarborenine B illustrates the advancement of methodology resulting in the improvement in synthetic efficiency.
文摘In recent years,a significant number of investigations have discovered up to 200000 unsubmitted sexual assault kits(SAKs)in the US.While the public outcry was largely directed towards DNA analysis,the SAKs also contained biological specimens specifically designated for toxicological analysis.Due to the sensitivity of analytes in potential drug facilitated sexual assaults,the preservation and maintenance of the specimens is crucial in providing accurate toxicological measurements.The investigations into the unsubmitted SAKs have identified subjective law enforcement officer(LEO)rationale for the unsubmitted kits,however the impact on toxicological specimens has not been examined.This brief review of policies and guidelines with respect to forensic specimens has identified potential sources of evidentiary degradation,despite the use of chemical preservatives.With respect to temperature-controlled environments,the variation in SAK submission policies established throughout the US are potentially detrimental to the preservation of toxicological evidence.Degradation as a result of time-delayed collection and poorly maintained storage temperatures plays a crucial role for/in the interpretation of qualitative and quantitative toxicological results.This review finds these delays can be addressed through modernisation of facilities;electronic tracking of unsubmitted SAKs;mandated transfer of biological evidence within 72 h;and documentation of temperature within the chain of custody or other records.Without identifying the range of temperatures in which the evidence was exposed,forensic toxicologists may unintentionally provide erroneous interpretations of toxicological analyses-potentially casting doubt on the survivor’s recall of events and negatively impacting future sexual assault investigations.