2016生物基材料专刊序言

生物基材料,是利用谷物、豆科、秸秆、竹木粉等可再生生物质为原料制造的新型材料和化学品等,包括生物合成、生物加工、生物炼制过程获得的生物醇、有机酸、烷烃、烯烃等基础生物基化学品,也包括生物基塑料、生物基纤维、糖工程产品、生物基橡胶以及生物质热塑性加工得到塑料材料等。生物基材料由于其绿色、环境友好、资源节约等特点,正逐步成为引领当代世界科技创新和经济发展的又一个新的主导产业。本期专刊报道了生物基材料总体发展情况,介绍了生物基纤维、聚羟基烷酸酯、可生物降解地膜、生物基聚酰胺、蛋白医用生物材料、生物基聚氨酯、聚乳酸改性与加工等几个方面行业状况及其研究进展。     

Accuracy of radioanalytical procedures used to determine the biobased content of manufactured products

Radiocarbon analyses were used to determine the "biobased content" of a variety of diverse samples. The theoretical biobased contents of those samples were compared to the biobased content values obtained by radiocarbon analyses. Results of this work indicated that the radiocarbon analyses provided accurate (within +/-3%, absolute) biobased content values for the samples tested. It is not practical to examine the accuracy of the radiocarbon analyses for every possible type of sample matrix. However, based on analyses performed on various types of samples, every indication is that the analyses provide accurate and reliable results on the biobased content of liquid and solid materials.     

Developments of biobased plasticizers for compostable polymers in the green packaging applications: A review

The demand for biobased materials for various end-uses in the bioplastic industry is substantially growing due to increasing awareness of health and environmental concerns, along with the toxicity of synthetic plasticizers such as phthalates. This fact has stimulated new regulations requiring the replacement of synthetic conventional plasticizers, particularly for packaging applications. Biobased plasticizers have recently been considered as essential additives, which may be used during the processing of compostable polymers to enormously boost biobased packaging applications. The development and utilization of biobased plasticizers derived from epoxidized soybean oil, castor oil, cardanol, citrate, and isosorbide have been broadly investigated. The synthesis of biobased plasticizers derived from renewable feedstocks and their impact on packaging material performance have been emphasized. Moreover, the effect of biobased plasticizer concentration, interaction, and compatibility on the polymer properties has been examined. Recent developments have resulted in the replacement of synthetic plasticizers by biobased counterparts. Particularly, this has been the case for some biodegradable thermoplastics-based packaging applications.     

Novel silicon-containing polyurethanes from vegetable oils as renewable resources. Synthesis and properties

Hydrosilylation of methyl 10-undecenoate (UDM) with phenyl tris(dimethylsiloxy)silane (PTDS) followed by a reduction of carboxylate groups was used to obtain a silicon-containing polyol with terminal primary hydroxyl groups (PSi194). Biobased silicon-containing polyurethanes, with a silicon content between 1.7% and 9.0%, were prepared from epoxidized methyl oleate-based polyether polyol (P184), PSi194, and 4,4'-methylenebis(phenyl isocyanate) (MDI). The thermal, mechanical, and flame-retardant properties of these materials were examined. The most notable change resulting from the incorporation of PSi194 is the appearance of melting endotherms of variable enthalpy and position and a downward shift in the T(g). The incorporation of silicon does not change the thermal stability but enhances the stability of the char under air atmosphere. Polyurethanes with higher silicon content no longer burn in ambient air without complementary oxygen, which suggests that these biobased materials are very interesting for applications that require fire resistance.     

2013生物基化学品 (Biobased Chemicals) 专刊序言

生物基化学品是生物经济和生物制造的核心内容之一。本专刊综述了国内外生物基化学品的重要研究进展,包括：丁二酸、己二酸、乳酸、3-羟基丙酸、葡萄糖二酸、甘油、木糖醇、高级醇、乙烯等生物基化学品的代谢工程和发酵调控,直接利用木质纤维素生产生物基化学品的菌株构建,生物基乳酸的衍生和生物转化技术,生物基化学品的盐析萃取分离纯化技术等。同时,本专刊也包括了国内学者在丁二酸、D-甘露醇、苹果酸、5-氨基乙酰丙酸、1,3-丙二醇和丁醇方面的研究论文。     

Polyurethane networks from fatty-acid-based aromatic triols: synthesis and characterization

Novel biobased aromatic triols (1,3,5-(9-hydroxynonyl)benzene and 1,3,5-(8-hydroxyoctyl)-2,4,6-octylbenzene) were synthesized through the transition-metal-catalyzed cyclotrimerization of two alkyne fatty acid methyl esters (methyl 10-undecynoate and methyl 9-octadecynoate) followed by the reduction of the ester groups to give terminal primary hydroxyl groups. A series of biobased segmented polyurethanes based on these triols, 1,4-butanediol as a chain extender and 4,4'-methylenebis(phenyl isocyanate) as a coupling agent, were synthesized. Samples were prepared with hard-segment contents up to 50%. The morphologies and thermal properties of these polyurethanes were studied by Fourier transform infrared spectroscopy, wide-angle X-ray diffraction, differential scanning calorimetry, thermogravimetric analysis, and dynamic mechanical thermal analysis. Partial crystallinity and phase separation were detected in samples with hard-segment content of 50%.     

Comparison of bioaerosol sampling methods in barns housing swine.

The air in livestock buildings contains bioaerosol levels that are sufficiently high to cause adverse health effects in animals and workers. These bioaerosols are complex mixtures of live and dead microorganisms and their products as well as other aeroallergens. The effectiveness of sampling methods used for quantifying the very high concentrations of microorganisms in these environments has not been well studied. To facilitate an accurate assessment of respiratory hazards from viable organisms in agricultural environments, three bioaerosol sampling methods were investigated: the Andersen microbial sampler method (AMS), the all-glass impinger method (AGI), and the Nuclepore filtration-elution method (NFE). These methods were studied in a parallel fashion in 24 swine confinement buildings. Measurements were taken in two seasons with three types of culture media in duplicate to assess total bacteria, gram-negative enteric bacteria, and total fungi. Methods were analyzed for the proportion of samples yielding data within the limits of detection, intraclass reliability, and correlation between methods. For sampling viable bacteria, the AMS had a poor data yield because of overloading and demonstrated weak correlation with the AGI. Conversely, the AGI and NFE gave sufficient numbers of valid data points (90%), yielded high intraclass reliabilities (alpha greater than or equal to 0.92), and were highly correlated with each other (r = 0.86). The AGI and the NFE were suitable methods for assessing bacteria in this environment, but the AMS was not. The AMS was the only method that consistently recovered enteric bacteria (73% data yield). For sampling fungi, the AGI and AMS both yielded sufficient data and all three methods demonstrated high intraclass reliability.(ABSTRACT TRUNCATED AT 250 WORDS)     

Uncertainty for Data with Non-Detects: Air Toxic Emissions from Combustion

Air toxic emission factor datasets often contain one or more points below a single or multiple detection limits and such datasets are referred to as “censored.” Conventional methods used to deal with censored datasets include removing non-detects, replacing the censored points with zero, half of the detection limit, or the detection limit. However, the estimated means of the censored dataset by conventional methods are usually biased. Maximum likelihood estimation (MLE) and bootstrap simulation have been demonstrated as a statistically robust method to quantify variability and uncertainty of censored datasets and can provide asymptotically unbiased mean estimates. The MLE/bootstrap method is applied to 16 cases of censored air toxic emission factors, including benzene, formaldehyde, benzo(a)pyrene, mercury, arsenic, cadmium, total chromium, chromium VI and lead from coal, fuel oil, and/or wood waste external combustion sources. The proportion of censored values in the emission factor data ranges from 4 to 80%. Key factors that influence the estimated uncertainty in the mean of censored data are sample size and inter-unit variability. The largest range of uncertainty in the mean was obtained for the external coal combustion benzene emission factor, with 95 confidence interval of the mean equal to minus 93 to plus 411%.     

Exergy-based accounting for land as a natural resource in life cycle assessment

Purpose

In life cycle assessment (LCA), literature suggests accounting for land as a resource either by what it delivers (e.g., biomass content) or the time and space needed to produce biomass (land occupation), in order to avoid double-counting. This paper proposes and implements a new framework to calculate exergy-based spatial explicit characterization factors (CF) for land as a resource, which deals with both biomass and area occupied on the global scale.

Methods

We created a schematic overview of the Earth, dividing it into two systems (human-made and natural), making it possible to account for what is actually extracted from nature, i.e., the biomass content was set as the elementary flow to be accounted at natural systems and the land occupation (through the potential natural net primary production) was set as the elementary flow at human-made systems. Through exergy, we were able to create CF for land resources for these two different systems. The relevancy of the new CF was tested for a number of biobased products.

Results and discussion

Site-generic CF were created for land as a resource for natural systems providing goods to humans, and site-generic and site-dependent CF (at grid, region, country, and continent level) were created for land as a resource within human-made systems. This framework differed from other methods in the sense of accounting for both land occupation and biomass content but without double-counting. It is set operationally for LCA and able to account for land resources with more completeness, allowing spatial differentiation. When site-dependent CF were considered for land resources, the overall resource consumption of certain products increased up to 77 % in comparison with site-generic CF-based data.

Conclusions

This paper clearly distinguished the origin of the resource (natural or human-made systems), allowing consistent accounting for land as a resource. Site-dependent CF for human-made systems allowed spatial differentiation, which was not considered in other resource accounting life cycle impact assessment methods.     

Respirometric 13C flux analysis, Part I: design, construction and validation of a novel multiple reactor system using on-line membrane inlet mass spectrometry

A novel method for (13)C flux analysis based on on-line CO(2) labeling measurements is presented. This so-called respirometric (13)C flux analysis requires multiple parallel (13)C labeling experiments using differently labeled tracer substrates. In Part I of the work, a membrane-inlet mass spectrometry-based measurement system with 6 parallel reactors with each 12 ml liquid volume and associated experimental and computational methods for the respirometric (13)C data acquisition and evaluation are described. Signal dynamics after switching between membrane probes follow exactly first-order allowing extrapolation to steady state. Each measurement cycle involving 3 reactors takes about 2 min. After development of a dynamic calibration method, the suitability and reliability of the analysis was examined with a lysine-producing mutant of Corynebacterium glutamicum using [1-(13)C(1)], [6-(13)C(1)], [1,6-(13)C(2)] glucose. Specific rates of oxygen uptake and CO(2) production were estimated with an error less than +/-0.3 mmol g(-1) h(-1) and had +/-3% to +/-10% deviations between parallel reactors which is primarily caused by inaccuracies in initial biomass concentration. The respiratory quotient could be determined with an uncertainty less than +/-0.02 and varied only +/-3% between reactors. Fractional labeling of CO(2) was estimated with much higher precision of about +/-0.001 to +/-0.005. The detailed statistical analysis suggested that these data should be of sufficient quality to allow physiological interpretation and metabolic flux estimation. The obtained data were applied for the respirometric (13)C metabolic flux analysis in Part II.     

Regional variations in greenhouse gas emissions of biobased products in the United States—corn-based ethanol and soybean oil

Background, aim, and scope  

Regional variations in the environmental impacts of plant biomass production are significant, and the environmental impacts associated with feedstock supply also contribute substantially to the environmental performance of biobased products. Thus, the regional variations in the environmental performance of biobased products are also significant. This study scrutinizes greenhouse gas (GHG) emissions associated with two biobased products (i.e., ethanol and soybean oil) whose feedstocks (i.e., corn and soybean) are produced in different farming locations.     

Evaluation of uncertainty in quantitative real-time PCR

Quantitative real-time PCR is one of the newer methods for measurement of the amount of nucleic material in biological systems. However, reliable measurement requires an appropriate estimation of uncertainty and this paper has developed the uncertainty budget associated with this procedure using as an example, data from a quantitative real-time PCR method for the enumeration of Campylobacter jejuni. This uncertainty is relatively large and for instance, a measured result of 151 units of DNA would have a 95% confidence interval of +/-84 units of DNA with the main sources of uncertainty being the measurement of the threshold cycle (Ct) value, the predicted DNA content of the unknown sample from the calibration line and the molar absorbance value for DNA.     

Uncertainty in life cycle costing for long-range infrastructure. Part I: leveling the playing field to address uncertainties

Purpose

Life cycle costing (LCC) is a state-of-the-art method to analyze investment decisions in infrastructure projects. However, uncertainties inherent in long-term planning question the credibility of LCC results. Previous research has not systematically linked sources and methods to address this uncertainty. Part I of this series develops a framework to collect and categorize different sources of uncertainty and addressing methods. This systematization is a prerequisite to further analyze the suitability of methods and levels the playing field for part II.

Methods

Past reviews have dealt with selected issues of uncertainty in LCC. However, none has systematically collected uncertainties and linked methods to address them. No comprehensive categorization has been published to date. Part I addresses these two research gaps by conducting a systematic literature review. In a rigorous four-step approach, we first scrutinized major databases. Second, we performed a practical and methodological screening to identify in total 115 relevant publications, mostly case studies. Third, we applied content analysis using MAXQDA. Fourth, we illustrated results and concluded upon the research gaps.

Results and discussion

We identified 33 sources of uncertainty and 24 addressing methods. Sources of uncertainties were categorized according to (i) its origin, i.e., parameter, model, and scenario uncertainty and (ii) the nature of uncertainty, i.e., aleatoric or epistemic uncertainty. The methods to address uncertainties were classified into deterministic, probabilistic, possibilistic, and other methods. With regard to sources of uncertainties, lack of data and data quality was analyzed most often. Most uncertainties having been discussed were located in the use stage. With regard to methods, sensitivity analyses were applied most widely, while more complex methods such as Bayesian models were used less frequently. Data availability and the individual expertise of LCC practitioner foremost influence the selection of methods.

Conclusions

This article complements existing research by providing a thorough systematization of uncertainties in LCC. However, an unambiguous categorization of uncertainties is difficult and overlapping occurs. Such a systemizing approach is nevertheless necessary for further analyses and levels the playing field for readers not yet familiar with the topic. Part I concludes the following: First, an investigation about which methods are best suited to address a certain type of uncertainty is still outstanding. Second, an analysis of types of uncertainty that have been insufficiently addressed in previous LCC cases is still missing. Part II will focus on these research gaps.

     

Uncertainty Distributions for Cancer Potency Factors: Combining Epidemiological Studies with Laboratory Bioassays—the Example of Acrylonitrile

For eight chemicals or chemical mixtures with clear positive epidemiological evidence of carcinogenicity by inhalation (acrylonitrile, arsenic, benzene, beryllium, cadmium, chromium VI, coke oven emissions, and nickel), the United States Environmental Protection Agency (USEPA) uses that evidence to obtain a single best estimate of cancer potency factor. The methods used have so far been ad hoc, because of the differences in published studies, although there are common factors. In every case, the uncertainties involved in the various stages of analysis are qualitatively acknowledged, and often quantitatively estimated, but no formal attempt has been made to propagate the uncertainties. I here provide a detailed case study for acrylonitrile that (a) incorporates all estimates of uncertainty mentioned by the US EPA in their analysis and propagates that uncertainty to produce an uncertainty distribution; (b) updates the USEPA analysis to incorporate more recent epidemiological data from the same study used in their analysis.

For most of the materials known to be carcinogenic to humans (through epidemiologic evidence), there are also available cancer bioassays performed on laboratory animals. If the procedures used for estimating human carcinogenic potencies from laboratory animal bioassays are to be believed in cases where there are no human epidemiological data, their evidence should also be used where there is epidemiological evidence. A consistent method of incorporating the results of both epidemiological studies and laboratory animal bioassays into a single probability distribution for a human cancer potency is here detailed, using acrylonitrile as an example for which there is positive epidemiological data. The methods are sufficiently general to allow the incorporation of any combinations of positive and negative bioassay and epidemiological data.     

Effects of elevated CO2 concentration on the quality of agricultural products: a review

The increasing concentration of atmospheric CO2 and the nutritional quality of human diets are the two important issues we are facing. At present, the atmospheric CO2 concentration is about 380 micromol mol(-1), and to be reached 550 micromol mol(-1) by 2050. A great deal of researches indicated that the quality of agricultural products is not only determined by inherited genes, but also affected by the crop growth environmental conditions. This paper summarized the common methods adopted at home and abroad for studying the effects of CO2 enrichment on the quality of agricultural products, and reviewed the research advances in evaluating the effects of elevated CO2 on the quality of rice, wheat, soybean, and vegetables. Many experimental results showed that elevated CO2 concentration causes a decrease of protein content in the grains of staple food crops and an overall decreasing trend of trace elements contents in the crops, but improves the quality of vegetable products to some extent. Some issues and future directions regarding the effects of elevated CO2 concentration on the quality of agricultural products were also discussed, based on the present status of related researches.     

Olefin versus sulfur coordination of benzo[b]thiophene (BT) in Cp(CO)2Re(η:η-μ2-BT)Cr(CO)3

Reactions of Cr(CO)₃(η⁶-BT), in which the Cr is π-coordinated to the benzene ring of benzo[b]thiophene (BT), with Cp′(CO)₂Re(THF), where Cp′ = η⁵-C₅H₅ or η⁵-C₅Me₅, give the products Cp′(CO)₂Re(η²:η⁶-μ₂-BT)Cr(CO)₃ in which the Cr remains coordinated to the benzene ring and Re is bound to the C(2)=C(3) double bond. An X-ray diffraction study of Cp(CO)₂Re(η²:η⁶-μ₂-BT)Cr(CO)₃ (3) provides details of the geometry. This structure contrasts with that of the Cp′(CO)₂Re(BT) complexes that exist as mixtures of isomers in which the BT is coordinated to the Re through either the double bond (2,3-η²) or the sulfur (η¹(S)). Thus, the electron-withdrawing Cr(CO)₃ group in 3 stabilizes the 2,3-η² mode of BT coordination to the Cp′(CO)₂Re fragment. Implications of these results for catalytic hydrodesulfurization of BT are discussed. Crystal data for 3: triclinic, space group

Full-size image

.     

Towards the development of a biobased economy in Europe and India

India has emerged as a key player with a high potential to develop a biomass and biobased economy due to its large geographic size and the massive amounts of agricultural and non agricultural biomass produced. India has joined hands with Europe to synchronize its efforts to create and facilitate the development of a biobased economy in this country. This paper aims to examine common research and development actions between the European Union (EU) and India to facilitate the development of these biobased economies. As a base, a thorough study has been performed considering the biomass potential and current status of the bioeconomy in both the EU and India based on the distillation of a series of 80 potential recommendations. The recommendations were grouped into four major categories: (1) biomass production, (2) by-products/waste, (3) biorefineries and (4) policy, market, and value-added products. A questionnaire was designed and distributed to key stakeholders belonging to: academia, industry, and policymakers in both India and the EU. A total of 231 responses were received and analyzed, based on the key recommendations made for the essential research and development topics that are of prime importance to develop biobased economies in both the EU and India. The findings of this study suggest recognizing the value-added contributions made by biobased products such as: food, feed, valuable materials and chemicals in both regions. It is important to reduce the overall process costs and minimize the environmental impacts of such a biobased economy.     

Life cycle assessment of a biobased chainsaw oil made on the farm in Wallonia

Purpose

The environmental issue is a particular concern for chainsaw oils because these fluids represent a total loss system. The aim of this study is to quantify the environmental impacts of a biobased chainsaw oil made on the farm in Wallonia (a region of Belgium) and to compare it with a model mineral chainsaw oil. With this study, the aim is also to participate in the development of the life cycle assessment (LCA) methodology applied to the biolubricant sector since LCAs on these products are quite limited and rarely sufficiently detailed.

Method

In this LCA, the attributional approach is applied. Seven impact categories are studied. The methods for life cycle impact assessment are IPCC, ReCiPe, CML and USEtox. The functional unit is 1 kg of base oil. Seven sensitivity analyses are performed.

Results and discussion

Results indicate that the biobased chainsaw oil made on the farm has a lower impact for the global warming potential, the abiotic depletion potential, the ozone depletion potential and the photochemical oxidation potential. On the contrary, it has larger acidification, aquatic eutrophication and aquatic ecotoxicity potential impacts. Regarding the contribution of the life cycle stages of the biobased chainsaw oil, the agricultural stage causes the highest contribution in all impact categories. For the mineral chainsaw oil, the refining stage is preponderant for all impact categories except for the global warming potential for which the end-of-life stage contributes the most. When taking additives into account, conclusions regarding the comparison between the oils are not reversed. Even if it was necessary to consume more biobased than mineral chainsaw oil, conclusions regarding the comparison of the oils would not be reversed. In the same way, a different allocation procedure for rapeseed oil and rape meal, a different rape seeds yield or different extraction yields in the refining stage of the mineral base oil do not change the results of the comparison. For the biobased chainsaw oil, the substitution of only one active substance in the agricultural stage could result in an important decrease of the freshwater ecotoxicity impact.

Conclusions

The biobased chainsaw oil has a lower impact in four out of the seven impact categories and a higher impact in three impact categories. By providing a detailed LCA on a biobased chainsaw oil, this study contributes to the development of LCA applied to biobased lubricants.     

The "systolic volume balance" method for the noninvasive estimation of cardiac output based on pressure wave analysis

Cardiac output (CO) monitoring is essential for the optimal management of critically ill patients. Several mathematical methods have been proposed for CO estimation based on pressure waveform analysis. Most of them depend on invasive recording of blood pressure and require repeated calibrations, and they suffer from decreased accuracy under specific conditions. A new systolic volume balance (SVB) method, including a simpler empirical form (eSVB), was derived from basic physical principles that govern blood flow and, in particular, a volume balance approach for the conservation of mass ejected into and flowed out of the arterial system during systole. The formulas were validated by a one-dimensional model of the systemic arterial tree. Comparisons of CO estimates between the proposed and previous methods were performed in terms of agreement and accuracy using "real" CO values of the model as a reference. Five hundred and seven different hemodynamic cases were simulated by altering cardiac period, arterial compliance, and resistance. CO could be accurately estimated by the SVB method as follows: CO = C × PP(ao)/(T - P(sm) × T(s)/P(m)) and by the eSVB method as follows: CO = k × C × PP(ao)/T, where C is arterial compliance, PP(ao) is aortic pulse pressure, T is cardiac period, P(sm) is mean systolic pressure, T(s) is systolic duration, P(m) is mean pressure, and k is an empirical coefficient. SVB applied on aortic pressure waves did not require calibration or empirical correction for CO estimation. An empirical coefficient was necessary for brachial pressure wave analysis. The difference of SVB-derived CO from model CO (for brachial waves) was 0.042 ± 0.341 l/min, and the limits of agreement were -0.7 to 0.6 l/min, indicating high accuracy. The intraclass correlation coefficient and root mean square error between estimated and "real" CO were 0.861 and 0.041 l/min, respectively, indicating very good accuracy. eSVB also provided accurate estimation of CO. An in vivo validation study of the proposed methods remains to be conducted.     

Analysis of local conformation of membrane-bound and polycrystalline peptides by two-dimensional slow-spinning rotor-synchronized MAS exchange spectroscopy

2D slow-spinning, rotor-synchronized MAS exchange spectroscopy (SSRS-MASE) was applied to study local secondary structure of three structurally different peptides, two of which were membrane-bound. Each peptide was ¹³C carbonyl labeled at two adjacent residues in the peptide backbone. In general, this methodology is attractive for membrane-bound peptides because of its lenient spinning, decoupling, and RF homogeneity requirements.For a single set of raw SSRS-MASE data, two linearly independent methods exist for obtaining a 2D spectrum and each spectrum can be fit to obtain conformational constraints. An approach is described for combining the results of these two fits and this method is shown to work for spectra with both resolved and unresolved labeled site resonances. A spectrum is often fit well to a few different conformations which have somewhat different values of the fitting parameter ². A simple statistical theory is developed which relates the ² difference between a local minimum and the global minimum ² to the likelihood that the local minimum conformation is the correct structure. Because uncertainty in the simulated data can also contribute to the overall fitting uncertainty, an empirical method is described for incorporating the simulation uncertainty into the ² analysis.These data analysis methods were tested on polycrystalline Ala-Gly-Gly and then applied to the membrane-bound melittin and HIV-1 fusion peptides. Melittin gave a best-fit helical structure at Ala-4 while the fusion peptide gave a good-fit strand structure at Phe-8. The melittin analysis is in agreement with the known overall structure of this peptide.